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By C. G. Rhodes, D. Kramer

The kinetics of precipitation of transient a phase during the transformation in U-16 wt pct Mo between 400° and 550°C were studied using quantitative metallography and electrica1 resistiuity measurements. The volume percent of a phase goes through a maximum in time, corresponding to a critical degree of progress of y' formation. prior to its re-solution after prolonged annealing. The fastest rate of a precipitation oc-cuvs at 500°C with a concomittant lowest peak of 9.5 vol pct a. At 450°C, 14 vol pct a, greatest fov any temperature, was observed after 24 hr witlz an associated slowest rate of formation. a precipitation at 400°C ceases after approximately 160 hr and the amount of a present remains unchanged after long times at temperature; no y' was observed metallographically at this temperature. IN the U-Mo system at 16 wt pct Mo, an ordering reaction takes place below 600°C, see Fig. 1, whereupon the random bcc solid solution, y, transforms to the ordered bct phase, y'."2 The new unit cell is constructed of three old unit cells somewhat distorted. While attempting to study the kinetics of this transformation it was observed that an unexpected phase was precipitating out early during the transformation anneal reaching appreciable amounts before disappearing after long times. The y' appeared in the presence of this new phase and after long times constituted the whole sample. Owing to the high optical activity of this unexpected phase under polarized light, it was suspected to be the a phase. Subsequent X-ray powder pictures confirmed this belief. The kinetics of a phase formation and disappearance is the subject of this paper. EXPERIMENTAL PROCEDURE A) Alloy Preparation. Alloys for this study were prepared by vacuum induction melting normal reactor grade uranium and 99.5 wt pct Mo pellets in thoria crucibles. Two ingots were prepared, and sections of the top and bottom of each ingot were chemically analyzed for uranium and molybdenum content. The results of the analyses appear in Table I. B) Metallography. Samples of 16M were wrapped in tantalum foil, sealed in evacuated (5 X 10"6 mm of Hg) quartz capisules, and annealed at 1110"C prior to being transferred directly to the transformation temperature. They were examined metallographically after increasing times to determine the progress of the transformation at 400°, 450°, 500°, and 550°C. The samples were prepared for metallographic examination by mechanical polishing with diamond paste and electrolytic polishing with a solution of glacial acetic acid and chromic acid. Since the y' phase is tetragonal, its presence can be detected by viewing the sample in polarized light. To increase the contrast between y' plates, the samples were electro-etched in a 10 pct oxalic acid solution. To reveal a phase in bright field (it can be seen in polarized light in the "as-polished" state), the samples were electro-etched in a solution of citric acid and nitric acid. To determine the vol pct a phase, a variation of the one dimensional systematic point count method as described by Hilliard and cahn3 was used. The

Jan 1, 1962

By Frank H. Macpherson

Few people realize the tremendously important part that Saline and Pulaski Counties in central Arkansas have played in the winning of the war The present favorable war situation might have been very different if we had not had the bauxite produced during the past two years from these two small areas, a total Of about 15 square miles. As a general statement, it can be said that the Arkansas bauxite deposits are, individually, relatively small, irregular in thickness, somewhat scattered and, therefore, compared with coal or iron-ore or open-pit copper deposits, relatively ill adapted to a rapid and drastic expansion in output. A few years ago it would have seemed an impossibility for these two counties to produce over six million long dry tons of bauxite in one year. However, with the cooperation of the operators, that is what happened in 1943, when the state of Arkansas achieved the seemingly impossible with a production of 6,020,684 1 long tons (dried equivalent) of bauxite ore during the calendar year, compared with an average annual production of 323,7252 tons in the period 1931 to 1941. It became apparent early in the year '94' that the united States soon might be drawn into the war, and, therefore, that an immediate study of the domestic metal situation was necessary. Aluminum is by far the most important metal used in the manufacture of aircraft and many other implements of war and it was evident that there would have to be a tremendous increase in the domestic production of bauxite, which is practically the only present source of this metal. AS more than 95 per cent of the known bauxite reserves of the United states was in Arkansas, careful preliminary studies were made in that state by representatives of the united States Bureau of Mines, the United States Geological survey and the War Production Board in the summer of 1941 Reserves in other states also were studied. The result of these studies was a recommendation by the War Production Board that mining in the bauxite.producing areas of Arkansas be geared for maximum production, in order to supply sufficient ore for this country's war requirements and, if necessary, to supply the war needs of Canada as well. The annual goal of eight million long tons (dry weight) set for Arkansas by the war Production Board was exceeded in 1943, when in August the output reached a rate equivalent to more than 8,300,000 long tons, dry basis. Because of the comparatively small tonnage of bauxite reserves, Congress appropriated funds for an extensive drilling program to be carried out by the Bureau of Mines in cooperation with the Geological Survey. Drilling began in May 1942 but owing to delay in delivery of drills, and trucks upon which the drills were mounted the program did not get into peak operation until early in 1943. By the end of July 1944, the Bureau of Mines records indicated an addition to the Arkansas reserves of 10,000,000 long tons (wet basis) in place,

Jan 1, 1946

By Frederic Becket

IN a recent article,1 which described the softening effect of columbium in plain high-chromium steels, the authors stated that their investi-gations had shown columbium to be also a particularly valuable inhibitor of intergranular corrosion in steels of the 18 per cent chromium, 8 per cent nickel type. It is the purpose of the present paper to record some of the results obtained through the introduction of columbium to the austenitic chromium-nickel steels. The damaging effects of this type of corrosion have become so widely known as to restrict considerably the applications of the steels under consideration, and therefore there is little question of the importance of the goal to be attained. Numerous contributions concerning the susceptibility of the aus-tenitic chromium-nickel steels to intergranular corrosion have appeared during the past few years, and among others who have dealt construc-tively with the subject are such well-known authors as Strauss and Houdremont of Germany, Hatfield of England, and Bain in the United States. Different theories have been propounded as to the cause of intergranular corrosion, and various remedial measures have been proposed, the majority of which involve the use of addition agents. Titanium is the addition agent at present most generally employed, as suggested by Houdremont and modified as described by Bain, Aborn and Rutherford.2 Little has been published on the effects of holding these steels for long periods at the relatively lower temperatures in the presence of

Jan 1, 1934

By R. I. Jaffee, H. R. Ogden, D. J. Maykuth

IN THE past year, Jaffee and Campbell&apos; and Finlay and Snyder2 reported on the mechanical properties of titanium-base alloys, some of which were in the same ranges of composition as are covered in this paper. In this paper, evidence confirming that given by Finlay and Snyder on the effects of carbon, oxygen, and nitrogen on titanium will be presented; and, in addition, new data will be given on the effects of these elements on the flow properties and phase transformation of titanium. Materials and Preparation of Alloys The preparation and general properties of iodide titanium have been adequately described elsewhere.&apos; , As-deposited iodide titanium rod, prepared at Battelle, of Vickers hardness less than 90 was employed as the base metal in the present work. This was the same material as that used by Finlay and Snyder.2 The probable analysis reported by them for standard quality metal holds here also: N 0.005 pct, 0 0.01 pct, C 0.03 pct, Fe <0.04 pct, A1 <0.05 pct, Si <0.03 pct, and Ti 99.85 pct. Carbon was added in the form of flake graphite supplied by the Joseph Dixon Crucible Co. Oxygen was added in the form of c.p. grade TiO, powder, produced by J. T. Baker Chemical Co. Nitrogen was added in Ti3N4 powder, supplied by the Remington Arms Co. Individual ingots weighed 7 or 8 g. Carbon, oxygen, or nitrogen was added by placing the corresponding powder in a capsule made from as-deposited iodide titanium rods and melting the capsule with the balance of the charge. The charge was are-melted with a tungsten electrode on a water-cooled copper hearth under a partial vacuum of very pure argon (99.92 pct minimum). Melting was practically contamination free. Vick-ers hardness increases of less than 10 points were normal for unalloyed iodide titanium control melts. Nitrogen analyses of are-melted iodide titanium showed a nitrogen content of 0.005 pct, about the same as is present in the as-deposited rod. No tungsten pickup was found in a melt of iodide titanium analyzed for tungsten. Weight losses in melting nitrogen-free alloys were very small and varied consistently from nil to 0.015 g (0 to 0.2 pct). This permitted the use of nominal composition for these alloys. Chemical analyses made for carbon, which can be analyzed conveniently by combustion methods, justified this procedure. Where nitrogen was added, considerable splattering took place. Here it was necessary to analyze for nitrogen by the Kjeldahl method. The ingots were hot rolled at 850°C to about 0.045 in. thick. After hot rolling, the strips were descaled by mechanical grinding, and then given a cold reduction of 5 to 10 pct to insure a uniform thickness throughout the length of the specimen. The edge strips and the tensile strips were annealed in a vacuum of 1x10-4 mm Hg pressure for 3 1/2 hr at 850°C and furnace cooled. Methods of Investigation Hardness Measurements: At least five Vickers hardness measurements were taken using a 10-kg load on each sample in the following conditions: (1) top and bottom of each ingot, (2) top and bottom surface of as-rolled and annealed sheet, and (3) on cross-section of annealed sheet and all quenched specimens. Tensile Tests: Tensile tests were conducted on Baldwin-Southwark testing machines having load ranges of 600 or 2000 lb. Tests were made on 1-in. gauge-length specimens, 3 1/4-in. overall length, 1/2 in. wide, 0.040 in. thick, with a reduced section 1 1/4 in. long and 0.250 in. wide. Two SR-4, A-7 strain gauges, one mounted on each side of the specimen, were used to measure the strain over a limited range to determine the modulus of elasticity. After the modulus of elasticity readings had been taken, load vs. strain readings were taken, using only one strain gauge, at increments of 0.0001 in. until the yield points were passed and then at 0.001-in. increments to the limit of the strain-gauge indicator (0.02 in.). Strain readings above 0.02 in. per in. were taken every 0.01 in., using dividers to measure the strain between the 1-in. gauge marks until the maximum load had been reached. Crosshead speed, when using the SR-4 gauges, was 0.005 in. per min, and, when using dividers, 0.01 in. per min. Flow Curves: Flow curves were determined using the true stress-true strain data obtained during the tension test. The usefulness of this type of information has been dealt with very adequately elsewhere by L. R. Jackson,&apos; J. H. Hollomon,6 and many others. Flow curves of true stress vs. true strain could be converted to the more conventional cold-work curve of 0.2 pct offset yield strength vs. percentage of cold reduction by means of the transformation, 1/1 = 1/1-R, where R is the fraction reduction in cold working. Thus, the true strains corresponding to percentage reduction can be calculated, and the 0.2 pct offset yield strengths scaled off the — 6 curve by taking the true stresses corresponding to the values of 6 + 0.002 strain. Heat Treatment: For the transformation studies, the alloys were heat treated in a horizontal-tube furnace using a dried 99.92 pct argon atmosphere, and quenched into water. Essentially no contamination was found after several hours of heat treatment at temperatures up to 1050°C. Metallography: Specimens were prepared in the

Jan 1, 1951

By J. T. Norton, N. J. Grant, I. S., Servi

Coarse grained high purity aluminum was tested in creep at temperatures of 400° to 1200°F to develop subgrain structures. Measurements of subgrain size, distribution, and rotation were made from X-ray diffraction patterns. Subgrain size and distribution were checked metallographically and the size was compared with average slip band spacing. The slip family was determined for several specimens. THE interest and research recently evident abroad in the role of subgrain formation and polygon-ization as a contribution to the creep of metals at elevated temperatures is deserving of greater attention in this country. Such metallic subgrains can be defined as macroblocks existing within the grains. The general observation has been that the macro-blocks which belong to the same grain have a maximum difference in orientation of a few degrees. In spite of the considerable amount of work that has been done since Jenkins and Mellorl observed the "division of existing crystals into smaller units when deformation occurs at an annealing temperature," the subject of subgrain formation is only now receiving truly active discussion and investigation. The existence of subgrains has been revealed by metallographic methods, as in the work of Jenkins and Mellor,1 and by X-ray methods, first applied to this problem by Homes.&apos; Hirst3 and Calnan and Burns4 applied the back-reflection Laue technique to the study of coarse grained specimens. Wood et al.5 and Greenough and Smith&apos; examined the ring obtained with a back-reflection camera for the study of fine grained specimens. In addition to the above, the transmission technique was used by Wood.6 A special technique was developed by Guinier and Tennevin8 in order to improve the resolution. Metallographically, the subgrains have been observed directly on the surface of deformed specimens by Wood et al.,3 or have been made evident on repolished surfaces by applying a suitable etching reagent. The latter technique, first suggested by Lacombe and Beaujard,9 was then improved by Wyon and Crussard.10 Subgrains can be formed in single crystals after small amounts of bending followed by heating after this cold work, or during deformation at elevated temperatures. The first phenomenon was analyzed by Cahn11 for the simple case of pure bending followed by annealing. Cahn suggested a mechanism of subgrain formation based on the dislocation theory and called this phenomenon "polygonization." He extended this mechanism to the more complex case of local bending, such as the bending which may occur when a polycrystalline specimen is deformed in tension. Cahn&apos;s suggestion was later found quite consistent with the results obtained by Dunn and Daniels." An explanation has been presented recently regarding the formation of subgrains during deformation at elevated temperatures by Chang and Grant.&apos;" In general, there are two schools of thought on the subject. One, according to Wood et al.,5 is that subgrain formation is a mechanism of deformation which is operative under certain conditions in the same way that the slip process is the mechanism of deformation which is operative under other conditions. The boundaries between the subgrains undergo a viscous flow which contributes substantially to the deformation of the material. The second, according to Cahn,13 Wyon and Crussard,10 and Chang and Grant,18 is that subgrain formation is the effect of simultaneous deformation and annealing and is,

Jan 1, 1953

By H. S. George

On one occasion when it seemed desirable to reveal under the microscope not only the metallic structure of an alloy, but certain small non-metallic inclusions that are ordinarily obliterated by etching, it was discovered that, by partly eclipsing the illuminating pencil of light rays, the residual light was thrown on the object from one side and the structure was brought out in relief. At the same time, the non-metallic inclusions were retained in clear view. In this first demonstration of lighting obliquely through the objective a card was thrust part way into the light beam between the arc iris and the light filter; the shadow of the card on the filter served to locate its position. Next several stiff-paper disks of various diameters were mounted on flexible wires; some plasticine on the other end of the wires made it easy to adjust and maintain a disk at any desired position in the light beam. To facilitate manipulation, an assortment of disks was mounted on a wheel, as shown in Fig. 1. The purpose of partly eclipsing the light beam was discussed in an earlier paper.&apos; There it was pointed out that the usual methods of illuminating opaque objects for microscopic examination lend an unnatural appearance to the view, while the new method, which has been termed conical illumination, revels the true relationship of constituents by simulating natural lighting. In nature, all objects are lighted diffusely, or by light predominating from one direction, or by a combination of diffuse and directed light. Under these conditions, objects appear to have three dimensions—they possess relief. The kind of illumination known to metallographists as vertical or axial results in an unnatural appearance, as a large proportion of the illuminating rays are parallel to the line connecting the eye with the object, a condition almost never met in nature. Microconstituents

Jan 1, 1924

By J. W. Hickman, E. A. Gulbransen

One of the important factors that determine the resistance of a metal or alloy to further chemical reaction is the structure of the superficial oxide film. A thorough understanding of the physical and chemical structure as well as the stability of the oxide film formed on the surface as a function of time and temperature of the chemical reaction might furnish clues as to the nature of the reaction process and the protective nature of the film. A comprehensive program has been undertaken to study these phenomena. This paper summarizes the structure of the oxide films formed on the metals iron, cobalt, nickel, chromium and copper at temperatures up to 700°C. Before the introduction of the electron diffraction technique, it was necessary to use either direct chemical analyses or X-rav diffraction analyses to determine the nature of the oxide film formed on the metal or alloy. Chemical analyses yields information on the percentages of the several atomic species present in the film while X-ray diffraction analyses yield information on the atomic geometry. In special cases the information obtained may be identical, but in general both viewpoints are necessary. Much of the early work was carried out on the oxidation of bulk samples where thick films were obtained. The products were identified after cooling to room temperature by X-ray diffraction and chemical analyses. Although much useful information has been obtained in this manner. little could be learned about the character of the protective oxides during the period when the films were actually protective. Evidence concerning the chemical structure of thin oxide films has been made possible by the development of the electron diffraction reflection technique. In this method the most fruitful investigations have been made by carrying out the reaction in situ at the temperature at which the film is actually protective. Literature The oxidation of iron has been extensively investigated by X-ray and electron diffraction. Jackson and Quarrelll found that oxide films formed and examined at the same temperature differed considerably from those allowed to cool to room temperature. The results showed that below 400°C the oxide that was stable in intimate contact with iron was Fe³O4; between 515° and 900°C. the stable film was FeO. Above the upper change point of iron the oxide was found to be Fe³O4. From 400&apos; to 515°C., FeO, Fe³O4 or a mixture of the two oxides was found. Recrystallization of the air-formed film below 400&apos; and above 900°C. led to the formation of Fe3O4. In the range where thicker films consisted of FeO, the air-formed film was converted to a new hexagonal oxide not previously described.

Jan 1, 1947

By E. A. Gulbransen, J. W. Hickman

One of the important factors that determine the resistance of a metal or alloy to further chemical reaction is the structure of the superficial oxide film. A thorough understanding of the physical and chemical structure as well as the stability of the oxide film formed on the surface as a function of time and temperature of the chemical reaction might furnish clues as to the nature of the reaction process and the protective nature of the film. A comprehensive program has been undertaken to study these phenomena. This paper summarizes the structure of the oxide films formed on the metals iron, cobalt, nickel, chromium and copper at temperatures up to 700°C. Before the introduction of the electron diffraction technique, it was necessary to use either direct chemical analyses or X-rav diffraction analyses to determine the nature of the oxide film formed on the metal or alloy. Chemical analyses yields information on the percentages of the several atomic species present in the film while X-ray diffraction analyses yield information on the atomic geometry. In special cases the information obtained may be identical, but in general both viewpoints are necessary. Much of the early work was carried out on the oxidation of bulk samples where thick films were obtained. The products were identified after cooling to room temperature by X-ray diffraction and chemical analyses. Although much useful information has been obtained in this manner. little could be learned about the character of the protective oxides during the period when the films were actually protective. Evidence concerning the chemical structure of thin oxide films has been made possible by the development of the electron diffraction reflection technique. In this method the most fruitful investigations have been made by carrying out the reaction in situ at the temperature at which the film is actually protective. Literature The oxidation of iron has been extensively investigated by X-ray and electron diffraction. Jackson and Quarrelll found that oxide films formed and examined at the same temperature differed considerably from those allowed to cool to room temperature. The results showed that below 400°C the oxide that was stable in intimate contact with iron was Fe³O4; between 515° and 900°C. the stable film was FeO. Above the upper change point of iron the oxide was found to be Fe³O4. From 400&apos; to 515°C., FeO, Fe³O4 or a mixture of the two oxides was found. Recrystallization of the air-formed film below 400&apos; and above 900°C. led to the formation of Fe3O4. In the range where thicker films consisted of FeO, the air-formed film was converted to a new hexagonal oxide not previously described.

Jan 1, 1947

By Joshua I. Tracey, Mackenzie Gordon

THE bauxite deposits in central Arkansas were formed by weather¬ing, in early Eocene time, of fresh or kaolinized nepheline syenite above the water table in a subtropical climate of fairly continuous moisture. Four types are recognized: (1) residual bauxite deposits on kaolinized nepheline syenite, (2) residual deposits on kaolin and bauxite detritus, (3) alluvial deposits of sorted pebbles and pisolites of early Wilcox age, and (4) rubble deposits of later Wilcox age. All were invaded by kaolin and siderite during subsequent burial by Eocene sediments. PART I-FIELD RELATIONS OF THE DEPOSITS The Arkansas bauxite region for years has produced about 95 pct of the domestic supply of bauxite of the United States and it contains today reserves of more than 40 million tons-nine tenths of the known domestic reserves. During World War II, the Arkansas bauxite deposits were explored jointly by the U. S. Geological Survey and the U. S. Bureau of Mines. Some 6000 holes were drilled by rotary rigs under contract to the Federal Govern¬ment, which resulted in the discovery and delimiting of approximately 20 million tons of ore in place. Detailed study of the many sections cored through the bauxite, of data from a much greater number of drill holes made available by all the operating companies, and of the extensive mine faces exposed in the strip pits, has yielded valuable geologic information about the origin of the deposits. It is now possible to piece together a paleotopographic picture of the deposits and the now-buried land surface on which they formed. The bauxite region in the center of Arkansas (Fig 1) contains two producing districts: one in Pulaski County, just south of Little Rock, and the other in Saline County, about 15 miles to the southwest. The deposits in both districts are associated with hills of nepheline syenite, bosses of a large batho¬lith that was intruded into Paleozoic rocks and later buried beneath coastal plain sediments deposited during Cenozoic time. The folded Paleozoic rocks are exposed in the northwest half of the state and are covered in the southeast half by the nearly flat-lying coastal plain sediments. The older rocks were intruded by nepheline syenite, probably in Late Cretaceous time, and sub¬sequently were eroded so as to expose the top of the batholith. In Paleocene time, marine limestone and laminated black silty clay of the Midway group were deposited in an advancing sea, and covered all but the most elevated parts of the batholith. Erosion of the islands of nepheline

Jan 1, 1952

By R. A. Wagstaff

SINCE the time of the early Egyptians, the use of copper has been a boon to the life of most of the civilized world. Its use has been varied; in many connections, the art by which it attained its greatest usefulness has been lost. In this paper an endeavor will be made to take into consideration some of the many changes that have occurred during the last 40 years of copper-smelting operations. During that period the copper blast furnace has been almost forced out of existence by new methods of ore concentration-first, gravity concentration, and then flotation. These new methods of concentration introduced many new factors into the metallurgy of copper. The product was wet, it was fine and it was high grade. To overcome all these factors many changes have been necessary throughout the smelting agenda. New equipment has been necessary for transportation, unloading, sampling, bedding and moisturing in all smelting plants, especially the custom smelter. During the early days of "flotation," little was known about filtering or the use of an alkaline circuit; often the concentrate going to the smelter contained 20 to 25 per cent moisture. It is easy to imagine the difficulty arising with a product of this nature when it had to be shoveled by hand labor. To meet these conditions, mechanical unloading and sampling devices were soon developed. In many instances such good progress was made that actual costs for handling this unfavorable product were lower than those formerly incurred on the old product. Today most sampling of copper ores and concentrates is being done by mechanical sampling, pipe or augur sampling, or shovel sampling. Where concentrates are uniform in metal content, a great many of the plants now use pipe or augur sampling. For spotty ores, the old shovel sample with cone and quartering during the final stages is still in use. Where big tonnages are handled, mechanical sampling of concentrates is being done, with satisfactory results. To curtail slow and tedious cutting and mixing procedure, mechanical mixing boxes, splitters and cutters are used to cut down labor costs. MILLING As crude ores become scarcer, the use of milling operations increases. The few crude ores that are still smelted are used as fluxing types. To use these ores finer grinding has been found advantageous. This has made for better bedding and fluxing conditions, which in turn makes for faster smelting, lower fuel consumption and better metal recovery. The degree of fineness is more or less determined by the nature of the product. Most plants have set a standard of through ¾ -in. mesh screen for roaster- reverberatory smelting and through ¾ in. mesh screen for converter fluxes. For some refractory ores; even finer grinding has been found to be advantageous for good reverberatory smelting.

Jan 1, 1944

By Ira B. Joralernon

THREATS of a coming metal famine in the United States have filled many columns in magazines and newspapers in the past three years. This asserted menace has diverted attention from the actual results of recent exploration. Because no one had bothered to look into the facts, the statistical experts assumed that little ore was being found. They often subtracted the staggering tonnage of metals produced during the war from earlier published reserves, and assumed that the difference was all we had left. Naturally, they shuddered, with all possible publicity. For their figures showed an imminent lack of nearly all the metals needed for an industrial civilization, as well as for mechanized war. They concluded that only wholesale imports and development and production of metals by Federal agencies could avert the famine.

Jan 1, 1948

By Leendert de Witte, Fred J. Radd

In many areas caring failures can be directly related to electrical currents observed in the casings. It is the thesis of this paper that the observed casing currents are mainly due to electrochemical potentials of the type in evidence on spontaneous potential curves of electrical logs. The general nature of these potentials are discussed and an equivalent circuit is given for current and potential distributions around open holes. The casing forms a short circuit to these potentials and tends to average the effects of local cells. The case of casing corrosion opposite the Dakota water sands in the salt-mud area of Kansas is discussed anil used us a qualitative, illustration of the relation between SP&apos;s and casing currents. A method of quantitative derivation of casing current distribution frorn electric log SP curves, using linear transform theory, is described and results are compared with a measured current profile. The effects of hydrogen over-potentials at the cathodic portions of the pipe are considered and some laboratory data are given in support of conclusions regarding the over-1.01tuge.s. INTRODUCTION To date an appreciable amount of work has been done on the measurement of oil well casing currents and on the correlation of the anodic portions of the current profiles with corrosive casing failures. Speculations on the origin of the casing currents have, however, remained rather vague; and although almost every plausible cause has been mentioned, there is to the writers&apos; knowledge no clear-cut expose&apos; on the details of the causes of the corrosive currents in the literature. A study of current surveys and casing failures in the N.W. Burnett field, Ellis County. Kan.. indicated the probability that concentration cell emf&apos;s between the Wellington salt section and the relatively fresh waters in the Dakota sands were a major cause of the corrosion currents. A more general concept evolved upon analysis of the severe corrosive conditions in the Pleistocene sands in the Ventura Avenue and San Miguelito fields in California. In this area no major variations in the salt content of the formation waters occur and yet large casing currents are observed. An explanation is found in the fact that the local spontaneous potentials which are set up due to concentration contrast between the drilling fluid and the connate water are short circuited when casing is set. The very conductive path through the casing increases the magnitude of the currents and has the tendency to average local sources over fairly large intervals. Current will flow between the sections that are predominently shaly and the sections that are mostly sandy. At the places where the current leaves the pipe, corrosive attack will occur. This same phenomenon will be present wherever unprotected pipe is set through sections that show large SP kicks on the electric logs over reasonably thick interval~. GENERAL- NATURE OF THE SPONTANEOUS POTENTIALS When a sequence of sedimentary rocks is penetrated by a drill hole filled with a mud which has a different salt concentration from that in the formation waters, various types of electrochemical potentials are established between the formations and different parts of the mud column. Opposite clean sand sections. a simple liquid-liquid junction potential will be observed; while opposite argillaccous formations, a membrane potential, often referred to as shale potential, will be established. The first quantitative analysis of these emf&apos;s in terms of liquid junction and membrane potentials is due to Wyllie.1

Jan 1, 1956

E P MATHEWSON, Disttrict 0 NEW YORK, N Y PAST PRESIDENTS EDWIN LUDLOW, District 0 NEW YORK, N Y ARTHUR S DWIGHT, District 0 NEW YORK, N Y FIRST VICE-PRESIDENT J V, W REYNDERS, NEW YORK, N Y TREASURER CHARLES F RAND, NEW YORK, N Y

Jan 1, 1923

By H. S. Cannon, F. N. Rhines

IT. H. Hausner( Sylvunia Electric Products Inc., Bay-side, N. Y.)—The results reported by the authors are interesting because they contribute some information on the principles of sintering and also because of a certain practical value for the manufacture of powder . metallurgical parts in production. Pressed powder compacts are frequently sintered in a boat in several layers so that the lower layers are actually sintered under the weight of the upper layers and, therefore, are frequently deformed. The authors gave information on this deformation process by determining the effect of the load on the density. The experimental setup of the authors, however, has a disadvantage—that the sintering occurred in a cylindrical container so that the deformation was stopped in the direction of the diameter. The authors should have rather called this a study of hot-pressing than of sintering. I want to call the attention of the authors and others interested in sintering under load to the experimental work described by Dawihl and Rix.&apos; These authors sintered cylindrical compacts under a lengthwise ten-sional load of 0 to 25 g and found that the shrinkage in length and diameter changes considerably with the load, but that the volume shrinkage is affected very little by the load. H. S. Cannon (authors&apos; reply)—We wish to thank Dr. Hausner for calling attention to the experimental work of Dawihl and Rix. The fact that they found volume shrinkage little affected by varying tensional loads during sintering seems to support the contention that the forces due to loading are equivalent to and additive to the forces which cause densification. This contention is the basis of our comparison of sintering and creep.

Jan 1, 1952

By G. V. Woody, J. D. Price

Many producers of by-product coke have spent considerable time and given considerable thought to the use of a substitute for low-volatile coal as an admixture with high-volatile coking coal for charging high-temperature by-product coke ovens. Generally speaking, there are two principal reasons for this, one being occasioned by the lack, in certain localities, of low-volatile coal delivered at a cost sufficiently low to permit its use, and another being the desirability of finding a substitute product with a delivered cost lower than the cost of the low-volatile coal. It was for the first of these reasons that the Colorado Fuel and Iron Corporation was particularly interested in this subject. This paper deals with the experimental work and the results obtained by that company in producing and using low-temperature char. Overcoming Defects in Coke from Colorado Coals Colorado coking coals are all of the high-volatile type and were all laid down during the Cretaceous period, which makes them something like 80 million or so years younger, geologically, than eastern coals. They behave, when coked alone, something like the Pittsburgh-seam coals. They make a very brittle, highly cross-fractured, fingery coke of fair shatter value but quite low in resistance to abrasion. Mixed with a low-volatile coking coal such as Poca- hontas or certain Oklahoma coals, they make a coke that is equal to virtually any of the eastern cokes. The inferior quality of Colorado coke has long been recognized, and a considerable amount of time, effort and money has been spent upon investigations of means for improving its physical properties. While it has been found that some improvement in quality of coke can be secured by the adjustment and control of such variables as pulverization, moisture content, oven temperature and bulk density of charge, and through the addition of certain inert materials such as pulverized coke breeze, pitch, high-volatile noncoking or semicoking coal, the benefits so gained have been comparatively small. There are no low or medium-volatile coking coals available within a reasonable freight-cost distance. Therefore a substitute for low-vol-atile coal was developed through low-tem-perature carbonization—or, more correctly speaking, through the partial devolatiliza-tion—of high-volatile coals. The blending of this lower volatile char with the high-volatile coking coal distinctly improves the quality of coke made from Colorado coal. There is nothing especially new about this idea. In 1908 a Japanese patent was taken out by Kotaro Shimomura, whose claim was: The method of making a nonfingery coke out of bituminous coals, without using natural coals of low-volatile matter; according to which a certain coal is heated at a temperature between about 300°C. and about 600°C. so as to leave about 15 to 25 per cent volatile matter in the coal; this coal is mixed with the

Jan 1, 1944

By J. D. Price, G. V. Woody

Many producers of by-product coke have spent considerable time and given considerable thought to the use of a substitute for low-volatile coal as an admixture with high-volatile coking coal for charging high-temperature by-product coke ovens. Generally speaking, there are two principal reasons for this, one being occasioned by the lack, in certain localities, of low-volatile coal delivered at a cost sufficiently low to permit its use, and another being the desirability of finding a substitute product with a delivered cost lower than the cost of the low-volatile coal. It was for the first of these reasons that the Colorado Fuel and Iron Corporation was particularly interested in this subject. This paper deals with the experimental work and the results obtained by that company in producing and using low-temperature char. Overcoming Defects in Coke from Colorado Coals Colorado coking coals are all of the high-volatile type and were all laid down during the Cretaceous period, which makes them something like 80 million or so years younger, geologically, than eastern coals. They behave, when coked alone, something like the Pittsburgh-seam coals. They make a very brittle, highly cross-fractured, fingery coke of fair shatter value but quite low in resistance to abrasion. Mixed with a low-volatile coking coal such as Poca- hontas or certain Oklahoma coals, they make a coke that is equal to virtually any of the eastern cokes. The inferior quality of Colorado coke has long been recognized, and a considerable amount of time, effort and money has been spent upon investigations of means for improving its physical properties. While it has been found that some improvement in quality of coke can be secured by the adjustment and control of such variables as pulverization, moisture content, oven temperature and bulk density of charge, and through the addition of certain inert materials such as pulverized coke breeze, pitch, high-volatile noncoking or semicoking coal, the benefits so gained have been comparatively small. There are no low or medium-volatile coking coals available within a reasonable freight-cost distance. Therefore a substitute for low-vol-atile coal was developed through low-tem-perature carbonization—or, more correctly speaking, through the partial devolatiliza-tion—of high-volatile coals. The blending of this lower volatile char with the high-volatile coking coal distinctly improves the quality of coke made from Colorado coal. There is nothing especially new about this idea. In 1908 a Japanese patent was taken out by Kotaro Shimomura, whose claim was: The method of making a nonfingery coke out of bituminous coals, without using natural coals of low-volatile matter; according to which a certain coal is heated at a temperature between about 300°C. and about 600°C. so as to leave about 15 to 25 per cent volatile matter in the coal; this coal is mixed with the

Jan 1, 1944

W. H. BASSETT,* Waterbury, Conn. (written discussion ?).-The effect of reducing gases on hot solid copper has been known for many years in the copper industry, and precautions taken to guard against it in the general practice in copper heating and annealing. In view of the statement that Bengough and Hill, in 1910, were the first to suggest the possibility of the formation of gas within the copper itself, it is interesting to note that in Harper&apos;s Magazine for April, 1904, an article, "Life and Diseases of Metals," by Professor Heyn, illustrated the effect of reducing gases on copper by a photograph, which is shown in Fig. 1. This he entitled "Copper burst asunder by disease." After referring to the effect of hydrogen on steel, he makes the following remark: "Similar symptoms of poisoning, caused by hydrogen or gases containing hydrogen (as gas for lighting purposes), are apparent in copper when exposed to red heat. Not every kind of .copper is susceptible to this poisoning in equal degree. Copper per-fectly free of cuprous oxide is entirely exempt from poisoning. Most of the various coppers of commerce, however, contain cuprous oxide, formed during the smelting process while exposed to atmospheric influences. In such coppers, containing cuprous oxide, hydrogen causes a terrible disease on the copper being heated red hot. The copper bursts asunder and is permeated by cracks. This disease is practically incurable and can be eradicated by resmelting only. The results work destructively according to the amount of cuprous oxide contained in the copper." It must have been evident to Professor Heyn, as it was to us on reading this article, that the bursting asunder of the copper was clue to the formation of steam. Practical copper heaters have known for many years that it was quite possible to produce blisters, or large gas holes, in the interior of copper plates or bars by heating to a high temperature in reducing gases. These facts, of course, do not detract from the value of the study of the action of hydrogen gas that has been made by Mr. Pilling, but simply illustrate that the practical effect of reducing gases on furnace-refined copper has long been a troublesome factor in the heating or annealing of that metal.

Jan 1, 1919

By H. L. Stone, A. O. Garder

A numerical method of solving the partial differential equations which describe the one-dimensional displacement of oil by gas has been presented. Possible extension of the method to treat multidimensional flow is discussed, and the limitations of this extension are indicated. Using this method, it is possible to allow for the existence of a gas cap, the presence of any number of gas-injection or oil-production wells and the evolution of dissolved gas from the oil. It is also possible to allow for variation in the cross-sectional area, elevation, porosity and permeability of the reservoir. The influence of relative permeability and the force of gravity in the direction of flow upon the displacement is considered. The influence of capillary pressure upon the flow and the effect of gravity in the direction perpendicular to flow are neglected. The physical properties 01 the fluids are considered to be Junctions of pressure only, and equilibrium between contiguous phases is assumed. The numerical calculations can be readily carried out by the use of a digital computer. Several example analyses have been performed using the IBM 704 computer, and about one-third of an hour of computing time was required per case. Reservoir behavior predicted by use of this numerical method was compared to data obtained by other methods for three cases — complete pressure maintenance, dissolved-gas drive and gas-cap drive. The independent solutions to these problems were obtained by analytical solution, laboratory experiment and field data, respectively. Agreement of the numerical solution with data from these sources was good; this agreement establishes the convergence and accuracy of the numerical method. INTRODUCTION Most petroleum reservoirs can be produced by any one of several alternative programs. When a reservoir is produced by primary methods, production economics can be influenced by controlling the number and location of wells and the flow rate of each well. An even greater influence may be achieved by augmenting the recovery of oil obtainable by primary methods. This can be accomplished by injection of fluids such as water, natural or enriched gas or a bank of light liquid hydrocarbons. Selection of the most desirable operation requires a means of predicting the reservoir behavior which will result from each of the several alternative programs. The purpose of this paper is to present a mathematical method for predicting the behavior of reservoirs produced by gas-cap drive, dissolved-gas drive or pressure maintenance by gas injection. The method described herein takes cognizance of phase changes caused by a decline or an increase (due to gas injection) in reservoir pressure, of the presence of a gas cap and of the effect of gravity on the flow of gas and oil. Relative permeability relationships are used to define the flow properties of the rock. Allowance is made for variation in cross-sectional area, elevation, permeability and porosity of the reservoir. Both the influence of capillary pressure upon the flow and pressure gradients in the gas cap are neglected. Whenever a liquid phase and a gas phase are in contact, they are assumed to be in equilibrium. The physical properties of the fluids are considered to be functions of pressure only. Therefore, if the method is to be used to predict the effects of a gas-injection program, mixtures of the injected gas and formation crude should-have the same physical properties as mixtures of formation gas and crude. The equations to be presented in this paper apply only to a one-dimensional case; therefore, they neglect the influence of gravity in the direction transverse to the flow. As is well known, this gravitational influence may lead to overriding of oil by gas. Consequently, this procedure as presented is most applicable to long, thin reservoirs for which gravity overriding is not important. On the other hand, the equations presented can be generalized to treat multidimensional flow and, hence, to consider gravity overriding, if desired. A word of caution on two points is advisable here, however. First, the authors have not demonstrated the accuracy of the numerical technique for multidimensional flow. Second, and more important, capillary pressure will often be of importance in multidimensional problems. Obviously, in such cases a generalization of the

By R. Schuhmann Jr., P. J. Ensio

John Chipman (Massachusetts Institute of Technology, Cambridge, Mass.)—The activity of FeO in silica-saturated slags shown in Table V is about 0.40 in the temperature range 1260" to 1350°C. Recent measurements by N. A. Gokeen at 1600" lead to about the same value. He finds the oxygen content of liquid iron in equilibrium with silica and ferrous silicate slags to be 0.088 pct. Under pure iron oxide slags at the same temperature, it is 0.225 pct. The ratio places the activity at 0.39.

Jan 1, 1952

By Hans Lundberg

AFTER the war years, great activity has been shown in geophysical exploration for ore. The appreciation by mining and government geologists of geophysical techniques and results is largely responsible for the popularity of these methods. In Canada, plans are being made to study, by geophysical methods, the structure of a portion of the Pre-Cambrian shield in the hope that such studies will not only give a clearer picture of the geology, but will be of direct aid to the mining companies when selecting areas for detailed prospecting. Although geophysics thus has become more popular, some engineers are still reluctant to employ the methods to their full extent. Allotted funds are often rather low, so that the least expensive

Jan 1, 1947