Search Documents

By I. Fatt

A recently developed system for measuring electrical resistivity of liquids without use of electrodes offers some interesting possibilities in electric logging technology. The equipment as supplied by the manufacturer is satisfactory for continuous mud logging on a drilling rig or for measuring mud or filtrate resistivity in the laboratory. A simple modification of the commercially available instrument makes it suitable for measuring resistivity of core samples in the laboratory. The continuous measurement of mud resistivity on a drilling rig is a convenient means for detecting mixing of formation water with the drilling mud. Such information is useful to the geologist, the mud engineer and the logging engineer. However, continuous mud resistivity logging by conventional electrode-type resistivity cells is beset with difficulties. The mud, sand and rock chips abrade the electrodes, thereby changing the cell constant and eventually destroying the cell. Also, additives and crude oil in the mud may poison the electrodes by coating them with a nonconductive material. An electrode-type resistivity cell. therefore, may give erroneous readings under certain conditions. Electric logging companies circumvent the electrode poisoning problem by using a four-electrode resistivity cell for measurement of mud resistivity. In this cell, change in electrode area does not change the cell constant. However, the four-electrode cell is difficult to adapt for continuous reading and does not solve completely the problem of electrode abrasion by the sand and cuttings in the mud. The measurement of electric logging parameters on core samples in the laboratory encounters some of the same problems discussed in connection with mud logging. Ideally, the electrical resistivity of a core sample should be measured by placing platinum black electrodes in direct contact with the plane ends of a cylindrical or rectangular sample. Platinum black electrodes however, are much too fragile and easily abraded to be brought in contact with a rock sample. Also, oil or other constituents in the fluid contained in the sample will poison platinum black. In practice, gold-plated brass electrodes, in an AC bridge circuit operating at about 1,000 cps, are used for routine core analysis. For more precise work in research studies, a four-electrode scheme is used.',' Preparation of the samples for the four-electrode method is much too involved for routine core analysis. An apparatus for measuring resistivity of liquids without use of electrodes was described by Guthrie and Boys3 in 1879. They suspended a beaker, containing the electrolyte, by a torsion wire and rotated a set of permanent bar magnets around the vessel. The eddy currents induced in the electrolyte reacted against the rotating magnetic field to develop a torque, which was measured as a deflection of the torsion wire. In 1879 this method could not be made precise or convenient because of the lack of strong permanent magnets. The writer described a very greatly improved apparatus similar to that of Guthrie and Boys, but it was not suitable for continuous measurements or core samples.' Many electrodeless resistivity devices using radio frequency current are described in the literature.5, 6 These generally are suitable only for noting the end-point in a chemical titration. They do not measure resistivity, instead measuring a complex quantity which includes the dielectric constant and the magnetic permeability. The first description of the apparatus to be discussed in this paper was given by Relis.7 Improvements and modifications are described by Fielden,s Gupta and Hills,> and Eichholz and Bettens.10 DESCRIPTION OF APPARATUS The apparatus used in this study is based on the principle that the solution under measurement can form a loop coupling two transformer coils, as shown in Fig. 1. For a fixed AC voltage applied across Coil A, the voltage appearing across Coil B is a function of the resistance of the liquid-filled loop. The details of the voltage generating and measuring circuits are given in Refs. 7, 8, 9 and 10. A block diagram of the equipment is given in Fig. 7. Special features worth mentioning are the operating frequency of 18,000 cps and the automatic temperature compensation which results in the given resistivity readings being automatically correlated to 25°C. The liquid loop supplied by the manufacturer, shown in Figs. 1 and 2, was modified for use in core analysis (Fig. 3). The core sample under test is substituted for a section of the original loop. As shown in Fig. 3, the unit accepts only plastic-mounted cylindrical core specimens. A Hassler-type sleeve easily can be designed for the unit if unmounted cores are to be measured. EXPERIMENTAL PROCEDURE MUD LOGGING A simulated mud line was set up in the laboratory.

By James Gardner

IN 1923, Oklahoma took second place as an oil-producing state; whereas in 1922 it was the leader. California surpassed it, in 1923, by nearly 100,000,000 bbl. In 1923, Oklahoma produced, according to statistics of The Oil & Gas Journal, 165,013,685 bbl., or an increase of approximately 10 per cent. over the preceding year; the increase in California was approximately 90 per cent. The number of wells drilled in Oklahoma and the results of the two years are contrasted in the following table from data published in a preliminary bulletin by the U. S. Geological Survey. 1922 1923 Oil wells 4,149,68%. 3,515, 60% Gas wells 571, 9 %u 587, 11% Dry holes 1,428,23% 1,731,29% Total wells 6,148 5,833 The initial production from wells drilled in Oklahoma in 1923, according to The Oil & Gas Journal, was the largest in the history of the state, being 1,277,936 bbl. It has been 32 years since oil development began in the state, last year being the largest in the amount of production. The production of the past year would have been considerably greater were it not for the shutdown order in the Burbank field and curtailment of production in the Hewitt and Tonkawa pools.

Jan 3, 1924

By Peter Haasen

INDIUM antimonide has the zincblende structure. A possible defect that does not disturb the indium tetrahedron surrounding any antimony atom in this lattice (or vice versa) is obtained when neighboring

Jan 1, 1958

By B. J. Nelson, F. N. Rhines

STUDIES upon the rates of oxidation of copper alloys containing small quantities of the alloying elements1,2 have shown that steady growth of the scales at predictable rates is limited to a small concentration range and to oxidation at temperatures above 600°C., whereas unpredictable and erratic oxidation behavior is found with alloys containing larger additions and at low temperatures. The latter effect appears to be associated with modifications in the geometric disposition of the oxides. At low concentrations of the baser elements in copper, simple oxidation behavior is typified by the formation of two distinguishable zones of oxidation: (I) a subscale composed of discrete particles of the oxide of the alloying element embedded in substantially pure copper and (2) an external scale composed of cuprous oxide (with a very thin layer of cupric oxide on the outside) containing particles of the alloying element distributed throughout, but most profusely near the metal surface (see Fig. 2, top). Where this type of structure obtains, the process of oxidation is believed to be implemented, and its rate controlled, by the diffusion of the reacting elements through a continuous matrix phase; i.e., through the alpha (metallic) phase of the subscale and alloy and through the cuprous oxide of the external scale. Copper is presumed to diffuse outward through the cuprous oxide layer to the external surface, where it reacts to form more cuprous oxide.3 Oxygen is delivered at the oxide-metal interface in the form of cuprous oxide, which may either react with the alloying element to deposit its oxide at the inner limit of the external scale or dissolve in the pure copper that remains at the surface of the metal after it has become depleted in its oxidizable alloying elements. Both oxygen and the alloying element are pictured as diffusing through the metal, the oxygen inward and the alloying element outward. Where the two diffusion streams meet in sufficient concentration the oxide of the subscale is precipitated. If the oxygen pressure in the surrounding atmosphere is just below the pressure necessary to maintain cuprous oxide undecomposed, no cuprous oxide can be formed; some of the oxide of the alloying element may form upon the external surface, if its decomposition pressure is below that of cuprous oxide, and a normal subscale appears. This condition is achieved experimentally by enclosing the alloy with cuprous oxide together with an excess of copper. At temperatures from 600°C. downward, the precipitated oxides tend to accumulate at the grain boundaries of the alpha phase where a relatively small volume establishes a partial barrier to the diffusion of the reactants. Similarly, large volumes of precipitated oxides tend to deposit in various patterns that may be expected to hinder the diffusion of the reactants in the

Jan 1, 1943

By Edgar C. Bain

Jan 1, 1932

By Frederick N. Rhines

Pure copper that has been allowed to oxidize at an elevated temperature in the air is found to be covered with two distinguishable layers of oxide scale. The outer of these, which is very thin, is composed of cuprie oxide, while the inner layer, comprising the bulk of the scale, is made up chiefly of cuprous oxide (Fig, la). If a small quantity of an alloying element, such as silicon, is present in the copper, silica particles are found disseminated through the cuprous oxide, deposited most abundantly near the metal surface, and, in addition, silica particles occur to a limited depth within the copper itself (Fig. 1b). It is this inner layer, composetl of oxide particles precipitated in a matrix of metallic copper, that is known as the "subscale" or the zone of internal oxidation. Under a low oxygen pressure it is possible to produce the subscale without the formation of external layers of copper oxides, thus leaving the metal surface bright and apparently clean while oxidation has occurred, in fact, to a considerable depth within the metal (Fig. 2). Although little is yet known in a detailed way of the mechanism of internal oxidation, the general nature of the process is evident. By virtue of the considerable solubility of oxygen in copper,' it is possible to bring the alloying element in contact with oxygen within the metallic solid solution. If the oxide of the alloying element is more stable than cuprous oxide, the foreign oxide may form and, since most oxides are relatively insoluble in copper, it will not long remain in solution, but mill separate as a precipitate. As the metallic solute is exhausted in the zone of precipitation, oxygen that is constantly being supplied at the surface diffuses farther into the alloy and thus produces an ever-thickening shell of subscale. The distribution of the reacting elements in the subscale and adjoining zones must be somewhat as indicated in Fig. 3. The conditions requisite to internal oxidation to be anticipated are thus: (I) a solubility of oxygen in the alloy, (2) the ability of oxygen to diffuse at an appreciable rate into the alloy, (3) the possibility of the

Jan 1, 1940

By Frederick N. Rhines

Pure copper that has been allowed to oxidize at an elevated temperature in the air is found to be covered with two distinguishable layers of oxide scale. The outer of these, which is very thin, is composed of cuprie oxide, while the inner layer, comprising the bulk of the scale, is made up chiefly of cuprous oxide (Fig, la). If a small quantity of an alloying element, such as silicon, is present in the copper, silica particles are found disseminated through the cuprous oxide, deposited most abundantly near the metal surface, and, in addition, silica particles occur to a limited depth within the copper itself (Fig. 1b). It is this inner layer, composetl of oxide particles precipitated in a matrix of metallic copper, that is known as the "subscale" or the zone of internal oxidation. Under a low oxygen pressure it is possible to produce the subscale without the formation of external layers of copper oxides, thus leaving the metal surface bright and apparently clean while oxidation has occurred, in fact, to a considerable depth within the metal (Fig. 2). Although little is yet known in a detailed way of the mechanism of internal oxidation, the general nature of the process is evident. By virtue of the considerable solubility of oxygen in copper,' it is possible to bring the alloying element in contact with oxygen within the metallic solid solution. If the oxide of the alloying element is more stable than cuprous oxide, the foreign oxide may form and, since most oxides are relatively insoluble in copper, it will not long remain in solution, but mill separate as a precipitate. As the metallic solute is exhausted in the zone of precipitation, oxygen that is constantly being supplied at the surface diffuses farther into the alloy and thus produces an ever-thickening shell of subscale. The distribution of the reacting elements in the subscale and adjoining zones must be somewhat as indicated in Fig. 3. The conditions requisite to internal oxidation to be anticipated are thus: (I) a solubility of oxygen in the alloy, (2) the ability of oxygen to diffuse at an appreciable rate into the alloy, (3) the possibility of the

Jan 1, 1940

By C. C. Koch, M. L. Picklesimer

PHYSICAL metallurgists interested in the alloying behavior and phase transformations in rare-earth metals and alloys require a strain-free polished and etched surface for both metallographic and X-ray examination. However, the rare earths have presented a problem in this respect since they are difficult to polish free from strain and are very reactive to the atmosphere. Their tendency to oxidize readily even at room temperature necessitates careful preparation and rather elaborate protection if their surface is to be examined for any length of time. The "light" lan-thanides (i .e., atomic numbers less than 63), especially lanthanum and cerium, are particularly bad in this regard; they oxidize very rapidly at room temperature. To eliminate the problem of plastic deformation remaining on the surface after mechanical polishing, electropolishingl and chemical polishing techniques2 have been developed. The electropolishing technique requires the specimen to be immersed in an electrolyte at -77°C and thus obviates a metallographic study of, for example, the fcc —double-hexagonal close-packed (dhcp) transformation in cerium which begins at -10°C. The chemical polishing solution has been used only on several of the "heavy" rare-earth metals. However, a convenient method for protecting the polished and etched surfaces from atmospheric corrosion has not been available. Our interest in the superconducting properties of lanthanum, and in the phase transformations in lanthanum and cerium, has led us to develop a technique for the metallographic preparation of lanthanum and cerium which clearly reveals the microstructure and preserves the etched surface for days. The specimens are chemically polished and anodized. The chemical polishing is performed at room temperature, the anodic oxide film provides the required protection from the atmosphere, and colors produced in the film provide a simple positive technique for phase identification. Lanthanum and cerium metal ingots obtained from Johnson Matthey and Co., Ltd., were remelted to suitable shapes and heat-treated to produce various microstructures. The samples were placed in epoxy mounts and, after a small hole was drilled in the back of the mount for electrical contact, were ground on silicon carbide

Jan 1, 1968

By Roy A. Lindgren

Since the year 1643, when the first blast furnace in America for treating iron ore was built at Saugus, Mass., out of mica schist quarried in the neighboring district, the procurement of a suitable refractory for furnace lining has been a problem of concern to the operators of furnaces. The stacks built of mica schist continued to smelt iron ore until about 1836, when, according to F. H. Norton, the first firebrick were produced1, at Queens Run, Pa. Other writers speak of brick having been molded and burned in Massachusetts about the year 1834. In 1841, Andrew Russell began to produce medium refractory plastic clay brick near East Liverpool, Ohio, that were used for lining blast furnaces1. The well-known Kentucky clay-producing district was not opened up until the year 1871, but since then it has produced a large percentage of the linings for iron blast furnaces. While some strides have been made by the refractories industry during the 100 years that have passed since the first firebrick were produced, it has been only during the last two decades that any real progress has been made towards bettering the product, even though the method of production had improved. Perhaps the fault lies with the user of the brick rather than with the producer, for not sooner demanding a superior product. During the past 15 years the tonnage produced per lining has increased from 500,000 gross tons to 1,000,000 gross tons, and now some furnaces are producing 1,600,000 gross tons and better on a single lining. It is true that enlarged capacity of furnaces and improved practice have accounted for some of this increase in tonnage, nevertheless better quality in firebrick must be given credit for its share. However, we are not yet ready to say that we have reached a maximum life of furnace lining. We believe that a better product can be produced and that the refractories industries of America will, through their extensive research depart-

Jan 1, 1937

By Adrian C. Dorenfeld, Theodore Balberyszski, Strathmore R. B. Cooke

This paper reports results of studies of sulfidiza-tion of base-metal oxides and silicates with gaseous sulfur, hydrogen sulfide gas and pyrite and of their subsequent flotation with xanthate collectors. It has been established that a 100% conversion of the oxides of lead, zinc, copper and manganese into their respective sulfides is possible and is a function of reaction time and temperature. Sulfidization of chrysocolla (with malachite and azurite inclusions) resulted in a product containing covellite, chalcocite and digenite in proportions depending on conditions of sulfidization. Reacting cassiterite with gaseous sulfur, H2S or pyrite at various reaction temperatures resulted in its partial conversion to a tin sulfide. Flotation of the products of sulfidization indicated that their behavior is similar to that of natural sulfide minerals, the recovery being a function of the con-version of the oxides to their respective sulfides. The gradual depletion of high-grade sulfide mineral deposits has turned the attention of the mineral industry to the recovery of metals from the oxides and silicates. Anionic (fatty acid) and cationic collectors have in some cases made flotation of nonsulfides possible, although, in general, flotation of oxide ores is not as yet an economic process. Consequently, many attempts have been made to sulfidize the surface of the relevant oxide mineral and thus make it amenable to to In recent years, Bautista and sollenberger4 have investigated the conversion of a number of oxides to sulfides by reacting them with molten sulfur. This paper presents the results of .investigations carried out at the School of Mineral and Metallurgical Engineering at the University of Minnesota to study the flotation characteristics of some sulfidized minerals. It is divided into two parts: The first describes the sulfidization of a number of oxides and a silicate, and the second presents the flotation behavior of the products of sulfidization. SULFIDIZATION OF METAL OXIDES AND SILICATES Experimental Procedure: SULFIDIZATION WITH HYDROGEN SULFIDE GAS — Sulfidization with H2S gas was carried out in a horizontal tube furnace (Fig. 1). The temperature of the furnace was regulated by means of a Variac and determined with a chromel-alumel thermocouple. The constant temperature zone in the furnace was about 6 in. in length, and it was within this zone that the experiments were carried out. The gases employed were supplied from standard compressed gas cylinders, and passed through a glass-wool filtering tower before entering the Pyrex reaction tube. Gaseous products were bubbled through a water tower (used as a flow indicator) and excess H2S was burned off at the end of the outlet tube. Samples of reagents or minerals were placed in a 3-in. Alundum boat and inserted within the constant temperature zone of the furnace. Nitrogen gas (6 ppm O2 content) was passed through the tubes at room temperature to remove air in the tube, and continued to pass while the furnace was heating up. When the required temperature was reached, H2S was allowed to enter the tube and the supply of nitrogen was shut off. At the end of the reaction period, the reverse procedure was carried out, the samples being cooled to room temperature in a nitrogen atmosphere. The flow rate of H2S gas was maintained fairly constant in all experiments, although the rate was not determined. SULFIDIZATION WITH SULFUR POWDER - To study the sulfidization of minerals with sulfur (liquid or gaseous), samples of the mineral, together with a measured quantity of sulfur powder, were placed in a stainless steel (SS316) reaction vessel (Fig. 2). The reaction vessel was heated in a vertical resistance coil furnace, the temperature being regulated through a Variac. At the end of the experiment the vessel was cooled to room temperature before the sample was removed. Cooled products were leached with CS2 to remove any free sulfur. SULFIDIZATION OF TIN CONCENTRATES - Fifty gram samples of sulfidized tin ore were prepared by mixing -48 mesh Bolivian tin concentrate with -48 mesh Ottawa sand in various proportions and sulfi-dizing these samples with H2S in the horizontal tube

Jan 1, 1969

By A. C. Freeze

The first use of electric punched card accounting machines as an aid in calculating reserves at the Sullivan mine in Kimberly, B.C., was made in January, 1948. At that time their use was limited to totalling individual reserve blocks for the various reserve classes and for calculating total metal content. The immediate objective was to increase speed, improve accuracy, and to effect some savings in labor that could be employed more usefully elsewhere. It was recognized also that the potential for achieving even greater advantages was excellent. The initial experiment proved so successful that it was inevitable that the use of the method would expand. Thus, for the past nine years assay data from core hole and development headings have been processed by these machines and the results integrated with the program of calculating reserves. It was also learned that the machines could store and classify a large amount of other information concerning the mining characteristics of each reserve block in addition to tonnage and metal content. This has proven very useful for the preparation of monthly production reports as well as in long term planning, in forecasting production schedules, and in analysing the results achieved.

Jan 4, 1961

By Charles E. Nelson

THIS paper will outline briefly the practices commonly followed in this country for the melting and refining of magnesium and its alloys. The processes used for the various forms of primary magnesium, as jar as there are differences in the physical shape or behavior, will be discussed. The refining of general fine scrap or secondary magnesium was presented in an earlier paper and will be discussed briefly.1 Inasmuch as the use of fluxes is an essential part of all the melting and refining processes, this paper will deal with these in sufficient detail to point out their unique characteristics, in order to make their use more effective. The outline of this discussion will closely follow that of an earlier paper,2 with such changes and additions as seem necessary to bring it up to date. TYPES OF MELTING PRACTICE All melting and refining processes for magnesium and its alloys require the use of fluxes. These fluxes have a magnesium chloride base and other halide salts or oxides are added to give a density or behavior exactly suited to the particular melting practice. The successful handling of magnesium depends upon the proper use of the correct fluxes. There are four general methods of melting, summarized in the following paragraphs and treated in more detail in the section on Melting and Refining. Open-pot Method The open-pot method makes use of No. 230 flux, which provides protection during melting and a molten pool of flux into which the solid magnesium melts. The flux is stirred through the molten metal bath and agglomerates oxide or similar foreign bodies;, on quiet standing, it separates away, leaving the refined metal ball floating in an encircling layer of molten flux. It forms only a thin fluid film over the surface of the molten metal, which may be parted for hand-ladling processes and tends to cover the metal again after the ladle is removed. A very light dusting of the pot surface with fresh flux immediately after the ladle is removed is desirable. The open-pot method is used generally in the following processes: (I) alloying and remelting in the production of ingot, (2) in sand foundries for premelting and to a smaller extent for the production of small castings, (3) in permanent-mold founding for premelting and also direct ladling to castings, (4) for continuous methods of preparing metal in the production of billets or ingots from which wrought products are fabricated, (5) in general scrap recovery. Crucible Process The crucible process makes use of No. 310 flux, which has the property of being thinly fluid at the start, to provide protection and refining qualities, and then drys out or thickens after a time, leaving a protecting crust on the pot surface until the time of casting. At that time it can be readily skimmed off or held back, thus allowing the contents of the crucible to

Jan 1, 1946

For the year ending February, 1936 PRESIDENT AND DIRECTOR HENRY A. BUEHLER ROLLA, Mo. PAST PRESIDENTS AND DIRECTORS FREDERICK M. BECKET NEW YORK, N.Y. HOWARD N. EAVENSON PITTSBURGH, PA. VICE-PRESIDENT, TREASURER AND DIRECTOR KARL EILERS NEW YORK, N. Y.

Jan 1, 1934

By Roy Lindgren

SINCE the year 1643, when the first blast furnace in America for treating iron ore was built at Saugus, Mass., out of mica schist quarried in the neighboring district, the procurement of a suitable refractory for furnace lining has been a problem of concern to the operators of furnaces. The stacks built of mica schist continued to smelt iron ore until about 1836, when, according to F. H. Norton, the first firebrick were produced1, at Queens Run, Pa. Other writers speak of brick having been molded and burned in Massachusetts about the year 1834. In 1841, Andrew Russell began to produce medium refractory plastic clay brick near East Liverpool, Ohio, that were used for lining blast furnaces1. The well-known Kentucky clay-producing district was not opened up until the year 1871, but since then it has produced a large percentage of the linings for iron blast furnaces. While some strides have been made by the refractories industry during the 100 years that have passed since the first firebrick were produced, it has been only during the last two decades that any real progress has been made towards bettering the product, even though the method of production had improved. Perhaps the fault lies with the user of the brick rather than with the producer, for not sooner demanding a supe-rior product. During the past 15 years the tonnage produced per lining has increased from 500,000 gross tons to 1,000,000 gross tons, and now some furnaces are producing 1,600,000 gross tons and better on a single lining. It is true that enlarged capacity of furnaces and improved practice have accounted for some of this increase in tonnage, nevertheless better quality in firebrick must be given credit for its share. However, we are not yet ready to say that we have reached a maximum life of furnace lining. We believe that a better product can be produced and that the refractories industries of America will, through their extensive research depart-

Jan 1, 1937

The Mining Journal Annual Review. The Mining Journal, London. $1.00, 200 pp., 1952.-Contains 70 specially contributed articles reporting on events in the metalliferous mining industry throughout the world during 1951. The articles are written from the standpoints of: Economics, world mining fields, progress reports on Empire mining companies, and British mining taxation. The review has appeared for a period of 20 years. Technical developments in mining, ore treatment, refining, and metallurgy are covered. Dun & Bradstreet Reference Book. Dun & Bradstreet Inc. 4000 pp., 1952. -Changes, brought about by the expanding economy, have been made for the three million listings for the United States and Canada. Planning for the changes started more than 10 years ago. New listings have been included for the metals and mining industries on all levels. The rapid development and specialization of industry have made the old symbols used in previous editions outmoded and a new system is substituted. Atlas of World Mineral Resources, . Edited by William Van Royen and Dr. Oliver Bowles. Prentice-Hall Inc. $10.75, 180 pp., 1952.-Scheduled for publication this fall, the book contains information that has never been published in map form before, as well as much that has not been presented in map form for many years. Facts on 29 minerals most important in world trade are dealt with, along with interpretation of all data available on each mineral, discussion of the world's mineral economy from viewpoint of specific minerals related to mineral exploration, geographical distribution of world's consumption, and appraisal of the adequacy of world's mineral resources.

Jan 1, 1952

By P. Chiotti, J. T. Mason

Metallographic, thermal, X-ray, and vapor-pressure data were employed in establishing the Ce-Zn phase diagram. Nine compounds and three eutectics were observed. The eutectic compositions in weight percent zinc and temperatures are 10 pct and 495"C, 37 pct and 795°C, and 56 pct and 810°C. Three of the compounds, CeZn, CeZnn, and CeZne.5, melt congru-ently at 825°, 87.505°, and 980°C, respectively; the other six compounds, CeZns, CeZns.67, CeZn4.5, CeZn5.25, CeZn,, and CeZnll, decompose peritectically at 820°, 840°, 870°, 885", 960°, and 795"C, respectively. The compound CeZn5.25 is an AB5 type with a small range of composition which lies on the zinc-rich side of the 1 to 5 stoichiometry. Zinc vapor-pressure data obtained by the dewpoint method were employed in calczilating the thermodynamic properties of both the liquid alloys and solid compounds. The data for the A critical review of the information available on the Ce-Zn system up to 1960 has been given by K. Gschneidner, Jr.' Of particular interest is the work by J. schramm2 who investigated the region between 55 and 100 wt pct Zn and reported a CeZn,, compound which decomposes peritectically at 785"C, a CeZn, compound which melts congruently at 972"C, and five temperature horizontals at 79@, 817", 840", liquid alloys were fitted to the relation from which the relation was obtained by integration. In these relations F XS is the excess partial molal free energy, N is atom fraction, and the constants c and d have the values c = (-22,000 + 7.0T) and d = 6171,000 + 74.0T). Relations for the standard free energy of formation for the solid compounds were derived from the data. At 973°K the enthalpy in kilocalories per gram-atom z)aries from —11.3 for CeZnz to —8.21 for CeZn~l and the free energy in the same units varies from —7.1 joy CeZn, to -3.82 for CeZn11. and 942°C in the region between 55 and 75 wt pct Zn. No attempt was made to identify other features of the system. I. Johnson and R. yonko3 used a fused-salt cell to measure the electromotive force between pure cerium and an alloy consisting of zinc-rich liquid in equilibrium with CeZnll. Solubility data for cerium in zinc has been reported by J. Knighton et u1 .4 Johnson and Yonko give the following equa-. tions for the mole fraction of cerium in zinc and the standard free energy of formation of CeZnll:

Jan 1, 1965

By S. F. Shaw

The Seminole field was first drilled in 1913. During the next 10 years other attempts were made to discover oil in this field, but without encouragement until March, 1926, when the Indian Territory Illuminating Oil Co. completed NO. 1 Dyer in the Hunton lime for 1100 bbl. On July 16, 1926, the Independent-Garland interests discovered oil in the Wilcox formation when No. 1 T. Fixico came in at 4055 ft. and on Sept. 9, 1926, production reached a peak of 8040 bbl. On Aug. 1, 1927, the daily production of the pools making up the Seminole district amounted to slightly over 500,000 bbl., practically all of which was coming from the Wilcox formation. The Hunton formation has not been very productive of oil, but has maintained a fairly high gas pressure; this formation has been encountered at from 3800 to 4200 ft., below which there is about 100 ft. of Sylvan shale. The shale is underlain by 75 ft. of Viola limestone in a few places in which formation oil has been encountered. Below the Viola lies the upper Simpson formation in which is found the Wilcox sand. The depth of the Wilcox in the Seminole field varies from 3900 to 4500 ft., and initial production has reached as much as 12,000 bbl. The gravity of the oil is about 41° Be. The general practice is to set 6 5/8 -in. casing above the Wilcox and drill in, though in several cases 5 3/16-in. casing has been set for the oil string, and in a few instances, casing as small as 4 3/4 in. has been employed. Production Statistics Production for the Seminole district for the various months since its discovery is shown in Table 1.

Jan 1, 1928

By G. H. Lair, B. J. Langford, S. H. Rockwood

Volumetric reservoir analysis is dependent upon a firm relationship between porosity, connate water, and net pay. Capillary presswe data on core samples interrelate these three factors. It is shown that other reservoir problems may be resolved: (I) whether water production is indigenous or extraneous to the oil producing interval, (2) an oil-water contact is being approached, and (3) whether the oil-water contact is remotely situated. INTRODUCTION Volumetric analysis of carbonate reservoirs challenges the ingenuity of the reservoir engineer due to an absence of data on the minimum oil-bearing and oil-producing pores of a given reservoir rock. Many studies with this as the ultimate objective are available on the physical characteristics and fluid-flow behaviors of the carbonate reservoir. Some of these publications are: Hassler, Brunner and Deahl's1 study of the role of capillarity in oil production; Jan Law's' and A. C. Bulnes3 statistical treatment of core analysis data; Chalkley's method4,5 or estimating specific surface areas and porosity; Walter Rose's9 report on porosity, reserves, and recovery; Archie's78 tex-tural classification of carbonate rocks; Stewart and Spurlock's9 large core analysis; Purcell'sl0 mercury injection method in studying capillary pressure phenomena; Stewart, Craig, and Morse's" model multiple-phase flow test in investigating the relative permeability effect; and Fatt's12 illumi-nating network model of porous me-dia. The present study shows that the static reservoir parameters of porosity, connate water, and net productive thickness may be interrelated by utilizing a statistical arrangement of mercury capillary pressure data in addition to routine core analysis. This report summarizes the techniques that are followed to obtain these relations which are applicable to carbonate and sandstone reservoirs that do not contain clays. Capillary pressure statistical studies may be extended to include clay-bearing rocks by utilizing water capillary pressure data. POROSITY It is necessary that the laboratory determine the porosity value that includes the pores that are filled with hydrocarbons and water in the reservoir. This is the reservoir's total porosity. When true total porosity values are not available, correlations between porosity and capillary pressure characteristics lose their significance since they cannot be related through oil-base mud core data to the porosity and connate water values found in reservoirs. Methods used to obtain reliable porosity data will not be discussed; however, care should be exercised in selecting samples for measurement. In homogeneously porous formations, small core plugs sampled frequently will furnish adequate information. Where heterogeneity, particularly vugginess, is present, large-core porosity data may be required; in such reservoirs a suite of capillary pressure samples may be selected from small plugs. CAPILLARY PRESSURE Capillary pressure data provide a method for relating two carbonate reservoir parameters, porosity and connate water saturation, which in turn permit delineation of productive rock types necessary for selecting the third parameter, productive thickness. Specific applications of capillary pressure data to petroleum reservoirs were suggested by Archie8 and Pur-cell."' Their work demonstrated that in preferentially water-wet rock, porc

Jan 1, 1958

By E. Maxwell, C. J. Bechtoldt, H. C. Vacher

IN the course of an investigation of the properties of metals at low temperature there was occasion to determine the constitution of four iridium-osmium alloys. There is very little information in the literature1 on the constitution of synthetic Ir-0s alloys. Zvyagintzev' s has made a comprehensive study of different natural Ir-0s alloys and concludes that alloys containing more than 32 pct 0s have the close-packed hexagonal structure of osmium, whereas those containing less than 32 pct 0s have the face-centered cubic structure of iridium. The alloys studied in this work were prepared by the American Platinum Works, Newark, N. J., and were received in the form of fragments approximately 1.5 mm average diameter. The fragments had been obtained by crushing ingots made by fusing charges of iridium and osmium under an arc and air cooling. The ingots were not given a homogenizing heat treatment. Sample fragments Table I. Results of X-Roy Diffraction and Microscopic Examinations Phases Present as Determined by X-ray Diffraction Osmium Alloy Close- Iridium Face- Packed Centered Osmium, Iridium, Hexagonal Cubic Mlcro- WtPot Wt Pct Structure Structure scope 0 99.9 None Present 1 23.6 76.4 None Present 1 38.7 61.3 Present Present 2 59.4 40.6 Present Present 2 79.0 21.0 Present Not detected 2 99.9 0 Present None 1 Note: Chemical analyses of the iridium, osmium, and alloys were furnished by the American Platinum Works. of the iridium and osmium used in making the alloys also were included. Several fragments of each metal and alloy were examined microscopically and by X-ray diffraction. For the X-ray method the fragments were crushed further to pass a 270-mesh screen, then sealed in evacuated fused-silica tubes, heated to 1100°C for 18 hr, and allowed to cool in the furnace. Powder X-ray diffraction patterns were obtained from the annealed fragments by means of a Norelco camera having a diameter of 114 mm, and unfiltered cobaIt radiation. For the microscopic examination several fragments in the as-received condition were mounted in Melmac, (American Cyanamid Co.) and ground using the conventional series of abrasive papers. The polishing was done with 0-2 diamond abrasive on a Microcloth (Buehler Ltd.) lap, wet with xylene. After polishing, the surface was etched electrolytically in a 10 pct solution of chromic acid or in a 10 pct solution of potassium cyanide. Both reagents attacked the osmium-rich constituent, whereas the iridium constituent was attacked slightly by the chromic acid reagent and not noticeably by the potassium cyanide reagent. The results of the X-ray diffraction and microscopic examinations are summarized in Table I. Fig. 1 shows the microstructure of a 21 pct Ir-79 pct 0s alloy. The results indicate an appreciable solid-solu-bility range of osmium in iridium as was reported by Zvyagintzev.' The solid-solubility range of iridium in osmium is more restricted, apparently less than 21 pct Ir. This implies a large range of composition in which two phases can coexist that was not reported by Zvyagintzev.

Jan 1, 1955

By Roger A. Gregg, Barry J. Piearcey

MANY of the nickel-base superalloys developed recently for use in the as-cast condition exhibit a massive "white-etching" constituent1 in the inter-dendritic regions. Commercial alloys in this category are SM 200,* IN 100, INCO 713, and Nicrotung. The appearance of a similar microconstituent in nickel-rich Ni-A1-B alloys has been reported by Schijbel and Stadelmaier. Their investigation revealed that this constituent was the binary eutectic of the terminal nickel-base solid solution and the inter metallic based on Ni3A1. This binary eutectic is degenerate and NhA1 is the major phase. At lower temperatures the eutectic composition lies within the NkA1 phase field and under equilibrium conditions is single-phase NisAl. Taylor and F&apos;loyd3 have shown that in Ni-Al-Cr alloys containing at least 8 at. pct Cr, liquid compositions which solidify by the eutectic reaction in the nickel-rich portion, precipitate nickel-base solid solution and NiAl rather than nickel-base solid solution and NkA1 in the binary Ni-A1 system. Since the nickel-base alloys contain chromium in excess of 8 at. pct and are further alloyed with one or more of the elements titanium, cobalt, molybdenum, or tungsten, it is possible that the eutectic could contain NiAl rather than NisAl. In addition, Benson4 has reported that in low-nickel austenitic high-temperature alloys, which possess Ni/(Al + Ti) atomic-weight ratios <18.0, the Ni (Al, Ti) phase may precipitate from the melt during solidification. Since SM 200 and similar high-temperature materials were developed from alloys which were designed for solution treatment, the appearance of a eutectic would indicate that the limit of solid solubility has been exceeded. The purpose of this note is to confirm that the massive white constituent in the complex nickel-base alloys investigated is based on the binary eutectic Ni + NbAl and that the limit of solid solubility need not be exceeded to produce it, in common with other observations of cast alloys. Successive polishing of a sample of SM 200 showed that, in agreement with Schobel and Stadelmaier, particles of the constituent were spherulitic and in particular were a) situated between cored dendrite arms, Fig. 1, and b) nucleated at the surface of dendrites, Fig. 2. The Ni/(Al + Ti) atomic-weight ratios for the nickel-base alloys which were observed to contain the massive eutectic constituent in the interdendritic regions are 12.1 (Nicrotung), 9.2 (IN loo), 19.5 (INCO 713), and 14.5 (SM 200). However, the results of X-ray analysis of these alloys in the as-cast condition failed to reveal the presence of the Ni (Al, Ti) phase. An electron microanalyzer was therefore employed to analyze the composition of this constituent in SM 200. The results of analyses of representative particles are as follows5: 8.4 at. pct Ti, 8.8 at. pct Co, 5.5 at. pct Cr, 0.9 at. pct W, 12.8 at. pct Al, and 63.6 at. pct Ni. Assuming that

Jan 1, 1964