Search Documents

By Berlen Moneymaker

THE development, within recent years, of core drills capable of drilling holes up to 72 in., or even more, in diameter, has made possible an entirely new and valuable method of geologic exploration, Although little used until recently as an exploratory tool except in the United States, by the Tennessee Valley Authority and the Corps of Engineers of the U. S. Army, for the exploration of damsites, the large-diameter core drill may be used to good advantage in other types of geologic exploration. Its princi-pal utility is that of supplementing, rather than replacing, other means of exploration. Although core is frequently recovered intact, the greatest advantage of large-diameter drilling is that the holes produced are large enough to be entered by the geologist and engineer, and thus afford an excellent means of examining undisturbed rock. The walls of the holes are smoothly cut, and in some rocks nearly or quite polished, so that the most minute details of structure and stratigraphy are clearly disclosed. Such features as faults, joints, bedding planes, weathered "seams," and beds or layers of soft materials, which are not always amenable to disclosure by cores recovered from small-diameter holes, are conspicuously displayed in the walls of large holes. Frequent reference to the drilling of large-diameter holes is made in engineering literature, but comparatively little emphasis has been placed on their value in geologic investigation. It is, therefore, intended that the present paper acquaint the geologist, as well as the engineer, with the large-diameter core drill and the technique involved in its use, and also with its advantages, disadvantages and limitations as an implement of geologic exploration.

Jan 1, 1938

By Richard A. Brown

The direct precipitation of uranium with hydrogen peroxide has been known since 1877. Commercial use of the process began in the 1960s. During 1967 the US Bureau of Mines (USBM) assisted the Climax Uranium Co., Grand Junction, CO in the development of a uranyl peroxide precipitation process to control a molybdenum impurity problem (Shabbir and Tame, 1978). Atlas Minerals, Moab, UT has used hydrogen peroxide to control vanadium and sodium levels in uranium concentrates since 1969 (Caropresso and Badger, 1973). Recently, the use of hydrogen peroxide by the uranium industry has grown, particularly since the increased demand for uranium has led to the processing of low grade ores. Impurities present in low-grade ores can be concentrated with the uranium during milling and will substantially complicate the refining of uranium yellowcake concentrates. Consequently, commercial nuclear fuel processors have imposed stringent specifications and penalties to control these impurities. The ability to produce a pure uranium yellowcake can eliminate penalty or reprocessing costs. Hydrogen peroxide precipitation of uranium is specific and quantitative, producing a very high purity product. Although the hydrogen peroxide precipitation of uranium has, and continues to be used primarily as means of producing a high purity yellowcake, it has also become an important process due to the superior physical properties of the precipitate. Under normal operating conditions, the precipitate produced by the reaction of hydrogen peroxide and uranium is dense, easily filtered and dried. The final dry yellowcake is pure, high U308 assay product. Consequently, processing costs such as filtering, drying and/or calcining and drumming, can be reduced compared to ammonia, caustic or Mag-Ox precipitation.

Jan 1, 1982

By George B. Lee

During the two years in which the new reduction-works of the Copper Queen Consolidated Mining Co. have been in operation at Douglas, Ariz., there has developed a remarkable condition in regard to the corrosive action of the water used to cool the jackets of the blast-furnaces. Were it not for the many contradictory features, it might pass as one of the unavoidable troubles due to the composition of the water. This water, obtained from wells 600 ft. deep, is also used in the steam-boilers, and its composition, as shown by the following analysis, does not indicate the presence of any ingredient which would explain the corrosion: Grains Per U. S. Gal. Silica,...........0.861 Iron oxide and alumina,....... 0.223 Calcium carbonate,....... 0.261 Calcium sulphate,................. Magnesium carbonate,........... Sodium and potassium sulphates,..14.850 Sodium and potassium chlorides,.9.732 Sodium and potassium carbonate, . 6.482 32.409 The jackets are made of inner plates 0.5 in. thick and an outer plate # in. thick, with 3/8-in. stiffeners between the inner and outer plates. In from 10 to 12 months the inner plates have been reduced by corrosion to a thickness of from + to & in., while the outer plate in the same time is reduced by less than 1/16 in., and the stiffeners show very little corrosion. The plates are pitted and eaten away in some places more than in others. There is practically no scale found on the jackets, but when cleaned considerable iron oxide is found in the bottoms. With an action so marked, serious trouble would be expected in the boilers, but, on the contrary, a recent inspection by a

Jan 1, 1908

By R. Lagneborg

WhEN mechanical twins initiate cracking it has been proposed1 that the friction stress for dislocation motion, in the Cottrell criterion for brittle fracture2 should be replaced by the stress required to propagate a twin, ttp. TF is the fracture stress, d the grain diameter, ß a geometric constant, u shear modulus, and y the effective surface energy. Since TTp is likely to vary with grain size, it cannot be substituted by a constant in Eq. [I]. If an expression for the energy change caused by a twin in a stressed material could be obtained, it is in principle possible to compute the critical size of the twin, i.e., the size at which the system can decrease its energy spontaneously, as a function of applied stress, thus giving the stress required to just barely propagate the twin, i.e., TTP. Consider a circular twin disc with a radius r and having a lenticular cross section, Fig. 1. Twin dislocations3 of strength b exist in the twin boundary parallel to the twin plane, one loop on each atomic plane. Assume that the total numbers of loops, n, can be replaced by one circular loop of a multiple dislocation, nb with a radius r. The energy change of the system, AW, due to such a twin in an applied stress field can then be calculated: The first term is the total twin surface energy, the second the elastic energy due to the twin dislocations, and the third the energy released by the twin in the applied stress field. yt is the twin boundary energy, r, the radius of the dislocation core, and T the applied

Jan 1, 1968

By Robert M. Yerkes

The following is a brief account of the methods of measuring intelligence especially prepared for use in the U. S. Army, of typical results, and of some of their immediately practical applications. It has been prepared for the assistance of army examiners and for the information of all who are interested in the relations of scientific placement to military efficiency. Purpose of the Intelligence Tests Under the direction of the Division of Psychology, Medical Department, and in accordance with provisions of War Department General Order No. 74, mental tests are given recruits during the 2-wk. detention period. These tests provide an immediate and reasonably dependable classification of the men according to general intelligence. Their specific purposes are to aid: 1. In the discovery of men whose superior intelligence suggests their consideration for advancement; 2. In the prompt selection and assignment to development battalions of men who are so inferior mentally that they are suited only for selected assignments; 3. In forming organizations of uniform mental strength where such uniformity is desired; 4. In forming organizations of superior mental strength where such superiority is demanded by the nature of the work to be performed; 5. In selecting suitable men for various army duties or for special training in colleges or technical schools; 6. In the early formation of training groups within regiment' or battery in order that each man may receive instruction and drill according to his ability to profit thereby; 7. In the early recognition of the mentally slow as contrasted with the stubborn or disobedient; 8. In the discovery of men whose low-grade intelligence renders them either a burden or a menace to the service.

Jan 1, 1919

By Will H. Coghill, Fred D. DeVaney

THE coercimeter, as its name implies, is an instrument for measuring the coercive force[+] of magnetic substances. It was developed by Davis and Hartenheim in the Special Studies Section, Metallurgical Division. A detailed description of this apparatus may be found elsewhere.2 The coercive force determinations of magnetic materials are interesting because of the relationship established by Gottschalk,4 who showed a linear relationship between the magnetization coercive force and the specific surface of comminuted particles. The value of this relationship in determining grinding efficiency has been shown by Dean.3 The determination of the surface contained in the subsieve sizes has always been a difficult problem for investigators. They made approximate measurements of the surface of coarse materials by sizing on screens, but for the determination of the surface of the sub- sieve sizes it was necessary to make detailed grain counts or elutriation tests, or to study dissolution rates. The technical literature contains many references to other methods for determining these surfaces, either by some special apparatus or by mathematical calculations based on distribution lines. Many of the methods are long and tedious, and the results of some, at least, are questionable. The turbidimeter gives quick results on ground cement. By using magnetite as the material to be ground, a simple determination of its coercive force by the coercimeter, requiring 10 minutes or less, can be transposed directly and accurately into units of relative surface. This subject has been pursued further by the U. S. Bureau of Mines in cooperation with the Missouri School of Mines and Metallurgy, Rolla, Mo., and the following is a description of the results.

Jan 1, 1938

THE following employment items are made available to AWE a non-profit basis by the Engineering Societies Personnel Service, Inc., operating in cooperation with the Four Founder Societies. Local offices of the Personnel Service are at 8 W. 40th St., New York 18; 100 Farnsworth Ave., Detroit; 57 Post St., San Francisco; 84 E. Randolph St., Chicago 1. Applicants should address. all mail to the proper key numbers in care of the New York Office and include 6c in stamps for forwarding and returning application. The applicant agrees, if placed in a position by means of the Service, to pay the placement fee listed by the Service. AIME members may secure a weekly bulletin of, positions available for $3.50 a quarter, $12 a year. MEN AVAILABLE Executive Engineer, Mining Engineer Graduate, 25 years' management experience from plant operation to vice president in charge of manufacturing for national concern. Management and operational experience in gypsum, asbestos, cement, paper, felt, asphalt products. West Coast or South location preferred. Prefer permanent position but would consider connection on consulting basis. M-663. Geologist and Engineer, E.M. (Geol.), Ph.D., 46, married, excellent health. Nineteen years' broad experience including appraisal, acquisition, large-scale exploration, special problems, planning, organization, and supervision in U.S., Africa, and South America. Sound approach and execution, writes clearly. Currently employed but available short notice. M-660. Mining Plant Designer. Over thirty years' broad mining experience. Graduate mining engineer, registered mechanical engineer, experienced structural engineer. Member AIME, NSPE. Fully experienced all phases design, from initial plant layout to final details. Excellent references. Presently employed but available reasonable notice. M-661-238-Chicago.

Jan 1, 1952

By Frank Foote, Willard L. Bruner, Eric R. Jette, Y. New york

The alloys of gold and iron were investigated in 1907 by Isaac and Tammann,l who determined the thermal diagram for the entire system by thermal analysis and microscopic examination. They also reviewed the previous literature. Since that time the present authors have been able to find only two additional references. Guertler and Schulze2 examined the electrical resistance of iron alloys containing up to 40 per cent by weight of gold between 0" and 200" C.; the alloys were in the form of wires. The main result of this work was to confirm the solid solubility limit found by Isaac and Tammann; namely, about 20 per cent Au. More recently, Shih3 has examined the magnetic properties of gold alloys containing up to 10 weight per cent iron and particularly the range below 5 per cent. The alloys in the lower range were found to be paramagnetic; the 10 per cent alloy was ferromagnetic. The present investigation was undertaken to determine the solid solubility limits at various temperatures, particularly below the a-y transformation point of iron, since these solubilities are of some importance in connection with the working of the alloys in the manufacture of certain "grey" and "blue" golds. Materials and Methods The gold was obtained from the U. S. Metals Refining Co. and contained 99.99+ per cent Au. The electrolytic iron had been annealed in hydrogen and contained impurities as follows: P, 0.035; Si, 0.001; S, C, Mn, Cu, each 0.01 per cent. Weighed quantities of the two metals were placed in small crucibles lined with pure sintered MgO; a saturated solution of magnesium nitrate

Jan 1, 1934

By C. E. Wood, T. L. Joseph

This paper is a brief report of experimental work undertaken determine whether barium oxide in any quantity increases the desulfur ing action of blast-furnace slags. Industrial furnace operation wi slag containing small quantities of barium oxide, referred to later, intc ested S. A. Sanford of the Commercial Chemical Co., Youngstown, Oh to conduct experiments to furnish comparative results on desulfurizati with normal slag and slag containing small quantities of barium oxic The U. S. Bureau of Mines agreed to assist on the problem because the possible saving in fuel if the desulfurizing action of blast-furna slag can be substantially increased, also because the experiments woi yield new information on sulfur elimination in general, a matter economic importance in furnace practice. A more complete and func mental study of desulfurization of iron by slag is in progress. Distribution of Sulfur iN the Blast Furnace More than 90 per cent. of the total sulfur entering the blast furnz is in the coke. Sponge iron formed by reduction of iron oxides absor part of the sulfur as ferrous sulfide. Kinney's examination of sample taken from various levels of a 3004,011 furnace, shows that the me continues to take up sulfur until it reaches a level near the tuyer Desulfurization must therefore take place as the metal falls through t slag and as the slag and metal exist as layers in the crucible. The relative amounts of sulfur removed while the metal falls throu the slag and while the slag and metal exist as layers in t crucible are not definitely known. Preliminary experiments by t

Jan 1, 1929

By T. Rosenqvist

From the chemical, metallurgical, and mineralogical points of view, the importance of thermodynamic data for metal-sulphides and sulphur dissolved in molten metal has long been realized. Such data will give a basis for thermo-dynamic calculations of processes such as roasting and the distribution of sulphur between molten metal and slags. Furthermore, it will help us understand the chemical forces which tie sulphur to the metal and to the melt. Thermodynamic studies of solid sulphides and the equilibria between solid sulphides and metals have been carried out in a rather large number of cases by several investigators. An excellent review of this work is given by Kelley.1 On the other hand, very little is known about the thermodynamic properties of molten sulphides and of sulphur dissolved in molten metal. The only system which previously has been investigated in this respect is the iron/sulphur system. The purpose of the present investigation was primarily to obtain further data for metalisulphur melts and the system silver/sulphur was chosen, not because this system was expected to be of special interest in itself, but because the silver/sulphur system is a typical example of a metal/sulphur system. Because of the low melting temperatures, the work could be carried out without appreciable furnace and refractory difficulties. The sulphur in this system possesses a rather high escaping tendency compared to most other metal/sulphur systems. By the method employed (reaction with hydrogen to form hydrogen sulphide) this gives ratios Ph2s/Ph2 up to 0.30, which may be determined accurately. 'rhermodynamic investigations of the heterogeneous reaction Ag2S +H2 —+ 2Ag + H2S have previously been carried out by Pelabon,2 Keyes and Felsing,3 Jellineb and Zakowski,4 Wat-anabe,6 and Britzke and Kapustinsky.6 Their results are in rather poor agreement. Experimental Part PRINCIPLE In the present invehgation the escaping tendency of sulphur from the condensed phase was determined by the reaction: S + H2 = H2S The ratio Ph2s/Ph2 is at constant temperature, directly proportional to the escaping tendency of sulphur and to its chemical activity in the condensed phase. (This ratio will subsequently be denoted by H2S/H2.) From this ratio and its variation with temperature and with change in the com- position of the condensed phase, thermodyrlamic quantities such as free energy and heat of reaction can be derived. The apparatus used is shown in Fig 1. The silver/sulphur alloy was placed in a crucible inside a refractory tube and mounted inside the furnace to the left. The tube was a part of a closed, gas-tight system in which the gas mixture could circulate until equilibrium was established. Circulation was maintained by the glass propeller to the right, driven by an external magnet, and promoted by the chimney action of the furnace. The gas passed up through the furnace, down into the crucible where it came in contact with the alloy, passed rapidly up through a narrow tube and out of the hot zone. After equilibrium was established between the gas and the condensed phase, the composition of the gas mixture was determined from its density. In its circulation, the gas mixture passed through a chamber (lower right on Fig 1) containing a buoyancy-balance, where the density of the gas was determined by magnetic balancing. From the measured density,

Jan 1, 1950

By John Riegle

To date. utility company underground storage of gas has generally been restricted to depleted dry gas fields. The Playa del Rey project is probably the first to successfully store gas in a partially depleted oil reservoir with the recovery of large volumes of pas at high rates as the main objective. Oil recovery has been a secondary consideration. Problems encountered unusual to those of storage in a dry gas zone were: (1) the removal and retardation of formation of emulsion. (2) the upstructure movement of fluid during withdrawal periods which formed fluid blocks, and (3) reservoir shrinkage resulting from encroachment of edgewater. The solution of these problems as outlined in the paper has resulted in increasing the withdrawal rate from the original design capacity of 4,000 Mcf per hour to the current 10.000 Mcf per hour. Additional increase is anticipated as the operations continue. Migration. reservoir performance. operational procedure and a historical record are included to make this a resume of the project from its war-time inception in 1942 to the first of 1952. INTRODUCTION The Playa del Rey underground gas storage project is probably the first project in which gas has been stored in a partially depleted oil reservoir, with the recovery of large volumes of gas at high rates as the main objective and the recovery of oil a secondary consideration. Problems unusual to those of storage in dry gas zones have made this a pioneer endeavor. The total storage capacity of approximately 1,500,000 Mcf of this reservoir is small in comparison with other underground gas storage projects. However. by study and experiment the deliverability into transmission lines. operating at pressures in excess of 150 lbs., has been nearly tripled in the past three years. to the current 10.000 Mcf per hour late, without the use of compression. It is anticipated this rate will gradually increase as additional fluid is removed from the formation. LOCATION AND HISTORY Playa del Key is located on Santa Monica Bay about two miles south of the beach commuity of Venice and 15 miles southwest of the renter of the City city Los Angeles. Fig. 1. The discovery well was completed at 6,194 ft in 1929. An upper zone at 3,905 ft was found on June 18. 1930. Townlot development was very rapid and by the end of 1930 there were 141 producing wells in the field. The Union Oil Co. completed a lower zone well south of the Townlot Field in May, 1931, which was believed to be an extension, until additional drilling of about 50 wells during 1934 and 1935 indicated this area to be a separate accumulation as shown on Fig. 2. The lower oil horizon, which is now the storage zone, had no original gas cap and is believed to be a continental detrital deposit of conglomerate that accumulated in valleys and depressions of a weathered schist high. which later subsided and was overlain by an impervious nodular shale. This type of formation has rapid variation of porosity. permeability and thickness due to lack of sorting action common to marine deposition. and the uneven surface of the original schist high. Production was limited on the upstructure sides by the pinching out of the conglomerate, and downstructure by edgewater. Unrestricted production, together with high permeabilities, led to large wastage of gas from this new area as facilities were not available for transport of gas to market. The decline was very rapid and by 1942 the portion of the new area south of Ballona Creek was nearly depleted. ACQUISITION OF PROPERTY The rapid increase in industrialization of Southern California during World war 11 forced upon the local gas com-

Jan 1, 1953

By Cyril Stanley Smith

Jan 1, 1949

By Cyril Stanley Smith

Jan 1, 1949

By James Douglas

Discussion of the paper of James Douglas, presented at the New Haven meeting, February, 1909, and published in Bulletin No. 29, May, 1909, pp. 439 to 451. JAMES DOUGLAS, New York, N. Y. (communication to the Secretary*) :-In my paper on the Conservation of Natural Resources, I referred to the slow replacement of bee-hive ovens by the by-product ovens as a most notable instance of waste. And I quoted from Mr. Parker's report for .1906 an explanation given by him in accounting for the small production of by-product coke. It was that the markets for the by-products of the coke-ovens was so limited that some of the ovens constructed were out of operation. His report on the manufacture of coke in 1908 1 does not record an improvement, and attributes the strange fact that we alone, of all the industrial peoples, delay the adoption of this cardinal improvement from the continuance of the same almost inexplicable cause. To quote again from his report, lie says (p. 241): "The year 1908 was not marked by any notable gain in the construction of by-product coking plants, though some new work was done. There was a net increase of 115 in the number of completed ovens in 1908 over 1907, the totals for the two years being, respectively, 3,892 and 4,007. The additional equipment consisted of 140 Koppers regenerative ovens built at Joliet, I11., by the United States Steel Corporation, but this increase was partly offset by the dismantling of Y5 Semet Solvay ovens at Sharon, Pa., the net gain being 115 ovens. Included in the total of 4,007 completed ovens in 1908 are 152 Newton-Chambers ovens at Vintondale, Pa., but as no recovery of by-products was made at this plant in 190S, the production of coke is included with that from beehive ovens. The 56 ovens of the same type at Pocahontas, Va., have not been in practical operation since they were first. installed. In addition to these there was one other by-product plant of 120 ovens. Oat. was not operated during the year. The number of retort ovens producing coke in 1908 was 3,679, as compared with 3,811 active ovens in 1907." In describing the anomaly he says (p. 249): It has been contended that the development of the by-product coking industry would have shown more rapid progress if markets for the by-products were * Received Feb. 2, 1910. Mineral Resources of the United States for 1908, Part I1., U. S. Geological Survey (1909).

Apr 1, 1910

By Henry R. Piehler

Continuous seven- and nine teen -filament close-packed silver-steel filamentary composites mere tested in tension. For purposes of comparison, the tensile behavior of the composite was predicted from the measured properties of the individual com-ponents. It was assumed that the axial strain is the same in both components and that the contribution of each component to the composite flow stress is proportional to its volume fraction. Good agreetnent was obtained between the observed and predicted tensile behavior. However, the composite elongation at fracture was about twice that observed when the individual steel wires were tested alone. Composites in which the filaments were widely spaced failed by the consecutive fracture of the filaments. In composites with closely spaced filaments, a composite instability preceded frachcre. These effects are explained in terms of a lateral restraint to the necking of the filaments which develops in the deforming composite. TWO-COMPONENT or composite materials are increasingly being developed and used as structural materials. Of all the composite geometries used, the filamentary configuration has proved to be the most successful. Polymer-bonded fiber-glas, the most common of the filamentary composites, has been investigated most extensively to date. One explanation of the behavior of fiberglas1 suggests that the load transfer between the glass fibers and the polymer matrix occurs primarily through friction. Bond separation between the fibers and the matrix is presumed to occur at very low stresses. Subsequently, only frictional bonding can provide for the transfer of load from the matrix to the fibers. The force normal to the fiber-matrix interface which gives rise to this friction is assumed to arise from the matrix shrinkage which occurs during solidification. The behavior of metallic filamentary-composite materials would be expected to differ from that of fiberglas in several significant aspects. Residual stresses resulting from differences in thermal contraction can be kept to a minimum by proper heat treatment. A strong wetted bond is formed between the two phases. In brazed joints,2 for example, the interphase bond is sufficiently strong that the weaker material will fail before separation occurs at the interface. Most metal filaments can undergo appreciable amounts of plastic deformation before failure. Failure by plastic instability or necking frequently occurs in metallic filaments, but not in glass fibers tested at room temperature. Differences between the behavior of fiberglas-polymer and metallic filamentary composites have indeed been observed in composites containing various types of metallic filaments in a silver matrix.3,4 At strains of the order of 10-2 pct, all the deformation was accommodated by the silver matrix. Hence, the strength of the composite depended only on the fiber concentration and not on the nature of the fiber. At higher strains, the strength of the composite increased when filaments with higher work-hardening rates were used. Surface slip line observations on a silver-mild steel composite that had been stretched 4 pct showed that an appreciable amount of deformation occurred in the filaments. Work on tungsten-copper filamentary composites5 has shown that the ultimate tensile strength for varying filament fractions followed a linear mixture rule. Assuming that the axial strains in both filaments and the matrix are equal, this linear mixture rule can be expressed as: The subscripts c, f, and m refer to the composite, filaments, and matrix, respectively. A and V are the area and volume fractions of each component. sc and of are the ultimate tensile strengths of the composite and the filaments. sm is the flow stress of matrix at a strain equal to the elongation at failure of the filaments. However, the tungsten filaments can undergo only a limited elongation before they fracture without an appreciable reduction in area. A composite containing more ductile filaments might indeed deviate from this linear mixture rule for the ultimate tensile strength, since filament failure by necking might be arrested by the matrix. SPECIMEN PREPARATION Specimens were prepared from 0.8 pct carbon steel piano wires of 0.015 in. initial diameter. The wires were given a thin nickel flash and a silver plate varying in thickness from 0.015 to 0.007 in., depending on the filament fraction desired. In order

Jan 1, 1965

By R. E. Ogilvie, J. I. Goldstein

The a and y solubility limits in the Fe-Ni phase diagram have been redetermined at temperatures above 500°C. Both a diffusion-couple and a quench and anneal technique were used. The solubility limits were measured with an electron-probe micro-analyzer. The nickel concentration at the phase boundary is increased below 700°C and the a solid-solubility range is much larger than had been previously measured. The solubility limits are also extrapolated to 300°C. It is suggested that the solubility of nickel in a FeNi reaches a maximum in the temperature interval 400o to 500°C. THE equilibrium diagram has been of great use in the field of meteoritics, where the phase relations between kamacite (a) and taenite (?) in metallic meteorites can be described by means of the Fe-Ni diagram. The study of metallic meteorites by electron-probe microanalysis has cast some doubt on the accuracy of the presently available Fe-Ni diagrams.1, 2 Recent thermodynamic studies of the Fe-Ni system also suggest that the diagram may be in error.3 For these reasons the high-temperature (800o to 500°C) part of the diagram was redetermined. INTRODUCTION The currently accepted Fe-Ni diagram is that of Owen and Liu.4 Above 910°C, there is a region of complete solid solubility, ? (fee). Below 910°C, the a (bee) phase is stable in pure iron. The effect of increasing amounts of nickel is to stabilize the y phase. The phases that form when Fe-Ni alloys are heated or cooled bear little relation to the equilibrium diagram. If an alloy is cooled from the y state and held at a temperature within the a + y field, no evidence has been found for the occurrence of the y - a transformation.5 If the alloy is cooled to low enough temperatures the y phase breaks down into a supersaturated bee phase called a2. In fact, in alloys over 27 pet Ni the y phase is retained at room temperature.6 The a, phase has the same composition as the original y. The temperature at which a2 forms, the M, temperature, has been determined experimentally.' A state of equilibrium can be approached by cooling below M, to form a2 and then reheating the alloy into the two-phase region of the diagram. The y phase will then begin to precipitate out of the a2 phase and grow. The growth of the phase, however, is quite slow. Using the interdiffusion coefficients -Da of Goldstein et al.,8 it is estimated that it takes about 1 year to grow a 10-µ-wide region of ? at 700°C in a 5 pet Ni alloy. Owen and Liu4 used the technique just described to form the equilibrium phases. The phases present were determined by means of X-ray analysis. The accuracy of their diagram depends on the number of alloys available near the phase boundary at a given temperature. In this study two different techniques were used to determine the a/a + ? and ?/a + ? solubility limits. The inherent accuracy of both techniques was greatly improved over that used by previous investigators because the phase-boundary compositions were measured with an electron-probe microanalyzer. PROCEDURE The two methods used to determine the Fe-Ni diagram are the diffusion couple (D.C.) and the quench-and-anneal (Q.+A.) techniques. In the first method, diffusion couples whose diffusion path goes through a two-phase region of the phase diagram were used. A description of the technique used for making the diffusion couples has been described in a previous paper.' After the diffusion treatment a discontinuity in the resultant concentration vs distance profile was measured. The nickel concentrations in the a and ? phases at the interface of the discontinuity are the solubility limits of the a and ? phases in the phase diagram at the diffusion temperature. If the interface com-

Jan 1, 1965

By Donald A. Brobst

The minerals barite (BaSO4 barium sulfate) and witherite (BaCO3 barium carbonate) are the chief commercial sources of the element barium and its compounds whose many uses are nearly hidden among the technical complexities of modern industrial processes and products. Barite, the major ore mineral, is extremely vital to the petroleum industry which in 1973 consumed at least 80% of the world's produc¬tion of 4.4 million tons as a major ingredient of the heavy fluid, called mud, that is circulated in rotary drilling of oil and gas wells. The re¬maining 20% of the barite production was consumed chiefly in the manufacture of barium chemicals and glass and as a pigment, filler, and extender. Barite occurs throughout much of the world and is available from three major geologic types of deposits-vein and cavity fill¬ing, residual, and bedded-in sufficient quantity at competitive prices to meet current demands. The world's demand for barite is expected to increase, and geologic circumstances are favor¬able for the discovery of new deposits of com¬mercial value. Witherite is much less common and abun¬dant than barite, although it is more desirable in many ways as a raw material for the pro¬duction of barium chemicals. The United States has not produced witherite since about 1950; England is currently the chief producer of witherite. End Uses Most of the world's barite production since 1926 has been used as a weighting agent for the muds circulated in rotary drilling of oil and gas wells. The muds fundamentally are mixtures of water, clay, and barite in different proportions that vary according to local reservoir condi¬tions. Muds with a specific gravity as great as 2.5 are used. The mud is pumped down the hollow drill stem, passes through the bit at the bottom of the hole, and rises to the surface in the space between the drill stem and the wall of the hole. In the course of this circulation the drill bit is cooled, cuttings are removed, the drill stem is lubricated, the walls of the hole are sealed, and the hydrostatic head of the column of weighted fluid helps to confine high oil and gas pressures. The latter feature aids in prevention of gushers, thus reducing both environmental pollution and waste of oil and gas resources as well as conserving the natural reservoir pressure for greater production and rate of recovery of the products contained in the rocks. Barite is particularly well suited for drilling mud because it is clean, easy to handle, soft (nonabrasive), heavy, virtually inert chemi¬cally, and relatively inexpensive compared to many other available heavy materials. Barite is used in the manufacture of glass in continuous tanks. The addition of barite ho¬mogenizes the melt and gives greater brilliance and clarity to the finished glass. Ground barite, both unbleached and bleached by sulfuric acid, is a common industrial filler, extender, and weighting agent. The rubber in¬dustry is a major consumer of barite as a filler. Barite also is added to bristolboard, heavy printing paper, playing cards, rope finishes, brake linings, clutch facings, plastics, and li¬noleum, to name but a few uses. Bleached barite has long been an extender in white lead paint because of its weight. The low index of refraction of barite, however, makes its ability to cover marks poorer than some other sub¬stances, but its low capacity for absorption of oil is a good feature. Off-color or unbleached barite can be used as a filler in colored paints. In the construction industry, some lump barite is used in concrete aggregate to weight down pipelines buried in marshy areas and to shield nuclear reactors. Because barite absorbs gamma radiation well, its use reduces the amount of expensive lead shielding otherwise

Jan 1, 1975

By B. E. Sundquist

The various methods based on solution models for obtaining free energies of mixing from miscibility-gap data have been applied to a number of binary-alloy systems. For nine of these systems there exist experimental thermodynamic data that permit a comparison of the results to experiment. It was found that the method of van der Toorn and Tiedema almost invariably leads to results that are physically unacceptable and that vary drastically with small changes in the miscibility-gap parameters. The subregular solution model is found in all cases, except the Al-Zn, Fe-Cr, and Cu-Pb systems, to exaggerate the free energy of mixing by 30 pct or more. The model developed by Lumsden is found to give results that are often in excellent agreement with experiment and which exaggerate the free energy of mixing by no more than 30 pct. These results and others give evidence that the Lumsden treatment of the effect of unequal atomic sizes and of imperfect configurational randomness due to deviations of AB bond energies from the mean of AA and BB bond energies is adequate for most systems. ANALYTIC expressions are frequently proposed for the dependence on composition of the activities of the components of a solution. Because the development of solution theory is incomplete, these expressions contain parameters which must be determined by experiment. The measurement of activities is often difficult and consequently such measurements are less readily available than are measurements of phase equilibria which, under certain conditions, can also be used to evaluate these parameters. For example, suppose it is known that two structurally dissimilar phases, each of known composition, in an n-com-ponent system are at equilibrium at a given temperature and pressure. n equations can be set up in terms of these parameters expressing the equality of the chemical potential of each component in the two phases. In addition, one can write the Gibbs-Duhem equation for each phase that also contains these parameters. Thus, if these n + 2 equations contain n + 2 parameters, these parameters can be determined (at the temperature in question) from the phase diagram alone. If the average number of parameters in each expression for the activity of a given component in a given phase is V then there will be 2nV parameters involved. Equating 2nV to n + 2 shows that, for n + 2, V = 1. If the temperature dependence of each parameter were to be expressed in some explicit form one could use equilibrium conditions at a number of temperatures to increase V. The situation is much improved when the two phases in equilibrium are structurally similar. It can then be assumed that, stably or metastably, two phases will become one at higher temperatures. Thus the number of parameters involved becomes nV instead of 2nV. Hence, V = 2 for n = 2 using only one temperature. (It is implied here that the activity expressions used are valid over the entire composition range.) In this investigation only the equilibrium of two structurally similar, two-component phases (miscibility-gap systems) will be considered. The various proposed solution models will be applied to a number of these systems and the results compared with available experimental results. All of the analytic expressions that have been proposed for the free energy of mixing of a two-component system are of the form where ?Gmix is the free energy of mixing per mole of solution, N1 and N2 are the mole fractions of components 1 and 2, respectively, and f(Ni, T) is some function of composition and temperature. In the "ideal" solution model f = 0. In the "regular" solution model f = a constant. Since these two models permit only a symmetric equilibrium diagram they will not be considered further here. The simplest model that permits a nonsymmetric miscibility envelope is the so-called "subregular" solution model proposed by Hardy.1 This model gives where the Ci(T) are functions of temperature only. The same expression for f is obtained from the "linear a function" model proposed by Darken and Gurry2 and applied to miscibility-gap systems by Wriedt.3 This model requires that the a function defined by be a linear function of composition (yi is the activity coefficient of component i). This model is not purely hypothetical for it has been found2 to hold true for a number of systems. It is readily shown3 that the f(Nl, T) obtained from this model is of the form given in Eq. [2]. It will be noted that the subregular solution model contains only two parameters and hence both of them can be determined at any desired temperature below the critical temperature, Tc, for a miscibility-gap systems in the manner described previously. At T, the two constants can be determined by equating the second and third derivatives of ?Cmix with composition to zero. Another two-parameter model was proposed by Lumsden4 who set

Jan 1, 1967

By C. R. Sandberg, L. S. Gournay, R. F. Sippel

The effect of fluid-flow rate and fluid viscosity on oil-water relative permeability determinations was studied using the "dynamic flow technique." In this work relative per-nleability curves were obtained for homogeneous small core .samples from several sandstorle outcrop form-utions. Radio-tracers were used for the determination of fluid saturation and for the detection of saturation gradients. Cobalt-60 in the form of cobaltous chloride was used as a water-phase tracer in some of the experiments. Iodine-131 in the form of iodobenzene and Mercury-20-3 in the form of mercury diphenyl were used as oil-phase tracers in other experiments. Flow rates for each phase were varied within a range of 2.5 to 140.6 ml/hr. Oil-phase vis-cosities under flowing condition,> were varied from 0.398 to 1.683 cp. The relative permbilities ob-tained were found to he solely a function of saturation and independent of flow rare, provided there was no .Saturation gradient induced in the core sample by "boundary effect." Even though equilibrium with re-sped to flowing conditions was obtained at the lower flow rates, where a saturation gradient exists, this equilibrium is of a "contingent"-type rather than the "steady-state" equi-librium implicit in the relative per-meability concept. The only effect of increasing the oil or non-wetting phase viscosity was to decrease the flow rate required for the elimina-tion of the boundary effect. Fairly good agreement between experimentally determined and calculated values of the boundary effect was obtained when the non-wet-ring oil phase was the only Flowing phase. INTRODUCTION In the characterization of reservoir rock, as well as in the solution of reservoir production problems, it is most desirable to have reliablc rela-tive permeability measurements for the rock and fluids of interest. Many techniques have been developed for the laboratory determination of the relative permeability of both large and small core samples. In varying degree, difficulties attend the use of all of the methods. Each of the methods requires the metered flow of fluids of known viscosity through the core sample under conditions wherein the pressure drop in the individual flowing phases can be measured or closely approximated. Since the relative permeability is a function of the saturation and distribution of the flowing fluids, some means of obtaining such information is also required. The laboratory determination of the relative permeability of a sample should give the same relative permeability saturation relationship that would exist if the sample were in place in the oil reservoir. The attainment of this objective is complicated by the fact that the use of small core samples for laboratory measurements is usually necessary. As a result, errors in measuring the relative permeability arise from boundary effects at either the fluid input or output ends of the sample; no significant boundary effect is anticipated at the sides of the sample normal to direction of fluid flow. At the input end of the sample a boundary effect exists if the flow fluids are not com- mingled as they would be in the reservoir. At the output end of the sample a boundary effect exists as a result of discontinuity of the capillary properties of the system. Here the flowing fluids leave the small flow channels and enter a collecting system having much enlarged flow channels. Thus, there is a tendency for the wetting phase to be retained by the core sample because of the attraction of the core sample for the wetting fluid. No reference is made to these boundary effects in either Darcy's equation or in the relative permeability concept. As a consequence the saturation effect peculiar to the input end of the core sample may cause an error in the effective permeability measurement, since some portion of the core sample must be utilized for commingling of the flow fluids. At the output portion of the core sample a saturation gradient or a saturation change along the axis of flow results. Since relative permeability is a function of fluid saturation, this saturation gradient may cause a variable permeability measurement, especially since extent and character of the saturation gradient can vary with fluid-flow rate. The most convenient method of minimizing the boundary effect, especially at the output end of the sample, is to flow the fluids of interest through the core sample at such high rates that the capillary forces arc insignificant as compared to the viscous forces involved in the fluid flow. Since recent work of a preliminary nature has indicated that fluid dispersion in the porous medium increases with the flow rate, the high flow minimizes the boundary effect at the input end of the core sample by enhancing the mixing of the fluids.

By C. J. Rodgers

The present day success of gravel packs to prevent or retard the migration of unconsolidated sands into the well bore is due to: (I) the use of a saline or non-aqueous, nonsolids drill fluid, (2) proper preparation of the well bore prior to gravel packing, and (3) pressure placement of the gravel. The experience gained from the "pressure pack" method of gravel packing indicates that sand-free fluid production can be maintained for a length of time sufficient to make the operation economically attractive. Data pertaining to the first 15 wells so completed by Gulf indicate that for each dollar spent to effect the completion, there will be a return of more than $2.92. The pressure pack technique of gravel packing is essentially the placing of gravel in and adjacent to the producing formations. This is done with fluid pressure and by the use of a drill fluid that will permit partial or complete loss of returns to the formation during placement. This technique was first intentionally used by Gulf in May, 1950, and since that time has been applied in more than 90 wells. Other advantages claimed for this type of completion are that the pressure placement of the gravel has a scouring effect on the casing perforations, that additional drainage channels to the well bore are created, and that the possibility of shifting of the formations adjacent to the casing is minimized and possibly prevented. During the past few years, the use of gravel to prevent or retard the migration of unconsolidated sands into the well bore has met with a favorable degree of success. Numerous methods and techniques of "gravel packing" have been used, each having its own relative merits, and with varying results. M. L. Cashion1 in 1939 ably reviewed the history of gravel packing to that time. As stated in his paper, ". .. the idea of gravel packing wells is not new." During the period 1939 to 1949, very little if any progress or change in technique in this type of completion was made. However, it was noted in some cases that during the placement of gravel, if there was a loss of drill fluid to the formation, there was a corresponding loss of gravel to the formation. Also, it was noted that in those gravel-packed completions (opposite casing perforations) that "sanded up," there was found to be an absence of gravel in the annular space between the liner and casing, although gravel had previously been placed in this space and no gravel had been removed from the well at the surface. These findings resulted in the placement of gravel with fluid pressure and by the use of a drill fluid that would permit partial or complete loss of returns to the formation during placement. Pressure placement of gravel became an accepted practice in late 1949 and early 1950. Another fact brought to light that has contributed to the current success of gravel pack completions is that drilling fluids containing solids will to some extent cause plugging of the screening medium or blocking of the producing section. The removal of these solids by chemical action, mechanical action, or a combination of the

Jan 1, 1955