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By J. W. Downey, M. V. Nevitt

DURING the course of the present investigation of alloy phases involving transition metals, phases were found in the systems Os-Ta, Os-W, and Ir-Ta. The (Os, W) phase was also recently reported by Raub.1 Pertinent information is given in Table 1. The approximate composition range of sta- bility was determined metallographically on arc-melted buttons that were annealed 72 hr at 1200°C and water quenched. X-ray powder patterns were obtained with a 114.6 mm diam powder camera using filtered copper radiation. The composition for (Os, W) given by Raub (66 atomic pct W) is in agreement with the composition range reported here. However, the lattice constants reported by Raub are: a0= 9.913±0.007, c/a= 0.515. The reason for the discrepancy between the lattice constants reported by Raub and those given here is not known. Acknowledgments The authors wish to thank M. H. Mueller and H. W. Knott for assistance with the X-ray diffraction work, and R. A. Morris for the preparation of the alloys. This paper is based upon work performed at the Argonne National Laboratory under the auspices of the Atomic Energy Commission.

Jan 1, 1958

By John D. Price

COAL blending, in the preparation of coal before coke making, is so commonly practiced as to be almost universal. But the reasons underlying this practice, the benefits resulting from it, and the materials used in blending vary widely. This paper will outline the various phases of the subject and present information which may be correlated with work that has been done elsewhere. It will deal entirely with work done on the high-volatile coking coals of the western part of the United States, special emphasis being given to the coals of Colorado and Utah. A surveyL of the 86 coke plants in active operation in the United States during 1949 indicates that only 9 plants, or 10.5 pct of the total, charged one single rank of coal into their ovens, while the remaining 89.5 pcl made use of blending in some form. This report indicated that of these total plants 5 used straight high-volatile coal, 4 used straight medium-volatile coal, 47 used blends of high and low-vola-tile coals, 25 used blends of high, medium, and low-volatile coals, 2 used blends of high and medium-volatile coals, 3 used blends of medium and low-volatile coals. The fact that certain plants operated on a single kind of coal should not be interpreted to mean that no blending was practiced there, for invariably such plants secure their coal from more than one source and in the interest of uniformity do blend the coals as received. The general term coal blending covers two fields, the first of which is the mechanical mixing of a number of coals to secure uniformity. Often it is found necessary to secure coal for coke production from a number of different mines; these coals, though of the same general type or rank, may differ in their chemical composition or in the physical qualities they impart to coke made from them. Again, it is not unusual to find that coal from different sections of the same mine may show variations in quality. Under such conditions it may be necessary, in the interest of a uniform final product, to introduce a system of blending bins, a bedding yard, or other mechanical methods of securing a uniform mixture. Unfortunately this form of blending has received very little attention up to the present time; it has not received the consideration its value merits. The second type of blending, while also for the purpose of coke improvement, deals more particularly with the use of a blending agent differing in character from the base coal: it is this form of blending that will be discussed here. To consider only the western coals, for blending may be found necessary for other reasons with other coals, blending has been practiced experimentally or commercially under the following conditions: 1—When a single coal or mixture of coals of the same rank does not produce a satisfactory coke. For example, a high-volatile coal when used alone is likely to contract when coked so that a comparatively weak coke is formed. Or, if of very low rank, the coal may be deficient in the necessary bitumens required for good coke production. 2—When a product of some special quality is required, for example, when a plant ordinarily producing blast furnace coke must operate at slow coking rate to produce a high-grade foundry coke. Under this condition the reduced daily production of all products which accompanies slow coking time may be undesirable, and the use of some blending agent to increase the size of coke made at faster coking rates may be necessary. 3—When greater yield of coke or its coproducts is needed. Depending upon economic values of the products it may be found desirable to increase the yield of one or the other. 4—When supply of a particular coal must be used, either to protect reserves of high quality coking coal or to utilize a surplus or inferior product not otherwise usable. Many materials have been used for blending purposes, the exact agent to be used depending both upon the condition to be corrected and the nature of the base coal. No universal blending agent that can

Jan 1, 1954

By H. L. Sauder, J. L. Newman, C. Waddell

An instrument capable of measuring subsurface flow rates is described. The instrument is self-contained and may be run on piano wire line. It detects flow by means of an impeller suspended between two torsion wires. The force of the well fluid striking the impeller causes the impeller to rotate, exerting a torsional force to the wires. This force is determined by recording the angle of rotation of the impeller on film using a battery-driven, clock-controlled camera. The impeller is sensitive to flow in either direction and the same instrument can be used to measure injection as well as production rates. Changes in direction of flow, such as might be caused by thief zones, are measurable and are indicated by a reversal of the direction of rotation of the impeller. Adjustment of the sensitivity of the instrument to measure a wide range of flow rates is accomplished by the use of different size torsion wires. An umbrella-type fluid trap, which contacts the casing or wellbore, diverts the flow through the flow tube. The fluid trap remains closed while rurrning in the hole and can be opened at any point in the well. The instrument with the trap closed is 1 3/4 in. OD and may be run through 2 in. tubing. Successful flow profiles have been made on wells with flow rates ranging from 60 BID to 4,000 B/D at surface pressure up to 4,500 psi. The instrument is designed for high-pressure and high-temperature operations. INTRODUCTION The need for an instrument that will measure flow rates in a wellbore is as old as reservoir engineering itself. A number of such devices have been designed within the past few years. Some of these have been described in the literature1,2,3,4,5,6 One of these devices1. a hot-wire anemometer type, made many successful jobs in dry gas producing areas. Difficulty was encountered when this flowmeter was used in wells producing liquids and development work was initiated to overcome this difficulty. The present flowmeter is the result of this work and provides an instrument with a wider range of application in the industry. Consider- able development work has been done on the tool involving many changes in the mechanics of recording the flow readings, however, the basic principle of flow detection has remained the same since its inception. PRINCIPLE OF OPERATION The basic principle of operation of the flowmeter is the utilization of a portion of the kinetic energy of flowing well fluid to impart a rotational force to an impeller suspended between two torsion wires. This impeller, Fig. 1, is a screw-type propeller with the blades having a pitch angle of 40. As the well fluid passes through the instrument it strikes the impeller. The resulting force rotates the impeller and twist\ the torsion wires to a balance point at which the torque imparted to the wires balances the force required for the impeller to deflect the well fluid. The impeller is symmetrical and a change in direction of the flow results in a reversal of the direction in which the impeller is deflected. Thus the direction of the flow as well as its velocity is indicated. A dial is attached to the impeller by means of a hollow tube through which the upper torsion wire extends. The angular position of the impeller is recorded by photographing the dial at frequent intervals. In any given set of torsion wires the modulus of shear and polar moment of inertia remain constant and the deflection varies directly with the applied torque. The deflection imparted to the torsion wires also varies as the square of the fluid velocity. Further, the velocities represented by any two given deflections hear the following relationships: and Where V = velocity of flow stream and O ;= deflection. This is the basic relationship which is used to calculate the relative velocities represented by a given set of deflections where the velocity represented by any one of the deflection readings is a known quantity. For a given torque, the deflection of the torsion wire varies inversely as the fourth power of the wire diameter. Wire sizes ranging from ,005 in. in diameter to .022 in. in diameter can be used. The range of

Jan 1, 1957

By E. G. Woods, A. G. Comer

A mathematical model is presented and solved for determinution of the saturation distribution and pressure in a radial gas-storage reservoir. The model consists basically of two parts: (I) the growing gas-bubble core, and (2) the surrounding aquifer. Since the total pressure at the injection well is a function of the two-phase flow in the gas bubble and the unsteady single-phase flow in the aquifer, the resistance to flow in both zones was taken into consideration. The assumptions involved for both the radial equivalent of the Buckley-Leverett two-phase-flow equation and the injection-pressure equation are as follows: (I) the geometry is radial, (2) the gas bubble is free to expand or contract, (3) compression or expansion of the gas within the bubble may occur at the beginning of a time step, (4) the fluids are immiscible, (5) water is incompressible within the gas-storage region whereas it is compressible outside of this region, (6) a stable gas-water interface exists and (7) gas injection occurs at a constant rate or a series of constant rates. The mathematical model was solved numerically using an IBM 650 computer. A comparison is presented between the predicted results of the model, the results assuming steady-state flow and the actual initial injection-pressure history of an operating reservoir. Using the initial field pressure for a basis, the average deviation between the predicted pressure and the actual field pressure was less than 4.3 per cent. INTRODUCTION Underground storage of natural gas in abandoned oil fields, in abandoned coal mines, in caverns and in aquifers has had varying degrees of success. The lack of these first three facilities in the vicinity of most major gas marketing areas is leading more and more to storage in virgin aquifers. For the most part, this storage in aquifers has led to the study upon which this paper is based. Several excellent papers have been published discussing the problems involved in the underground storage of natural gas; however, to these writers' knowledge, none of them considered the two-phase flow of fluids in the gas bubble and the fact that the gas bubble will grow or shrink in size depending upon the injection and withdrawal history of the reservoir. Not only will both of these factors influence the required injection pressure, but also they will have a definite bearing upon the amount of water production occurring upon withdrawal from the storage area. To solve this problem on an IBM 650 computer, several simplifying assumptions were made. Only the drainage portion of the relative-permeability curve was considered, thereby neglecting any hysteresis effects introduced during an imbibition cycle. The quantity of gas withdrawn during the period of the field study was only a small percentage of the total gas in place; therefore, this assumption is justified. For the problem studied in this case, the combined effects of capillarity and gravity were assumed to be negligible. This assumption becomes less valid as the formation thickness or the average pore diameter increases markedly. The justification of these assumptions should be studied in each case. THEORY This mathematical model for the prediction of saturation distribution and pressure for a radial gas-storage aquifer is based upon the equations for radial two-phase fluid flow'.' and for radial, unsteady-state, single-phase fluid flow.' The two-phase flow is considered to take place in a "core" whose radius is equal to the maximum radius that the gas zone will attain, as indicated in Fig. 1. The injection-withdrawal history is approximated by a series of constant flow rates. Within the "core", gas is assumed to behave as a semi-compressible fluid; that is, the gas is assumed to have a constant density based on the average gas-zone pressure for the flow period. Between each constant-rate time increment, the gas density is allowed to change. This involves an iterative solution of the pressure equation. The liquid phase in this zone is considered to be incompressible, whereas it behaves as a compressible liquid outside of this region. The equations of incompressible flow in the "core" may be written for the gas phase

By Galen G. Waddell

Several years of rock-burst research conducted by the U.S. Bureau of Mines in cooperation with the mining companies of the Coeur d'Alene mining district, Idaho, in addition to progress made by others throughout the world, have led to a good understanding of the rock-burst problem. This paper describes conditions which have caused specific bursts, present capabilities of detecting stress buildup and bursts, control methods, and a suggested approach to analyzing any individual mine-burst problem. A rock burst is the sudden, violent release of stored strain energy in rock by some mechanism of rock failure, generally accompanied by expulsion of rock with consequent damage to the mine. A burst may be audible for only a few hundred feet, or on the surface it may sound like a sonic boom miles away. A Dictionary of Mining, Mineral, and Related Terms, U.S. Bureau of Mines (USBM)* 1968yand defines a burst as Bureau "That phenomenon which occurs when a volume of rock is strained beyond the elastic limit and the accompanying failure is of such a nature that accumulated energy

Jan 1, 1971

The following list comprises the names of those persons who became members during the period May 10, 1919, to June 10, 1919. ALAYZA, CARLOS Box 850, Lima, Peru, S. A. BALLARD, P. A Surveyor, Midwest Refin. Co., Custer, So. Dakota. BARNEBL, A. J., JR.... Mech. Eng., The Dorr Co., 101 Park Ave., New York, N. Y. BILLINGS, GOODSELL Platteville, Wis. BRONSON, C. B., Mech. & Met. Engr., New York Central Lines, Room 1520, Grand Central Terminal, New York, N. Y. BUNCE, E. H Met., The New. Jersey Zinc Co., Palmerton, Pa. CHARLTON, D. E. A., Editorial Staff, Engrg. & Mm. Journals 10th Ave. & 36th St., New York, N. Y. DAVIS, JOHN N., Supt. of Mills, Engels Copper Min. Co., Engelmine, Plumas Co., Cal. DUKES, GLENN H., Chief Engr., The Sunday Creek Coal Co.,1001 Outlook Bldg., Columbus, Ohio. ERICKSON, ARTHUR .... Engr., United Smelt., Refin. & Min. Co., Mldvale, Utah. FLYNN, A. E Supt., Rand Consolidated Mines, Ltd., Goudreau, Ont., Canada. HIBBARD, WALTER R 63 Ashley St., Bridgeport, Conn. HOBSBAWN, I. BERKWOOD, Cons. Tech. Chem., Messrs. Gibbs. & Co., Valparaiso, Chile, S. A.

Jan 7, 1919

By Y. C. Liu, W. R. Hibbard

Based on pole figure data and microstructural observations, the re-crystallization orientation found in a copper strip previously cold-rolled 99.5 pct from a single crystal with an initial (110) [112] orientation may be described as: a 30° rotation, clockwise and counterclockwise, about octahedral poles of the cold-rolled texture such that all four poles function at a low annealing temperature (400°C) and only three of them function at high temperatures (500' to 1050°C). The relative intensity of deformation stresses on various slip planes can be correlated with the choice of poles affecting the rotations found in the recrystallized orientations. ROTATIONAL reorientation about the poles of densely packed crystallographic planes is an important characteristic of secondary recrystallization" in face-centered cubic metals. Some evidence has also been interpreted to show that such a rotational relationship also exists in the primary recrys-tallization process." In an investigation of the crystallographic relationships in the recrystallization process, several aspects of the experimental procedure should be considered. With cold-rolled poly-crystalline metal as the initial material, pole figure analysis leaves many ambiguities as to whether or not simple indices can be assigned to adequately represent its orientation. The rolling texture does not consist of a single texture. Minor deformation textures are usually present. In all cases, twin textures are present. The presence of both minor and twin deformation textures influences the recrystallization texture. In order to study the recrystallization mechanism, a more precise knowledge of the history of the material before recrystallization is necessary. Tensile deformation of a single crystal usually produces residual stresses which are concentrated at slip bands. Since the exact nature and orientation of these potential nuclei sites cannot be experimentally evaluated, the tensile deformation of a single crystal was not considered adequate. From the work done by Barrett and Steadman6 n copper, it appeared that cold rolling of a single-crystal specimen with an initial (110) [112] orientation would yield a specimen which fulfills the conditions required for the present investigation, namely a highly preferred single rolling texture with relatively homogeneous stress distribution. By investigating the recrystallization texture of this material, additional details of reorientation during recrystallization might be obtained. The purpose of this paper is to describe such an investigation. Experimental Procedure Copper used in the present investigation was cathode sheet with a purity of 99.94 to 99.97 pct. A copper single-crystal specimen, 1.15x0.8720x0.5322 in. (thickness) was cut from a cylindrical crystal which was grown in a Bridgman furnace.' The cutting was accomplished on a horizontal milling machine operated at a very slow speed to obtain a (110) plane in the rolling plane and a [112] direction in the rolling direction. The disturbed surface was removed by electrolytic polishing in dilute orthophos-phoric acid (H3PO4) with a specific gravity of 1.14, and a current density of about 1 to 2 amp per sq cm. A 3-min polishing was needed to eliminate the disturbed surface causing Debye-Scherrer rings and a 45-min polish produced a surface which yielded sharp rounded Laue spots. It was estimated that about 1/16 in. of metal was removed from the original cut surface. The final orientation of this specimen before rolling was about 2" from the (110) plane in the rolling plane with a [112] direction aligned in the rolling direction. It is possible that a small amount of strain was still present in the cube despite the fact that the Laue spots seemed very sharp. It is doubtful, however, that this would be an important factor after a subsequent rolling reduction of 99.5 pct. This copper specimen was rolled on a laboratory rolling mill with two highly polished rolls 37/8 in. in diam in the following manner: 0.010 in. per pass to 50 pct reduction, 0.005 in. to 70 pct, 0.002 in. to 85 pct and, finally, 0.001 in. per pass to a 99.5 pct reduction. Specimens, about 1 in. sq with the rolling edges intact, were cut from the rolled strip by the electrolytic method previously described, after the strip

Jan 1, 1954

NEW MEMBERS The following list comprises the names of those persons who became members during the period Feb. 10, 1919, to Mar. 10, 1919. ALLEN, ROLLAND CRATEN State Geol., Appraiser of Mines, Lansing, Mich. ALTMAYER, MAURICE ERNEST, Ingenieur des Arts et Manufactures, 145 Rue de la Pompe, Paris, France. AUSTIN, CHARLES L., Assayer, Highland Boy Mine, Utah Cons. Min. Co., Bingham Canyon, Utah. BARTLETT, ARTHUR J., Chief Engr., Louisville Coal & Coke Co. Goodwill, W. Va. BOIES, ORLOW W., Research Chem., Roessler & Hasslacher Chemical Co., 1632 Tenth St., Niagara Falls, N. Y. BRAGG, G. A., Mgr., Experimental Copper Leaching Plant, Mellon Inst. of Industrial Research, Thompson, Nev. BRUSCANTINI, GIOVANNI, Min. Engr., Gen'l Mgr., Sindicato Minero de Cuba, Box 370, Santiago, Cuba. COLONY, R. J Instructor in Geol., Columbia University, New York, N. Y. DAVENPORT, FRANK B., Cons. Engr., 806 Coal Exchange Bldg., WiIkes-Barre, Pa. EATON, S. FORD 120 E. 85th St., New York, N. Y. EBY, J. H., Min. Engr Box 433, Spokane, Wash. ENGELHARDT, EDWARD A., Mgr., Surinaamsche Bauxite Mij, Paramaribo, Dutch Guiana, S. A.

Jan 4, 1919

By Guy Crane

I. INTRODUCTION THE geology of the Tintic mining district, fully treated, would occupy an elaborate monograph. This less comprehensive paper is devoted primarily to the occurrence and origin of the orebodies of the district, while space is given to those phases of the general geology only which seem necessary to a proper setting of such a discussion. The first geological report on the Tintic district to be issued was that by Tower and Smith, published in 1899, in the form of a paper in Part III of the Nineteenth Annual Report of the U. S. Geological Survey, and also as Folio No. 65, Geologic Atlas of the United States. About four years ago a second investigation was begun by Waldemar Lindgren and G. F. Loughlin, of the U. S. Geological Survey. With the exception of a paper on the oxidized zinc ores of the Tintic district by Mr. Loughlin, the results of their work are still unpublished. The writer's acquaintance with the district began in the fall, of 1913, and has extended over a period of about two years.

Jan 10, 1915

By Norman Yarborough

Much has been written about the energy fuels including their standing with respect to reserves, their delivered Btu costs, their potential in the electrical generating market and their capabilities to meet a burgeoning demand. Yet, when all factors are placed in their proper perspective, the spiraling electrical energy market alone should guarantee each fuel a better than average market for the foreseeable future. In fact, a study made by the U.S. Federal Power Commission on the spare capacity utilities have on hand indicated that 39 of the 181 major utility systems had less than 10% reserves on hand at the end of 1969. Fuel supplies are critically low in some areas, especially in the Southeast, South Central and Midwest areas of the U.S. In other systems equipment shortages resulting from faulty equipment or delays in getting new equipment deliveries causes power failures during peak loads. In addition, lack of labor curtails the erection of some new facilities and prevents many other facilities from operating at capacity.

Jan 1, 1970

Society of Economic Geologists, 65 East 56th St., Princeton, N. J. Edward Sampson, Secretary. Publications of the Society constitute a part of "Economic Geology," a semiquarterly journal published by: The Economic Geology Publishing Co., W. S. Bayley, Business Editor, University of Illinois, Urbana, Ill.

Jan 1, 1933

By H. Rumfelt

Surface excavators for mining coal and such non- metallic minerals as quarry stone, gypsum, phosphate and the like have advanced tremendously in the last 50 years, and their advancement has paralleled that of excavators used in the construction industry during the same period. Up to a certain stage, the construction industry led the way with this development and even pioneered in how the equipment was used. Afterwards, however, new mining machinery and related operating techniques progressed along a different path than their construction counterparts because of the different demands of the two industries. The word "stage" as used above quite generally connotes a transition period, possibly of several years' duration, during which mining development followed the construction industry. Later, mining branched out and responded to its own needs. Most readers are familiar with the events which led to the development of the power shovel. The first dredge was recorded as having been used in England in the latter 1700's and was no doubt developed along the lines of some notes written in the late 1400's by Leonardo da Vinci.

Jan 1, 1971

Mansfield MERRIMAN,Lehigh University, South Bethlehem, Pa. (communication to the Secretary*):—The formulas established by Mr. Campbell require the use of tables in order to take into account the influence of manganese on the tensile strength of steel. On examining these tables I find that the quantities given therein may be expressed by simple algebraic forms, so that formulas for tensile strength may be written which can be used without the help of tables. Referring to the case where the carbon is determined by

Jan 1, 1906

By John D. Wiebmer

Kansas, with its thin seams and tough overburden, may not be anyone's first choice for a coal mining operation. But there are operators making it pay through careful attention to mining techniques and aggressive marketing in the local region. One of the few Kansas coal operators is Bill Patch, who has been in the business for 28 years. Beginning with a single dragline operation near his home in Welch, Okla., Bill's Coal Co. weathered some lean times during the "soft" coal market of the 1950's and 1960's. But his tenacity paid off when new markets began opening up, and the company has grown by leaps and bounds in recent years. In 1975, the Fort Scott mine opened in Bourbon County, Kansas; in 1976, the Porter mine began production in Wagoner County, Okla.; in 1977, the Fulton mine opened near Fulton, Kansas. In addition, the original Welch mine in Oklahoma is still a producer, and this year the company will open a new mine at Chetopa, Kansas.

Jan 9, 1978

By C. K. Leith

CERTAIN ideas on iron and steel sanctions to follow originated in a series of conferences held under the joint auspices of the War Department and Brookings Institute in Washington last spring. The views presented may be regarded as those of substantial segments of the steel industry. In view of the fact that steelmaking capacity can be so quickly converted to the production of armament, any effective control must necessarily include the entire steel industry and not solely the parts devoted to the production of implements of war. It must also be exercised all the way from production and shipment of raw materials through their ultimate conversion into finished products and use. Control will be dis- cussed under two main headings: (I) control of raw materials at the source; (2) control of steel capacity within the Axis countries.

Jan 1, 1944

Howland Bancroft (A Modern Approach To Foreign Mineral Development, P 666) was born in Denver, Colo and attended the University of Colorado, University of Michigan and received a B S and B A degree From 1907 to 1912 he was with U S Geological Survey In 1911 he was involved in study of mining resources of Peru Mr Bancroft resigned from Federal Survey and opened offices as consulting mining geologist in Denver in 1912 From 1919 to 1920 he was a consulting engineer in San Francisco He was manager of Sinclair Panama Oil Corp in Panama City in 1920 From 1921 to 1923 he was vice president and managing director of same corporation He did independent examinations in Western states and an exploration trip through Turkey in Asia from 1924 to 1925 Mr Bancroft was vice president and general manager of Lago Petroleum Corp in charge of operations in Venezuela Mr Bancroft has spent time in 34 different countries in the world and in a number of different Latin American States, Europe, Asia Minor and Africa

Jan 1, 1952

By Ta M. Li

Recent start-up of the Pinto Valley mine and mill is expected to add to domestic copper mine capacity by some 62,500 tpy. Owned and operated by Cities Service Co.'s Miami Operations, the complex lies approximately 5% miles west of Miami, Ariz. The estimated $100- million project, the largest single construction project ever undertaken by Cities Service, includes the Pinto Valley open pit mine, a 40,000-tpd concentrator, and a 10-mile slurry pipeline that will transport a 28% copper concentrate slurry to a new filter plant located in Miami. Concentrate will be treated nearby at Inspiration Consolidated Copper Co.'s new smelter complex. The current pit design contains reserves of approximately 350 million tons of ore averaging 0.44% Cu. Based on an initial production target of 40,000 tpd ore and 60,000 tpd waste, mine life is estimated at 24 years. The current stripping ratio is 1.5: 1, requiring the ultimate removal of more than 500 million tons of waste and leach-grade material.

Jan 6, 1975

University of Alaska College, Alaska Mining Society RAYMOND SMITH, President KEN \PIER. Secretary HOWARD, G. WILCOX Faculty Sponsor BERT OGBURN Counselor University of California Berkeley, California Mining Association D. J. MCNEIL, President S. A. YOUNG. Secretary LESTER C. UREN Faculty Sponsor GRANVILLE C. BORDEN, Counselor

Jan 1, 1943

Mining Methods LUCIEN EATON, Chairman S. R. ELLIOTT, Vice-chairman CHARLES W. WRIGHT, Secretary Alluvial Mining CLINTON BERNARD CHARLES JANIN O. J. EGGLESTON CHARLES H. MUNRO N. L. WIMMLER Open-cut Mining Iron MAX H. BARBER J. A. MACKILLICAN KENNETH DUNCAN W. R. VAN SLYKE

Jan 1, 1932

By Robert K. Steunenberg, Irving Johnson, James B. Knighton

The activity coefficient of plutonium in liquid magnesium, over the temperature range 650° to 800°C, was obtained from measurements of the distribution of plutoninm between a 50 mole pct MgC12-30 mole pct NaCl-20 mole pct KC1 molten-salt mixture and liquid Zn-Mg alloys. For dilute solutions (0.08 at. pct Pu) the activity coefficient of plutonium was found to vary from 10.1 at 650°C to 12.2 at 800°C. The activity coefficients of plutonium in dilute liquid solutions of plutonium in uranium, silver, lanthanum. cerium, and calcium were estimated to be. The distribution data indicate a value of about 0.1 at 800°C for the activity coefficient of PuCl3 dissolved in the above ternary salt mixture. LIQUID magnesium and several liquid alloys of magnesium with metals such as zinc and cadmium have been shown to be useful solvents in pyrochemical processes for the recovery of uranium and plutonium from discharged nuclear fuels,' and for the separation of transuranium elements.' The present study was undertaken to determine the activity coefficient of plutonium in liquid Pu-Mg alloys in support of process-development work. The activity coefficient of plutonium in liquid magnesium was determined from experimental data on the distribution of plutonium between a liquid ternary MgC12-NaC1-KC1 salt mixture and various liquid Zn-Mg alloys. The distribution data were used to calculate the ratio of the activity coefficients of plutonium in liquid zinc and in liquid magnesium. The activity coefficient of plutonium in liquid magnesium was then computed from the known activity coefficient of plutonium in liquid zinc. It was not necessary to know the thermodynamic properties of the molten-salt system explicitly. The major features of the Pu-Mg system have been reported by Schonfeld.3 At the temperatures of interest in the present study, i.e., above about 600°C, the phase diagram indicates the existence of a wide liquid-miscibility gap, with the plutonium-rich liquid containing about 8 at. pct Mg and the magnesium-rich liquid containing about 10 at. pct Pu at the intersection with the solidus regions. Additional data on the compositions of the two equilibrium liquid phases obtained in this laboratory4 have defined the miscibility gap up to the consolute temperature (at about 1040°C). EXPERIMENTAL PROCEDURE AND RESULTS Materials. The 50 mole pct MgC12-30 mole pct NaC1-20 mole pct KC1 salt mixture was prepared by melting the required proportions of reagent-grade NaCl and KC1 with anhydrous MgC12. The molten salt was then purified by contacting it with liquid Cd-30 wt pct Mg alloy (at 450°C) to reduce oxidizing impurities, followed by filtration through a stainless-steel frit (pore size, 65 µ) to remove solid MgO formed during the reduction. The purity specifications of the zinc, magnesium, and plutonium were 99.999, 99.8, and 99.85 pct, respectively. Apparatus. The liquid salt and metal were contained in a tantalum crucible inside a graphite secondary vessel. The crucible assembly was located inside a resistance-heated stainless-steel furnace tube. The furnace tube was closed by means of a stainless-steel cover, which was attached by bolts, with a neoprene O-ring serving as a gas-tight seal. The top of the furnace tube was water-cooled to protect the O-ring. The furnace-tube cover was provided with a tantalum thermowell, a tantalum stirrer, and a port through which sampling tubes could be inserted and materials could be added to the melt without admitting air to the furnace tube. Vacuum and an argon atmosphere were available through a side-arm on the furnace tube. The furnace temperature was regulated by a proportional controller that was actuated by a chromel-alumel thermocouple between the furnace tube and the heating elements of the furnace. The melt temperature was measured by means of a chromel-alumel thermocouple in the tantalum thermowell. The accuracy of temperature measurement was ±3°C. The salt and metal phases were intermixed by a motor-driven tantalum paddle positioned at the liquid interface. The tantalum crucible was provided with four baffles to increase the turbulence. The sampling tubes consisted of 1/4-in.-OD tantalum tubing that terminated in a tantalum frit (Kawecki Chemical Co.; average pore size, 30 µ). Procedure. The zinc, magnesium, plutonium, and salt were charged to the tantalum crucible; then the system was evacuated and filled with argon. The melt was brought to the desired temperature, and agitated for 1 to 2 hr. After allowing the salt and metal to separate, both phases were sampled. Filtered samples were obtained by immersing the end of the sampling tube in the liquid and increasing the argon pressure sufficiently to force the liquid salt or metal through the frit into the tantalum tube. The sample was then partially withdrawn into the cooler portion of the furnace tube and permitted to solidify before being removed. The temperature sequence for sampling at each magnesium concentration was 800°, 700°, 600°, 650°, and 750°C. The composition of the liquid-metal phase was varied by incremental additions of magnesium in a series of experiments at low magnesium

Jan 1, 1967