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By Harold M. Feder, Irving Johnson

Tkermodynamic functions for dilute solutions of uranium in liquid cadmium were obtained from galvanic cell measurements. Deviations from Henvy's law were observed at concentvations down to 2 x 10-3 atom fraction. Unusually large negative values of the pavtial molal relative enthalpy and excess entvopy of uranium, suggestive of the occu,vvenctwe of partial ovdering of cadmium around uranium in these solutions, were found. The negative relative partial molal enthalpy of uranium at the liquidus accounts for the observed retrogvade solubility of metallic uranium between 473" and about 630°C. The standard free enevgy of formation of UCd,, from a-uranium and liquid cadmium is given by F,° THE constitutional diagram of the U-Cd system,' Fig. 1, is unusual in several respects. The near equality of the Goldschmidt atomic radii2 (Cd, 1.52A U, 1.56A) might be expected to give rise to extensive mutual solubility of the elements except for the restrictions imposed by differences in valence and electronegativity.3 The latter factors must be strongly influential because mutual solubilities in the terminal solid phases are probably negligible, and the solubility of uranium in liquid cadmium in the readily accessible range is only about 1 at. pct. Interestingly, the solubility of uranium in liquid cadmium actually decveases slightly with increasing temperature from 473" to about 630°C. Such a retrograde solubility in a liquid phase is a rare phenomenon in metallic systems; no other authenticated examples were found among the nearly 700 binary phase diagrams compiled by Hansen and Anderko.2 These observations suggested the existence of some unusual interaction between uranium and cadmium. Greater insight into the nature of this interaction was sought by measurement of the thermodynamic properties of the system. EXPERIMENTAL PROCEDURE The emf of cells denoted by the scheme was measured. Each cell consisted of two uranium and two alloy electrodes immersed in a molten lithium chloride-potassium chloride eutectic mixture containing uranium trichloride. The physical arrangement is shown in Fig. 2. The potential between any pair of electrodes could be measured with a Leeds and Northrup Type K-3 potentiometer. The measurements were made at points marked in Fig. 1. It should be noted that points on the phase boundaries represent the concentrations of uranium in the saturated liquid phases of heterogeneous alloys. Uranium Electrodes. Uranium, which is not a particularly soft metal, is capable of retaining residual stresses, and its potential may depend upon its physical condition. Electrodes were prepared from 3-mm diam rods of hot-rolled high-purity4

Jan 1, 1962

By A. T. Shurick

THE present economic crisis in bituminous coal is substantially the most insidious, and critical, in the modern history of the industry. The large consumption deficit that has gradually developed (almost unawares), has culminated in a situation that has forced home the urgent necessity for prompt and radical remedial measures, such as the various mergers now in course of negotiation. Conditions today are sufficiently comparable with those in the iron and steel industry, preceding the formation of the United States Steel Corpn., to suggest the possibility of a sweeping super-consolidation, that all but staggers the imagination. The important function of the banker in this, and lesser projects, is too well known to require comment, and it is important that we understand clearly just what these functions are. Certain features in banking practice came up for consideration in connection with a rather exhaustive economic study into the prospective future of the coal industry, upon which I was recently engaged for an Eastern bituminous interest. This survey was made for the purpose of effecting a decision on certain pressing questions of policy, involving considerable capital expenditures, that would be compatible with the flattening out in the curve of production in recent years. An examination of the TRANSACTIONS, and the coal literature generally, failed to disclose any pertinent, and authoritative data, on this subject. This was more or less characteristic of the whole survey, which had involved a large amount of original research, and measures were taken to procure the required information. The following notes have been compiled largely from the data thus collected, supplemented with material, suggestions and criticisms, by several of the larger banking houses active in coal, together with personal memoranda of my own.

Jan 1, 1928

Discussion of the paper of WALTHER MATHESIUS, presented at the New York meeting, February, 1915, and printed in Bulletin No. 99, March, 1915, pp. 539 to 555. JOSEPH W. RICHARDS, So. Bethlehem, Pa.-This paper answers. partly the difficult questions which have come up as to why it is not economical to use higher blast temperatures in the smelting of Mesaba ores, such as the high temperatures used in European practices, and the answer is very plain that the ores will not stand the higher temperature. But the paper does not go into detail as to what special difficulties were found with the higher temperature of blast, and I would ask the author to kindly specify them. W. A. FORBES, New York, N. Y.-A large part of the troubles that furnace men experienced in using high-blast heats in smelting Mesaba ores in the early days of using Mesaba ores, was clue to the attempt to use these soft ores on furnaces having the same lines as the furnaces used in smelting the hard Old Range ores. As the result of observation and study, the dimensions of the lower part of the blast furnaces have been changed and the difficulties of the blast-furnace men in operating with a large percentage of Mesaba ore and high-blast temperatures have been largely overcome. The changes I refer to in particular are: (1) steepening the angle of the bosh; (2), decreasing the height of the bosh; (3) increasing the diameter of the hearth. JOSEPH W. RICHARDS.-Mr. Forbes's answer is quite satisfactory, and the moral which it points is that when the furnace is run with a higher temperature in the smelting zone, the furnace lines which were adapted for the lower temperatures are not necessarily those best suited for the higher hearth temperatures. If. enriched blast were used in a furnace, and higher temperatures run, it would be found necessary to further modify the lines of the furnace to meet the new conditions and to get the maximum output with economy. J. E. JOHNSON, JR., New York, N. Y.-It seems to me this is one of the few papers which could well have been a little longer. The data which Mr. Mathesius has given us, I think should be considered in connection with the paper which Mr. Brassert read before the American Iron and Steel Institute last spring, in which he described how they had obtained remarkable results with furnaces with steep but very short boshes; the angles have been raised to 80°, and the boshes made so short that they no longer appear as a conspicuous part of the shape of the furnace.

Jan 5, 1915

By L. G. Austin

The procedure for scaling breakage parameters determined in a laboratory mill to values for a full-scale mill is briefly presented. A simulation model of a closed circuit mill also requires a model of residence time distribution, a mass transfer law to predict over-filling as a function of flow rate through the mill, and a model to describe classification action. For fine dry grinding, or viscous slurry grinding, it is necessary to allow for slowing-down of breakage rates for a fine mill charge. Four examples of comparing simulation models to actual plant data are presented. The first is wet grinding of copper ore in normal closed circuit at 50 tph (metric) production, under conditions where the mill does not overfill. The second is the wet grinding of copper ore in reversed closed circuit at production of 87, 102 and 108 tph, with flow through the mill of approximately 150, 200 and 300 tph. The third is dry grinding of coal with a hot air sweeping stream to remove all of the coal as air-borne material, in open and normal closed circuit. The fourth is grinding of cement clinker in a two-compartment, air-swept tube mill in normal closed circuit with two different classifiers, producing 120 tph of 3250 Blaine cement. In all cases the simulated capacities and product size distributions were in reasonable agreement with actual plant performance.

Jan 1, 1984

By Charles J. Potter

There are many sources of energy available for consumption. Some available are solar, tide and wind. However, in terms of relatively large usage, only four principal sources are used for primary energy today. They are coal, oil, natural gas and water power. Such additional items as wood and nuclear energy, although supplying quantities of energy today, do not in the aggregate amount to any real significant quantity, but nuclear energy must be considered for future use. In addition, such a thing as gas from distillation of coal and oil is not considered primary energy. The principal markets for primary energy are the electric power utilities, space heating, industrial uses and transportation. The electric utility use of energy is primarily from coal, followed by natural gas and water power. Space heating is primarily a gas market, followed by oil and then coal. Space heating by electricity is only considered in the generation of electric power. Transportation's principal source of energy is oil. Coal has practically no market left in this field.

Jan 4, 1962

By Norman B. Pilling

Practical limitations to the usefulness of silicon steels are the hardness and brittleness silicon imparts to iron, making iron-silicon alloys of more than 8 per cent. silicon content unusable except where castings can be employed. In the use of commercial silicon steel, in thin rolled sheets, as in transformer construction, when the silicon content exceeds 4.2 per cent. the sheet is too brittle for satisfactory shaping by punching or similar operations. When such a brittle steel is sheared, it frequently breaks along a haphazard path in advance of the cutting tool. In Fig. 1 is shown a slightly enlarged view of the sheared edge of a 14-mil enameled sheet of nominally 4 per cent. silicon steel. In 5 in. along the sheared edge, only 44 per cent. was actually cut; the rest was torn, with the path of fracture varying widely from the path of travel between the shears. This is probably an extreme case of such brittle-ness, but a shearing or punching test is not necessary to reveal brittle-ness of this order; narrow strips will break when bent between the fingers. In Fig. 2, the proportion of actual cut edge is greater, but secondary fractures branch off at about 30" from the line of shearing in advance of the cut. Deprived of the support of adjacent parts of the sheet, the tips of the angles are bent out of the plane of the sheet by the shears, leaving a peculiar flared effect, like the set of the teeth on a saw. An end-on

Jan 1, 1923

By Dorsey Lyon

I. INTRODUCTION THE utilization of hydro-electric power in electro-metallurgical indus¬tries, aside from purely mechanical operations, may he of two kinds. The electric energy may be used to supply the heat necessary for the per¬formance of the chemical reactions of a metallurgical process, or the elec¬trolytic action of a direct current may be employed for extraction of metals, either in a reduction process or a refining process. In discussing this subject, it is well to distinguish between established industries, which are producing metals and alloys at a profit by use of the electric current, and the many processes which are either still in the experimental stage or have not even passed the paper stage of development of a patent. That is, we consider electro-metallurgical industries as commercial operations which are now consuming large blocks of electric energy, while processes which are not in commercial operation are only prospective consumers. Also, owing to the difficulty and risk of any attempt to foresee the effect of the European war upon electro-metallurgical industries, we have felt obliged to disregard the war entirely, and state our opinions regardless of its existence.

Jan 8, 1915

By Alfred G. Heggem

It is the purpose of this article to describe methods recently introduced into the oil and natural gas industry to safeguard the lives of the workmen and to protect property from destruction. Only such drilling methods are described as pertain directly to the operations necessary to maintain the well under complete control at all times. Wells Formerly Drilled Without Controlling Equipment It may seem incredible that practically all wells, until rkcently, were drilled without the provision of any means for control. To drill a hole into a boiler carrying high-pressure steam without first providing means to control the escape of steam would be unthinkable, yet in oil fields wells are drilled into a gas or oil formation with a possible pressure of 300 to 1,800 lb. per square inch and a daily flow of 20,000,000 to 80,000,000 cu. ft. of gas or 1,000 to 15,000 bbl. of oil per day. Some wells have produced in excess of 100,000 bbl. of oil per day, but these are exceptional cases. In addition to the loss of product, one must consider the great danger attendant upon the promiscuous liberation of such an amount of explosive and inflammable substance. Introduction of Metal Casing for Deep Drilling The introduction of metal casing to secure a permanent and impervious wall in a well made the drilling of deep wells possible and removed many of the original problems encountered in well drilling, but it did not insure the control of the well. To obtain the full value of the casing it was essential that a pressure-tight joint be made between the wall of the well and the lower end of the casing. Many materials in various forms were used, including cotton, hemp, stable refuse, oats, rice, cloth, leather, cork, rubber, lead, clay and cement, resulting, after a slow process of evolution, in the general adoption of two types of bottom fittings for

Jan 1, 1916

By Thomas Fraser, David R. Mitchell

THE primary purpose of the loading plant is to transfer the finished product from the preparation machines to the railroad car, truck, or barge in which it is to go to market. Secondary purposes of the loading plant are: to prevent excessive degradation of sizes during loading, to reduce segregation as much as possible, and to prevent excessive quantities of very good or off-grade coal from entering any one car. Nonuniformity of consignments is one of the chief sources of complaints by consumers and coal merchants. A properly designed loading plant will do much to reduce complaints and insure uniformity, not only from shipment to shipment but also in each individual consignment along the length of the car and in cross section. DEGRADATION IN STORAGE, LOADING AND SHIPMENT The object in loading is not only to handle the coal without breakage and segregation, but also to produce a well-trimmed load that will ride to its destination without spillage o~ breakage en route. The small sizes present in a car-of prepared coal as received by the purchaser consist of: missed small sizes not screened out in the preparation plant, breakage during loading, and breakage caused by handling en route. For domestic sizes of anthracite shipped from the Pennsylvania anthracite field to Atlantic coast cities, the dealers' loss because of breakage in loading and shipment amounts to from 2 to 5 per cent and for anthracite shipped to Middle West cities, the loss is 8 to 9 per cent. This difference is in part because dealers in the Middle West rescreen their coal more thoroughly than is usual in the East. One dealer handling Illinois No. 6 coal shipped from southern Illinois mines to Chicago reports an average size loss of 10 per cent when lump coal is unloaded with a fork. This runs as low as 5 per cent for carefully loaded coal and as high as 15 per cent for carelessly loaded coal. An Ohio dealer estimates the degradation in loading and shipment of West Virginia coals consigned to Ohio cities as follows: Pocahontas lump

Jan 1, 1950

I. PRESIDING OFFICER. At all business meetings of the Institute the President, or, in his absence, the First Vice-President, or, in the absence of both of them, any other Vice-President or Director, chosen by the meeting, Shall preside. At all other meetings of the Institute the President, or, in his absence, one of the Vice-presidents, Shall preside. If none of these be present the meeting Shall elect a Chairman. The President Shall do and perform Such other duties as may from time to time be assigned to him by resolution of the Board of Directors of the Institute. IL ORDER OF BUSINESS. At each business meeting of the Institute the order of business Shall be as follows: 1. Reading of minutes of preceding meeting. 2. Report of the President. 3. Report of the Treasurer. 4. Report of the Secretary. 5. Election of Directors. 6. Reports of Standing Committees. 7. Reports of Special Committees. 8. Special Orders. 9. Miscellaneous business. This order of business may be changed at any meeting, by a vote of a majority of the Members and Associates present. At all sessions of the Institute, other than business meetings, the order of proceedings and the time of adjournment Shall rest in the discretion of the presiding officer. III. SECRETARY OF THE INSTITUTE. The Secretary Shall keep a record of the proceedings of all the meetings of the Institute. He Shall be custodian of the corporate Seal, of the minute books and of all the legal documents belonging to the Institute. He Shall have charge on behalf of the Institute of all correspondence. He Shall notify all Officers and Directors and all members of committees of their election and appointment; Shall issue notices of all meetings of the Board, and of the annual and other business meetings of the Institute; and Shall, in calling Special meetings of the Directors, Specify the objects of Such meetings. He Shall act as clerk at all the meetings of the Board of Directors and at all meetings of the Institute. The Secretary Shall be custodian of all technical or Scientific papers Submitted to the Institute for its consideration and Shall have general charge and supervision of the editing and proof-reading of all material published by the Institute, and. of the distribution thereof. The Secretary shall be the custodian of all back numbers of the Transactions and other publications of the Institute. There Shall be kept under his direction an account

Jan 1, 1925

By Walter O. Roberts

A TOTAL eclipse of the sun is a brief, exciting spectacle witnessed by most men but once or twice during a lifetime. But to an astronomer an eclipse of the sun is an event of utmost scientific importance. For then, certain phenomena of the sun normally obscured by the brilliant glare of sunlight become spectacularly visible. For over seventy years prior to 1930 astronomers vainly attempted to discover a means of observing all of these eclipse features of the sun without a natural eclipse. But in 1930, through the genius of the French scientist, Bernard Lyot, astronomers met final success. Dr. Lyot invented a new kind of telescope known as a coronagraph, which made possible photography of all of the eclipse features of the sun. In 1940 Harvard University completed final testing of its Lyot-type coronagraph. the only one in the Western Hemisphere, and shipped it to Climax, where Donald H. Menzel, of Harvard College Observatory, supervised its establishment on the southeastern edge of the mining community of the Climax Molybdenum Co., with whose help and advice the modern residence and telescope dome of the observatory were constructed. Ever since that summer the station has been operated by me, first as a graduate student, and now as a staff member of Harvard College Observatory.

Jan 1, 1946

By Seymour G. Epstein

Using a modified capillary-reservoir technique, electromigration of dilute solutions of silver in liquid bismuth has been measured with relatively good precision. The effects of experiment duration, temperature. current density, and silver concentration have been investigated. Chemical diffusion coefficients of silver in liquid bismuth were also measured at temperatures ranging from 300°to 600°C. The effective valence of silver in bismuth was calculated as a function of temperature from a comparison of electric mobilities and diffusion coefficients. In an alloy containing 1 wt pct Ag, the electric mobility of silver increased from 1.65 x X sq cm per v-sec at 300°C to 2.38 x 10-4at 600°C; the diffusion coefficient in-creased from 3.0 to 17.5 x 10-5 sq cm per sec over the same temperature range. Calculated values of effective valence decreased from 0.28 at 300°C to 0.10 at 600°c. ALTHOUGH there has been considerable progress in the theoretical treatment of electron-transport properties in liquid metals, the mechanisms of mass-transport phenomena in liquid metals are still not clearly understood. This is especially true for the case of electro migration, alternatively termed elec-trotransport or electrodiffusion, which is mass transport induced by an applied electric field. A thorough knowledge of the mechanisms governing electromigration will considerably aid in understanding the electronic state of an impurity atom in a liquid metal. Electromigration has been long observed and studied in liquid metals and alloys. However, no satisfactory theory to explain the observed effects has been developed. The disparity in the present theoretical treatments, summarized by Verhoeven,1 has been attributed to the difficulty in describing the momentum transfer between electrons and ions and to the lack of precise measurements in liquid metals, especially at elevated temperatures. Prior to the last decade most of the electromigration studies were qualitative, in that only the direction of migration of alloy constituents was determined with any degree of reliability. These results have been summarized by schwarz,2 who was able to measure the electric mobility of several elements in mercury. More recently electromigration in liquid metals has been measured by a variety of techniques, with a varying degree of success. Mangelsdorf3,4 made precise measurements on dilute amalgams at room temperature, using a technique relating changes in composition to changes in alloy resistivity, but was unable to make measurements at elevated temperatures. Using a modification of this technique, Verhoeven and Hucke5 measured electromigration and resistivities in liquid Bi-Sn alloys. However, the resistivity technique is not sensitive to small composition changes and is impractical for very dilute alloys. Verhoeven and Hucke6 also measured electromigration of several solutes in liquid bismuth by adapting the capillary-reservoir method for determining diffusion coefficients in liquids. The reported precision of these measurements was poor, however, primarily due to the large uncertainties in the chemical analyses to determine concentration changes. Belashchenko7 has summarized the recent Russian investigations of electromigration, many of which, however, are of questionable accuracy. The present study was initiated to develop an experimental technique which would be both versatile and sufficiently sensitive to yield precise measurements of electromigration of solutes in dilute metal alloys at elevated temperatures. Using this technique, a comprehensive study of silver in liquid bismuth was made to determine the effects of experimental variables on the apparent electric mobilities. Chemical diffusion coefficients of silver in liquid bismuth were also measured over the same temperature range for comparison with the electromigration data. EXPERIMENTAL TECHNIQUE Electromigration Measurements. Electromigration of silver in liquid bismuth was measured by the capillary-reservoir technique, similar to that used by Verhoeven and Hucke,6 but modified to yield more

Jan 1, 1967

By B. A. Cheadle, K. P. Steward

Axial tensile, ring tensile, closed end burst, and free end burst tests were done at room tempe.vature and 300°C on three batches of Zircaloy-2 sheathing zuith different textures. Knoop hardness tests were also done on all batches. The mechanical properties of the tubes were largely dependent on the percentages of cold work, but were also markedly affected by the textures, particularly with respect to deformation behavio'r. The deformation behavior observed confirmed Picklesimer's predictions, zuhereas Knoop hardness results could be correlated with texture and yield strength anisotropy after the ,method of Wheeler and Ireland. From the mechanical properties, and from efjectiue strain values deterrlzined at the fractures using a photoqid technique, it zuas concluded that tubing witlz a single preferred orientation of radial basal poles best combines strength and ductility for any given deqee of cold work. THE mechanical properties required in collapsible Zircaloy-2 fuel sheathing for water-cooled power reactors are strength to resist wrinkling deformation by coolant pressure and ductility to accommodate a small amount of deformation in service without rupturing. Zircaloy-2 tubing during fabrication develops pre- ferred orientations of the a Zr grains due to aniso-tropic deformation behavior, and these textures markedly affect mechanical properties. Picklesimer' had predicted the deformation behavior of tubes with various textures, but the texture required to provide the optimum strength and ductility for a given degree of cold work has not been reported. To investigate this problem, tests at three transverse to axial stress ratios were done at room temperature and 300°C on three batches of Zircaloy-2 tubing covering a wide range of textures and percentages of residual cold work. Knoop hardness values were also measured to correlate with preferred orientation and yield strength anisotropy after the method of Wheeler and relland.' 1) MATERIAL For this investigation, three batches of tube-reduced tubing were chosen from the Zircaloy-2 sheathing produced for the Douglas Point Reactor. Individual tubes were 191/2 in. long, 0.600 in. OD, and 0.0165 in. nominal wall thickness. The identities of the batches, together with their textures, are shown in Table I. The tubes had the normal Zircaloy-2 composition3 of 1.5 wt pct Sn, 0.3 wt pct Fe, Ni, Cr combined with the following oxygen concentrations: Batch VII 1140 to 1390 ppm 0 Batch VIII 1400 to 1750 ppm 0 Batch IX 880 to 1320 ppm 0

Jan 1, 1968

By K. K. Clark

Excessive injection pressures in water injection wells may create deeply penetrating fractures, or may open up existing reservoir fractures. If these fractures are oriented toward offset producing wells, oil recovery at injected water breakthrough and ultimate recovery will be impaired. A method of calculating fracture lengths from pressure fall-off test data is presented. The method is based on a linear flow model that simulates conditions present during the early-time period after shutting in an injection well. Fracture lengths can be calculated directly if formation permeability is known. A graphical technique is presented that provides fracture lengths based on permeabilities calculated from normal fall-off tests, where those permeabilities are adjusted for flow geometry. Test data from four injection wells and results obtained from applying the method to these wells are discussed. Introduction Rates of water injection into nonstimulated wells in low permeability reservoirs frequently fall below economically desirable levels. Therefore, some form of stimulation such as hydraulic fracturing often is performed on these wells. Usually these fractures penetrate a short distance from the well — short as compared with interwell spacing — and therefore should not create problems of water channeling to offset producing wells. In the past, some operators have been tempted to increase injection pressures continually to maintain a specified injection rate. But pressures cannot be increased indefinitely. Field data indicate that continued injection above fracture opening pressure can cause excessively long fractures to approach between well distances. If these long fractures intersect or closely approach offset producing wells, premature water breakthrough can result. It is difficult to seal effectively these fractures by various workover procedures after premature water breakthrough has occurred. This paper describes testing procedures that are potentially capable of detecting premature water breakthrough before it occurs. Knowledge of fracture lengths and fracture opening pressures can assist field engineers in selecting optimum operating conditions for water injection wells. Fracture lengths should be calculated from pressure fall-off tests on injection wells, and maximum permissible iniection pressures should be determined from step-rate injectivity tests. Equipped with this information, the field engineer is in a better position to recommend for a particular injection well the optimum operating conditions that will lessen the chances of channeling to offset producers. Historically, pressure transient tests have been conducted primarily on producing wells and analysis procedures have been based on radial flow concepts. Several authors have suggested that these same procedures be applied to tests conducted on water injection wells. This application is justified for wells that are not connected to extensive fracture systems. However, if the formation is severely fractured, the interpretation methods must be modified. Several authors have presented the pressure response of various systems that are intended to simulate reservoir conditions. A paper by Russell and Truitt* on vertically fractured svstems is probablv the most useful from the standpoint bf the fieid engineer. Russell and Truitt presented the pressure-vs-time behavior of a well connected to vertical fractures with various fixed lengths. Their permeability adjustment technique is used in this paper to refine methods of calculating fracture length and interwell permeability. Theory and Definitions Three flow-system geometries are considered in analyzing injection well test data. These various geometries are applicable during specific time intervals of transient pressure tests. Schematic drawings of the flow models, and the time intervals over which they are applicable, are shown in Fig. 1 in the chronological order that they are applied to the pressure response of water injection wells in fractured formations. The very early response is simulated by an infinite linear system as shown in Fig. 1A. This representation permits the calculation of matrix surface area exposed to the fracture. The model shown in Fig. 1B is identical with the one studied by Russell and Truitt. They evaluated the transient pressure response of this vertically fractured system by finite difference techniques. The results were presented as tabulations of dimensionless pressure drop functions for a range of fracture lengths. A semilog plot of these data shows that the apparent matrix permeability can be related to the true matrix permeability by a simple exponential function. Their adjustment factor is used in this paper to improve the accuracy of matrix-permeability and fracture-length calculations.

Jan 1, 1969

By N. A. Gokcen, John Chipman

SILICON is the most commonly used deoxidizer and an important alloying element in steelmak-ing; hence a detailed study of this element in liquid iron containing oxygen is of considerable interest. The equilibrium between silicon and oxygen in liquid iron has been studied by a number of investigators but generally with inconclusive or incomplete results. The variation of the activity coefficients of silicon and oxygen with composition is entirely unknown. Published investigations deal with the reaction of dissolved oxygen with silicon in liquid iron and the results are expressed in terms of a deoxidation product. For consistency and convenience in comparison of the published information, the deoxidation product as referred to the following reaction is expressed in terms of the percentage by weight of silicon and oxygen in the melt in equilibrium with solid silica: SiO (s) = Si + 2 O; K'l = [% Si] [% 012 [I] Theoretical attempts to calculate the deoxidation constant for silicon in liquid iron from the free energies of various reactions yielded results which were invariably lower than the experimental values. Thus, the deoxidation "constants" calculated by McCance,1,2 Feild,3 Schenck, and Chipman were of the order of 10, which is below the experimental values by a factor of more than 10. Experiments of Herty and coworkers" in the laboratory and steel plant resulted in an average deoxidation constant of 0.82x10 ' at about 1600°C. The technique employed in their investigation was crude and the reported temperature was quite uncertain. The concentration of silicon was obtained by subtracting silicon in the inclusions from the total. Since at least some of the inclusions resulting from chilling must represent a fraction of the silicon in solution at high temperatures, such a subtraction is not justifiable. Results of Schenck4 for K'1 from acid open-hearth plant data yielded a value of 2.8x10-5, which was later revised as 1.24x10 at 1600°C. Similarly Schenck and Bruggemann7 obtained 1.76x10-5 at 1600OC. The discrepancies and errors involved in the acid open-hearth plant data as compared with the results of more reliable laboratory techniques were attributed by these authors to the lack of equilibrium and the impurities in liquid metal and slag, and are sufficiently discussed elsewhere." Korber and Oelsen" investigated the relation between dissolved oxygen and silicon in liquid iron covered with silica-saturated slags containing varying concentrations of MnO and FeO. The deoxidation products obtained by their method scatter considerably, and their chosen average values of 1.34x10, 3.6x10-5, and 10.6x10-5 1550°, 1600°, and 1650°C, respectively, represent the best experimental results which were available until quite recently. Darken's10 plant data from a steel bath agree approximately with their data at 1575° to 1625°C. Zapffe and Sims" investigated the reaction of H2O and H2 with liquid iron containing less than 1 pct Si and obtained deoxidation products varying by a factor of more than 20. Inadequate gas-metal contact and lack of stirring in the metal bath should require a longer period of time than the 1 to 5.5 hr which they allowed for the attainment of equilibrium. Furthermore, their oxygen analyses were incomplete and irregular and confined to a few unsatisfactory preliminary samples. Their results did indeed indicate that the activity coefficient of oxygen is decreased by the presence of silicon, although they made no such simple statement. They chose to attempt to account for their anomalous data by the unlikely hypothesis that SiO is dissolved in the melt. Hilty and Crafts" investigated the reaction of liquid iron with acid slags under an atmosphere of argon, making careful determinations of silicon and oxygen contents at several temperatures. Despite erroneous interpretation of the data at very low silicon concentrations, their data represent the most dependable information on this equilibrium that has been published. In the range 0.1 to 1.0 pct Si, their data yield the following values for the deoxidation product: 1.6x10-5, 3.0x10- ', and 5.3x10 at 1550°, 1600°, and 1650°C, respectively. The purpose of the work described herein was to study the equilibrium represented by eq 1 as well as the following reactions, all in the presence of solid silica: SiO2 (s) + 2H2 (g) = Si + 2H2O (g);

Jan 1, 1953

By M. E. Wadsworth, T. L. MacKay

Sintered UO, samples were leached in sulfuric acid solutions of various concentrations. A pressurized system was used so that it was possible to investigate the kinetics of the reaction to 270°C with oxygen overpressures as high as 900 psi. The rate was observed to be a function of the concentration of hydrogen ions and directly proportional to the partial pressure of oxygen. Evidences are presented which indicate that a UO2 surface site reacts with a molecule of water to form a hydroxyl complex which in turn can dissociate with the characteristics of a weak acid. A rate determining step has been proposed which involves the reaction between an oxygen molecule and the hydroxyl complex on the surface of UO,. ThE 2 principal methods for uranium dissolution are carbonate and acid leaching. The sulfuric acid leach is the more popular and is used for the treatment of the majority of the ores of Africa, Canada, and the United States. Low recoveries in basic leach circuits led investigators at the University of British columbia1 to study leaching of uranium ores in pressurized vessels. Early in the study of dissolution of uranium it was found that only uranium in the hexava-lent state could be leached in acid or basic circuits. Therefore, the use of oxygen over-pressure in an autoclave offered an interesting approach to solving the low recovery problems of carbonate leaching. UO, was used in this study because it could be obtained in high purity and also because it is representative of the most refractory of the primary uranium minerals. A pressurized system was used to provide a means whereby important temperature and pressure parameters could be varied for the evaluation of the kinetic processes. The mechanism for the dissolution of UO2 should be similar for any of the uraninite type minerals. At the present all of the kinetic studies that have been conducted have been in carbonate media. Peters and Halpern2 carried out a kinetic study of the leaching of pitchblende. Their specimens were pitchblende ores selected on the basis of high grade and homogeneity. Pearson and wadsworth3 conducted a kinetic study of the dissolution of UO2 in carbonate solutions with results very similar to those obtained by Peters and Halpern. EXPERIMENTAL The UO2 as received* was found by spectroscopic *Mallinckrodt reagent, supplied by the Atomic Energy Commission. analysis to have a purity of 99.94 pct 0.03. It was ground in a mechanical agate mortar and screened through a 400-mesh sieve. Thin flat disks of UO2 were prepared by pressing the sized powder in a specially constructed die at a total pressure of approximately 25 tons per sq in. The pressed disks were approximately 0.25 cm thick, 1.6 cm diam, and 3.5 g in weight. As pressed, the samples were approximately 65 pct of theoretical density. It was essential that a binder such as poly-vinyl alcohol be added before pressing to prevent formation of cracks when fired. It was found by trial and error that pressed disks sintered close to 1870°C in a hydrogen atmosphere, reach densities between 91 and 91.5 pct of the theoretical density. At this density the samples had no measurable porosity based upon a 2-hr emersion in boiling water. An X-ray examination of these sintered UO2 disks showed them to be identical with the original UO2 received. Reaction of UO2 with the alundum furnace core was prevented by placing molybdenum between the samples and the core according to the method of Corwin and Eyerly.4 Leaching studies were carried out in a specially designed autoclave, the details of which have been presented e1sewhere.6 The main features of the equipment as applied to a kinetic study are: 1) solution samples may be removed during the course of a single run; and 2) temperature and agitation are carefully controlled. Two-ml samples removed from the autoclave during the course of a run were analyzed for U3O8 content with a Beckman model DK-2 spectrophotometer by the method of

Jan 1, 1959

By M. E. Wadswort, A. S. Peck

Infrared data disclose that phenacite reacts with oleic acid to form a chemisorbed oleate monolayer on the mineral surface. The absorption band characteristic of the antisymmetrical C = 0 oleate structure appears at a spectral wavelength of 1623 cm-'. Chemisorption also results in the displacement of OH- and silicate from the mineral surface. Infrared absorbance at 1623 cm-1 is correlated with float-ability at different pH for -60-mesh phenacite particles. Phenacite, Be2SiO4, is an ore mineral often associated with quartz, microcline, and chrysoberyl in pegmatites and mica schist. Experimental phenacite beneficiating processes have been confined principally to the flotation of low grade ores occur-ing in several mountain ranges of Utah and Nevada. The U.S. Bureau of Mines ' has recently reported on the separation of phenacite from ore deposits of Mount Wheeler, Nev. Infrared techniques were previously applied by the authors to characterize the role of sodium oleate and oleic acid in the flotation of several non-sulfide minerals.23 A parallel study was projected to the flotation of the orthosilicate mineral phenacite with oleic acid. Infrared spectra provided a 'molecular fingerprint' of the mineral surface and permitted identification of the reaction mechanisms. Infrared data were complemented with flotation and chemical tests. EXPERIMENTAL PROCEDURES The experimental procedures used in this investigation, for which data are presented in graphical or spectral form, are described in chronological test order. Phenacite crystals from Mt. Antero, Colo., were obtained from Ward's Co., Monterey, Calif. The crystals were fragmented in a porcelain mortar to -60 mesh and then pretreated with 0.5 molar HC1 for 15 min to remove iron. Then, the mineral particles were washed free of acid with distilled water and dried. Part of the dried material was ground to a fine powder with a Fisher Grinder using an agate mortar and pestle. Next, the powder was placed in a graduated cylinder and mixed with 500 ml of distilled water. The mineral in suspension was decanted from the settled fraction after 5 min, and the colloidal suspension was used for adsorption tests in which a high specific mineral surface area was required for adsorption and infrared analysis. Conditioning was performed in 50 ml glass centrifuge tubes for both infrared and flotation test determinations. Twenty ml of colloidal suspension was used for the infrared adsorption tests. One and a half g of deslimed -60-mesh HCl pretreated phenacite was added to 20 ml of distilled water for flotation conditioning tests. Six mg of oleic acid was used for each infrared adsorption test, and 0.2 mg of oleic acid was used for the flotation conditioning tests. HCl and NaOH were used for pH modification. The pulps were stirred at a speed of about 1500 rpm for 3 min. Then, the solids were separated out and either dried at 50°C or immediately transferred to a float cell. The pH of the residual liquid was determined with a Beckman Zeromatic pH meter. The flotation procedure is described as follows: 1) A 325-1111 glass micro-float cell was filled with distilled water. 2) Conditioned mineral was placed in the cell and the pulp was aerated through the glass fritted bottom at 7 psi pressure. 3) Floated mineral was skimmed from the cell with a glass slide until flotation ceased. (The end point was reached in all tests in less than 2 min.) 4) The flotation products were dried, weighed, and the recovery was calculated. Samples for infrared analysis were made into mulls using either oleic acid or series 13-21 Halocarbon oil obtained from Halocarbon Products Corp., Hacken-sack, N.J. The mulls were placed between two sodium chloride windows. A characteristic phenacite infrared band at 1868 cm-' was used as an internal standard for quantitative determinations in which absorbance at this position was quantified by the baseline-tangent method4 and related to absorbance at 1623 cm-'. The ratio obtained by dividing absorbance at 1623 cm-' by absorbance at 1868 cm-' was defined as an absorbance quotient for use in graphical presentation.

Jan 1, 1968

By Strathmore R. B. Cooke, Eugene L. Talbot

THE perfluoro acids and derivatives show unusual surface-active properties that qualify them as possible flotation reagents. They lower the surface tension of water from 15 to 20 dynes below that obtainable with the corresponding hydrocarbon compounds.1, 2 Fluorochemicals adsorb very strongly on solid surfaces to give films that exhibit larger contact angles than films of the corresponding hydrocarbons."' * The large contact angles probably result from the terminal —CF3 group. The perfluoro acids are made by electrolysis of the corresponding carboxylic acid in anhydrous hydrogen fluoride.5 From the perfluoro acids many derivatives may be obtained, such as amides, amines, alcohols, xanthates, ethers and esters and others. Since the fluorinated analogues of the conventional hydrocarbon flotation collectors possess enhanced surface properties, a few were selected for testing. Because a survey of all possible minerals and reagent combinations would be out of the question, hematite was chosen to represent a nonsulphide system and pyrite to represent a sulphide system. The fluorinated reagents used in these experiments were prepared in the research laboratories of Minnesota Mining & Mfg. Co. Some were synthesized especially for this research. They are not available cokmercially. Separation of Nonsulphide Ores: The separation of oxides from silica has always been a challenge to the flotation industry because differences in surface properties of the minerals are normally insufficient to produce clean concentrates. Oleic acid," rosin acids,' and amine salts% ave been used to considerable extent to effect separation of metal oxides and silica. The system hematite-silica was chosen to represent the nonsulphides both because of its difficulty of separation and because large tonnages of easily obtainable material are available, such as gravity concentration tailings and nonmagnetic taconites on the Mesabi Range. The wash-ore tailings used here contained approximately 35 pct iron after desliming. Samples of the material used in this work were part of the same lot used by Chang, Cooke, and Huch9 and were prepared in an identical manner. Reagents for Nonsulphide Ores: Since one of the purposes of this investigation was to compare hydrocarbons with fluorocarbons, reagents of known behavior such as oleic acid, and the alkali metal salts of certain resin acids (Dresinates), were established as standards. Hydrocarbons and fluorocarbons of comparable chain length and other experimental fluorocarbons were tried as collectors for hematite. A list of the materials used and the concentrations of their stock solutions are given in Table I. Since silica can be selectively floated from hematite by conventional reagents," a few fluorocarbon reagents were also tried for this purpose. Their composition and concentrations are given in Table 11. Most of these reagents served the dual function of collector and frother. In the case of F-11 flotation did not occur but it served as a frother when F-6 was employed as a collector. Reagent grade sulphuric acid and sodium hydroxide were used to regulate the pH. Deionized water containing less than 0.1 ppm of salts expressed as NaCl was used for all solutions and flotation tests. The pneumatic flotation cell consisted of a 350-ml fritted glass Buechner funnel with a source of filtered air which could be controlled by a needle valve." A 50-g sample of ore and 250 ml of deionized water were added to the flotation cell and stirred slowly. The reagents were added and the pulp was conditioned before air was admitted to the cell. Approximately 15 ml of the pulp were removed for pH determination before flotation was started and were then returned to the system. The pH was again measured after flotation. Air was admitted to the cell until no further flotation occurred or until the character of the float changed markedly. Both the float and the nonfloat products were filtered, dried, weighed. and assayed for iron. The cell was washed in hot water and rinsed with deionized water after each test. Occasionally the cell was cleaned with concentrated hydrochloric acid to remove iron oxide particles from the glass frit. Experimental Results: Above a pH of 8, sodium oleate was an effective collector for hematite. The emulsification of equal parts of heavy fuel oil (20"

Jan 1, 1956

The Joint Session on Continuous Cast- ing, of the Institute of Metals Division and the Iron and Steel Division of the American Institute of Mining and Metallurgical Engineers, convened in the Jade Room of, the Hotel Waldorf-Astoria, New York City, on Feb. 23, 1944, at 9:15 o'clock, Carl E. Swartz presiding. C. E. SWARTZ.-It is gratifying to see so many out at what may seem an early hour for the beginning of A.I.M.E. sessions, but I think this number-some fifty or sixty of you-is an adequate expression of the interest in these processes all over the United States, and possibly in foreign countries. I would like to ask those who feel that this type of program is of value to you to write or speak to some one of the Institute of Metals Division officers and suggest other topics for symposiums. We have a feeling that some of these current practices are of interest and we believe that under proper sponsorship many of the companies will be willing to give publicity to processes such as those that will be discussed today. Also, we would like suggestions and criticisms, so that the next ones can be better. The subject of continuous casting is not new, of course. The two papers on the program this morning will adequately cover the history and some of the earlier processes, some of the theory and some of the practice, some of the reasons why these various methods did not work. I was rather interested in discovering, when thumbing through one of the A.I.M.E. publications the other night, an article on continuous casting. I was not aware that the A.I.M.E. had published any papers on continuous casting, but there may be a number. The one that I happened to find was published in the 1915 volume, on the Mellen rod- casting process, and so we might say this is not the first session in which these subjects have been under discussion. However, there have been many improvements since then in all fields of metallurgical and mechanical engineering; consequently, I think that the papers today will be a little more involved and a little more complete in their technique. The first paper today will be given by one of our gentlemen of the press, who has done one of the outstanding jobs in this country in calling to our attention some of the newer processes that are being considered and being used in the metallurgical indus-

Jan 1, 1945

By Thomas J. Menner

Jan 1, 1983