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By S. Isserow

RECENTLY, a description of the wartime work in this laboratory on the U-Si phase diagram was published. This diagram was available earlier in the open literature; as were Zachariasen's crystal structure identifications for the compounds in the system. The uranium end of the phase diagram is shown in Fig. 1. The most recent work on this system has emphasized the peritectoid E phase, of particular interest for a number of reasons. The early work provided evidence of this phase's resistance to corrosion in water and of its slight ductility. Further information on these properties has been obtained here. Work elsewhere4 has provided evidence of stability under irradiation. This body-centered-tetragonal phase is relatively isotropic compared to the more usually applied a or ? uranium phases. Unlike the other compounds in this system, it contains no Si-Si covalent bonds.3 In addition, consideration on the basis of Pauling's concepts leads to the conclusion that in the E phase, uranium has a higher valence than in any of the other phases. Definition of the composition of the ? phase has been of prime concern in the study of this alloy. Evidence is presented below that its silicon content is slightly higher than that of stoichiometric U8Si, the composition frequently assigned this phase on the basis of Zachariasen's identification. This work on the composition required careful attention to the method of dissolving the alloy for analysis, since apparently low silicon contents could be found under certain conditions, see Appendix. Preparation: Melting, Casting, and Heat Treatment—Almost all the samples were from castings with a diameter of 13/4 or 2 in. and about 1 ft long, weighing 10 to 15 lb. The U-Si charge was melted by heating to about 1650°C in an induction heated vacuum furnace. Beryllia crucibles were used at first, but were replaced by zirconia-washed graphite as the technique of keeping the carbon content low enough (about 500 ppm) was mastered. The alloy was bottom-poured at about 1650°C into graphite molds. A few small buttons, weighing no more than 50 g, were prepared in a small arc melting unit.' Since cast material has a preponderance of uranium and U8Si2, heat treatment is necessary to ob-tain the ? phase by the solid-solid peritectoid reaetion. Once obtained, the ? phase is stable to room temperature, obviating the need for speeial attention to the method of cooling after epsilonization, see Fig. 1. It was found desirable to epsilonize at 800°C for a week. For some purposes, in which residual uranium and/or U8Si2 are tolerable, shorter periods may be adequate. The temperature of 800°C is not critical, since essentially the same results were obtained from 785° to 825°C. Further departure from this epsilonization range is inadvisable.

Jan 1, 1958

By R. E. Zimmerman

THE separation of fine sizes of coal from its impurities by means of various flotation methods has become of increasing importance in the coal industry. This, no doubt, will be even more so in the future as the quantity of high grade coal is depleted, particularly that used for metallurgical purposes. The purpose of this paper is to describe and report the results of research work done under the auspices of the Pittsburgh Coal Co. to determine the amenability of their bituminous fine sizes of coal to flotation, to investigate the value of various reagents and factors affecting their use, and compare the results between froth flotation and bulk oil flotation. Compared with the preferential flotation of complex minerals, or ores, the flotation of coal is comparatively easy. However, this statement should not lull one into the feeling that there are no special problems involved. For instance, the separation of coal from pyrite in high sulphur coals is still far from being 100 pct successful. Size consist has considerable effect on reagent consumption and recovery. Other factors will be described and finally it must be remembered that in the flotation of coal a low priced material is being treated and thus economic considerations govern more closely its application than is generally the case in treating other minerals. As a result of the research work done by the Pittsburgh Coal Co. on the flotation of coal, it was concluded that it was practical to clean the -48-mesh coal commercially by froth flotation and after several different types of flotation units and circuits were investigated by means of pilot plants, large scale units were installed at their Champion Nos. 1, 4 and 5 Preparation Plants for the cleaning of -48-mesh slurries. These large scale operations have been recently described by D. H. Davis. 1 C. P. Proctor and C. B. Carlson2 in their chapter on Froth Flotation of Coal in the AIME Seeley W. Mudd series book on Coal Preparation describe some of the practical applications of our Pittsburgh Coal Co. laboratory work in actual plant practice as well as summarizing part of the investigational work. The author presents this paper, however, as a supplement to their reports, and records the basic research accomplished in the laboratory investigational work as well as the results of experi¬ments using bulk oil flotation. In presenting this work the author wishes to state much more work must be done in applying the principles of flotation to cleaning coal, especially in view of recent studies and practices in other mineral beneficiation fields. METHODS OF CONDUCTING LABORATORY TESTS The bulk of the research work was conducted in the laboratory of the Champion No. r Preparation Plant. This plant has elaborate facilities for sampling and analyzing coal and proved to be an admirable location

Jan 1, 1948

By G. H. Alani, H. T. Kennedy

One of the major difficulties in predicting the performance of oil reservoirs from their early pressure history lies in the uncertainty of estimating the volume of the liquid hydrocarbons contained in them. As a first step in filling this need, an equation was developed to determine the Inolal liquid volume of pure hydrocarbons over a wide range of temperature and pressure. The second step consisted of adapting the equation to apply to mixtures, with the heary hydrocarbons expressed as c The equatious are similar in form to van der Waals equation. hut the constants a and b tire considered as furnctions of temperature. In addition to the gas constant R, there are four constants characteristic of each hydro- When comptired with experimental values jound in the literal the. the average absolute deviation in the calculated molal volumes is found to be a Maximum of 0.33 per -cem for any of the pure liquid hydrocarbons studied. This maximum deviation was that found when comparing the calculated and observed values over a temperature range of 86° to 482°F and a pressure range from the bubbl-point ro 10,000 psis. The equations expressing the correlation for. mixrurrc were developed from 647 experimental measure-rilents of volume on 47 bouom-hole samples covering ; temperature range of 72" to 250°F and a pressure znge from bubble-point ro 5,000 psig. The average absotute deviation was found to he 1.6 per cent with the maximum for any measurement of 4.9 per cent. INTRODUCTION Accuratc information of the pressure-volume-temper-iiture behavior of hydrocarbon liquids is of considerable importance in the field of both applied and theoretical science and, especially, in the solution of petroleum reservoir engineering problems. These PVT relationships can be expressed graphically, in tabular form or as equations of state. Equations of state for gases have been developed based on the ratio of pressure, temperature and volume to the pressure, temperature and volume at the critical points of the hydrocarbons. These equations have been successful in yielding values fairly accurate for reservoir engineering purposes. For liquids, however, relations of this type are more complex and have not yielded useful results. The composition of reservoir liquids is normally expressed in terms of the moles of hydrocarbons C,? C,. C,. elc, per mole of mixture. The composition must include the fraction of a mixture such as C,,, which cannot be separated with reasonable time and effort into specific hydrocarbons. Although there are several equations of state having variable degrees of accuracy applicable to pure liquid hydrocarbons, none includes a means for estimating the volume of mixtures as a function of temperature. pressure and composition expressed in this manner.

By R. E. Mussler, F. E. Block, T. T. Campbell

An exploratovy study was made to deternzine the feasibility of preparing beryllium by the metallother-. mic reduction of beryllium oxide. The procedure involved heating a relatively nonvolatile metal reductant in contact with beryllium oxide in a vacuum. Beryllium vapors formed in the reaction were condensed as a coherent deposit on a heated surface. Reductants tested included tanthanun, yttrium, thorium, Th-Mg, and Zr- Ti alloys, and the hydrides of lanthaniir~z, yttriunz, and zirconiur?7,. Test ten7pevatures ranged from 1350'to 175O' C, and reaction times ranged frot 30 to 100 lzr. In most cases metal recoveries were lola, although yields close to 90 pct of theoretical were obtained with latzthanum, yttrium, and zirconium reductants. In most cases metal deposits were contanzinated by beryllides, /ls/cally of the Beln M or Bel3 M type. BERYLLIUM has a variety of unique properties including light weight (sp gr 1.85), low thermal neutron absorption cross section, high scattering cross section, excellent dimensional stability, high strength to weight ratio, high melting point (1285"C), high specific heat, and high thermal conductivity. Interest in beryllium as a structural material in aerospace and nuclear-reactor applications is based on these properties. In general, the potential of beryllium has been only partially realized, largely because of the brittleness of poly crystalline forms of beryllium, difficulties associated in its fabrication, and joining problems encountered in its use in structural applications. Several excellent books and monographs are available to those interested in the occurrence, extractive metallurgy, and utilization of beryllium.1"* Although an extensive amount of research on beryllium has been in progress during the past 10 years, much of the work has been concerned either with the so-called "ductility problem" or with the development of methods of fabrication and evaluation of properties of various commercial or purified grades of metal. A recent survey of the literature indicates that only limited efforts are presently being directed toward developing new methods for reducing beryllium compounds to metal. Two major commercial methods now used to produce beryllium are the magnesium reduction of beryllium fluoride and e lec trow inn ing of beryllium from fused sodium chloride-beryllium chloride salt baths. Only a limited amount of work has been done on the direct reduction of beryllium oxide. Major factors which complicate this method are the great stability of beryllium oxide and the reactive nature of beryllium metal. The stability of the oxide necessitates extremely high reduction temperatures and vacuum operation to liberate beryllium metal vapor and cause reactions of the following type to proceed: XBeO(s) +YM(s)-MYOX(s) + XBe(& As early as 1939, roll' used this reaction for the direct reduction of beryllia by zirconium and titanium, and later in 1952 ~a~el~ studied the reduction of beryl-

Jan 1, 1967

By J. H. Keeler

The tensile characteristics of Zr-Fe binary alloys containing up to 5 atomic pet Fe are reported for the temperature range —195o to 500°C. A linear relation between stress at constant strain and volume fraction ZrFe2 was found. The coincidence of data from unalloyed zirconium with zero volume fraction ZrFe2 indicated little or no solid solution in IL-zirconium, in agreement with Hayes, Roberson, and O'Brien.' The absolute increase in strength due to particle strengthening, although decreasing with increasing temperature, was a greater percentage at high temperature. ZIRCONIUM is of interest for use in nuclear reactors because of its low neutron absorption, good corrosion resistance, and high melting temperature. The alloying of zirconium with iron has been considered as a means of increasing the mechanical strength of zirconium without seriously increasing the neutron absorption " over that of unalloyed zirconium. The Zr-Fe system has a eutectic at 934°C and 23.7 atomic pet Fe and a eutectoid at 800°C and 4.0 atomic pet Fe. The zirconium-rich end of this system determined by Hayes, Roberson, and O'Brien' is shown in Fig. 1. The intermetallic phase coexisting with a and ß-zirconium has been reported as Zr2Fe3,1 with a,, - 7.04A, and as ZrFe2,2 face-centered-cubic, the phase being of the MgCu, type (C-15). It was more recently agreed to be ZrFe33 and face-centered-cubic. This intermetallic phase is essentially insoluble in a-zirconium, the hexagonal-close-packed modification; and the lack of solubility makes the system particularly interesting metallurgically. The system is strengthened almost exclusively by particles of in-termetallic phase, and there is very little solid solution strengthening to complicate the analysis. The Bureau of Mines, in its survey of zirconium-base alloys,' reported the tensile properties of Zr-Fe alloys made from chloride process zirconium, induction melted in graphite crucibles, and swaged at 850°C in iron sheaths. Additional data on these ZrFe alloys were given by Hayes, Roberson, and O'Brien.' Chubb and Muehlenkamp% have recently reported the strength of Zr-Fe alloys containing up to about 1.25 atomic pet Fe. These alloys were made from crystal bar zirconium, hot worked at 820°C, annealed at 700°C, and tested both at room temperature and at 316°C. Experimental Procedure The materials used in this investigation were high purity zirconium made by the iodide process and electrolytic iron. The composition of the zirconium as obtained by spectrographic analysis and the nominal composition of the iron are given in Table I. Alloy ingots weighing 100 g were made by are-melting under argon in water-cooled copper crucibles in a multihearth furnace."

Jan 1, 1957

By H. H. Stout

IN the early fall of 1025, the writer was conducting, in the Ledoux and Co. labora-tory, New York, experiments directed to-ward ascertaining the effect on its impurity content when cathode copper was subjected to a current of various gases at an elevated temperature below the melting point. The apparatus consisted of a vertical I-in. dia. silica tube about 12 in. long, heated on the outside. The cathodes were broken to pass 3/8-in. mesh, and a current of various differ-ent gases was passed up through a 4-in. long column of these loose cathode particles in the vertical tube furnace. Temperature was maintained to 1500° to 1600°F. and the gas treatments lasted from 3 to 6 hr. The writer observed that whenever reducing gas (H2 or CO) was used, these cathode par-ticles stuck together at points of contact with each other. The cohesion was so marked and tenacious that an examination was made of the fractured surfaces, when cathode particles were broken from the cluster. Crystal growth was always found to have taken place across the surfaces where separate particles were in contact, but only after all oxides, sulphates, etc., had been completely removed. The idea of a possible new process was then conceived and was disclosed to A. M. Smoot (V. P. Ledoux and Co.) with intent to obtain his views. The first conception as given Smoot was "to gas-clean broken cathodes, put them in an extrusion press, solidify and extrude them at around 1500°F." Smoot's reaction, after a few moments considera-tion, was, "It looks perfectly all right to me." The writer and his assistants, W. H. Osborn and H. H. Stout, Jr., after confer-ring as to ways and means, decided to go ahead with preliminary laboratory experi-ments, which, it was thought, would move the new process from the possible to the probable. This program followed a course indicated by three basic considerations: I. Since brittle cathodes were often unin-tentionally produced, it seemed probable that the laws controlling this type of deposi-tion could be ascertained. 2. We had already proved the gas-clean-ing feature. 3. There remained to prove: whether a sound, homogeneous metal billet could be produced with crystal growth established over the entire surface of each individual particle in the billet; and, if so, what would be the physical properties? Osborn arranged with Columbia Uni-versity for conducting experiments in its research laboratory to prove or disprove the third item; Columbia assigned C. A. Phillipi, Jr. to assist in the project. A press with a cylinder 2 in. high and of I-in. dia. was used. It was surrounded and heated by a resistance coil of Nichrome wire. Broken tough cathodes were used.

Jan 1, 1940

By Worthen Bradley, R. G. Hall

THIS paper will attempt to show how a metallurgical problem at one California quicksilver mine was solved, and how the solution was applied successfully at another mine. The pronouns "we" and "our," as used below, refer to the Bradley Mining Co. of San Francisco. The term "concurrent firing" for the purpose of this paper can be defined as feeding and firing a rotary kiln at the same end-that is, of course, the upper end. This is as opposed to "counter-current firing," the orthodox method, in which a kiln is fed at the upper and fired at the lower end. The terms "quicksilver" and "mercury" are used interchangeably. EARLY REFERENCES The earliest work on nonferrous metallurgy, we believe, was The Pirotechnia of Vannocio Biringuccio,1 its first edition having been printed in Italy in 1540. Quoting from its chapter entitled "Concerning Quicksilver and Its Ore": Quicksilver . . . is one of the gods and has divine strength in itself, and also, to the annoyance of the alchemists, it is winged. Hence, when it sees that it is in gravest danger, it loosens itself from . . . every bond . . . and flies away into the heavens, escaping from the hands of those who crucify it. Almost laughing, it leaves all its adversaries mocked and scorned, with their phials and filters empty . . . How thorough a job, under certain conditions, it can do of mocking its adversaries and leaving their phials and filters empty, was found out four centuries later at the Sulphur Bank mine, on the east shore of Clear Lake, in Lake County, California. The other mine mentioned in the title is the Reed, in Yolo County, California, 35 miles by road southeast of Sulphur Bank. Reed and Sulphur Bank ranked respectively fifth and seventh in U. S. production in 1943. The earliest direct reference we can find to furnacing troubles at these mines was by Thomas Egleston in 1890.2 Speaking of Sulphur Bank, Egleston says: Sometimes there is more sulphur than cinnabar in the ore, which is a detriment to both . . . making the sulphur impure, and rendering the cinnabar difficult to work on account of the soot. In some of the early . . . furnaces the accumulation of soot from the excess of sulphur has been known to penetrate as far as the fan blower at the end of the . . . condensers, and completely prevent its revolution. In order to get rid of the inconvenience of this accumulation . . . , as well as to get a commercial value from the sulphur, it (the sulphur) is now separated by steam and sold. It is claimed that the sulphur alone pays all the expenses of . . . the mine. The mine was first worked for sulphur, and the cinnabar it contained was considered to be an inconvenience, and was carefully picked out and thrown away. as its richness and value were not

Jan 1, 1945

By Otto F. Pfordte

In my paper on " The Refilling of Sulphides Obtaihed in the Lixiviation-Process with Hyposulphite Solutions " (Trans., xx., 37), I gave the outlines of a process for refining sulphides. In a subse-

Jan 1, 1893

By AIME AIME

MORTIMER ELWYN COOLEY, dean of the College of Engineering and Architecture of the University of Michigan, has been elected president of the American Engineering Council of the Federated American Engineering Societies. This was announced at a meeting of the Executive Board of the Council held at the Cosmos Club in Washington on Sept. 30. Dean Cooley assumes office at once. The new head of organized engineering is a past president of the American Society of Mechanical Engineers and has a long record of distinguished service in education, under the government and in private capacities. He was born in Canandaigua, N. Y., March 28, 1855, and was graduated from the United States Naval Academy in 1878. With his classmate, Dr. Ira N. Hollis, he was ordered to the U.S.S. "Quinnebaug," then fitting out at the Norfolk Navy Yard preparatory to a cruise in the Mediterranean.

Jan 1, 1921

By ELIHU THOMSON

IN 1877, Professor Thomson delivered at the Franklin Institute, [Philadelphia, five lectures on electricity. The object of the lectures and the demonstrations, which were numerous and many of them original even to the employment of special apparatus constructed by the lecturer, was to show clearly that electricity, of whatever name, was the same., differing only in tension (as it was termed) and in the current flowing, or quantity (the old term), in steadiness or in wave-like character. In those days, the textbooks divided the subject into statical and dynamic electricity, with sub-divisions such as frictional electricity, voltaic electricity, magneto electricity, electromagnetism, thermo electricity, and animal electricity. The well-known Ruhmkorff coil,' or spark coil as it is now called (as when used for the ignition of automobiles), was employed to step, up a battery current to a high-tension discharge which would charge condensers, such as Leyden jars.

Jan 1, 1921

By AIME AIME

M ODERN metallurgy properly belongs to this century. The great advance made in this science is directly attributable to the discovery of the Roentgen rays. Application of the results of this discovery, together with the more recent corroborating studies in electronic diffraction have definitely and for all time established this science. Metallurgists today speak with familiarity of the atoms of the different metals in terms of their orientation, atomic volumes, lattice structures, dimensional lattice constants distance of nearest approach, and the like. One matter of profound interest, which is quite staggering to the imagination of the human mind, is the enormity of the number of atoms even in a small particle of metal. As an illustration, let us compute the number of atoms in the volume of one cubic centimeter in a single grain of absolutely pure copper. Eighteen and a fraction cubic centimeters equal the volume of one cubic inch.

Jan 1, 1940

By L. D. Mullins, E. B. Elfrink, W. L. Wahl

In the past few years several articles and papers presenting results of solution gas-drive depletion calculations have appeared in the lit-erature. Such calculations are of interest to the oil industry, for investment decisions must often be made before much is known about a reservoir. At other times, an estimate of the possible benefits to be realized from alternate production methods is desirable, and theoretical depletion calculations can serve as a floor or reference level from which to work. In any case, an estimate of ultimate oil recovery based upon engineering data is commonly required. An engineer confronted with the problem of obtaining, for a specific reservoir system, an estimate of ultimate oil recovery by solution gas-drive depletion usually will be forced to perform the calculations himself. This is despite the quantity of data in the literature. Rarely will either experience or the literature provide results from a reservoir system similar in all important respects to the one under consideration, and calculated results are not so plentiful that satisfactory interpolation procedures can be devised. Performing the calculations, however, is a tedious, time-consuming task unless an electronic computer is available, and, in practice, time and manpower are not always available for this purpose. A quick, simple, consistent method was needed for reducing the uncer- tainty in estimated oil recovery from solution gas-drive reservoirs when only minimum information about the reservoir system is available. PROCEDURE Method of Calculation The usual requisite assumptions were made so that the material balance equation could be used to calculate data for the charts. The following assumptions were made: (1) the reservoir is homogeneous and isotropic; (2) oil recovery is due entirely to solution gas drive and neither a gas cap nor a water drive nor gravity drainage is present; (3) the initial reservoir pressure is the bubble-point pressure of the reservoir fluid; (4) initial total liquid saturation is 100 per cent of pore space; (5) interstitial water saturation remains at the initial value as the reservoir pressure declines from the bubble-point pressure to atmospheric pressure; (6) equilibrium gas saturation is 5 per cent of pore space; and (7) oil and gas saturations are uniformly distributed throughout the reservoir at all times. There are no saturation gradients due to a wellbore, nor is the geometry of the reservoir system considered. The material balance equation was written in the form of a differential equation' which was integrated to determine the change in oil saturation for an assigned pressure drop. Formal integration was not possible, so recourse was made to the Runge-Kutta method' of numerical integration. All computations were performed on IBM equipment. Numerical integration yielded the change in oil saturation within the reservoir as the pressure. declined from the bubble-point pressure to atmospheric pressure. The initial oil saturation minus the change in oil saturation yielded the oil saturation at atmospheric pressure. The oil originally in place was obtained by dividing the initial oil saturation by the initial formation volume factor (differential liberation) while the oil in place at atmospheric pressure was obtained by dividing the final oil saturation by the formation volume factor at atmospheric pressure. U1timate oil recovery, expressed as a percentage of the initial oil in place, was obtained by dividing the difference between the oil initially in place and the oil in place at atmospheric pressure by the oil initially in place and multiplying by 100. PVT Data Charts were based upon 135 solutions to the material balance equation. PVT properties of the reservoir fluids were variables in this equation and had to be known as functions of pressure. The required PVT data might have been obtained from either actual reservoir fluid systems or correlated data. However, correlated PVT data were developed and employed in the calculations for the following reasons: (1) it is doubtful that 135 sets of PVT data could have been obtained for the values of variables investigated in this study, and (2) results of recovery calculations from randomly obtained PVT data could not be correlated as well as rssults from selected PVT data. The PVT data used to develop the

By A. V. Bradshaw, R. I. L. Guthrie

The behavior of large bubbles in the size range 4 to 25 cm3, rising through molten silver, has been studied. It was found that rising velocities were equivalent to those in aqueous systems of low viscosity. Mass transfer coefficients for oxygen bubbles dissolving in silver were found to be 0.036 ± 0.007 cm sec-1, being close to those predicted for transfer through the front surface of the spherical cap bubble only. It is suggested that the surface active nature of oxygen in silver could account for the relatively low coefficients obtained. MANY metallurgical processes involve interactions between gas bubbles and liquids. Examples include the removal of carbon monoxide in Open Hearth Steelmak-ing, the removal of sulfur by blowing air through copper matte during converting, and the removal of hydrogen from steel during vacuum degassing or inert gas flushing. The steps involved in such refining processes include; transport of the dissolved species to the bubble interface, adsorption and chemical reaction of the species at the interface, desorption of product molecules from the interface, and transport of product gas into the bulk gas phase of the bubble. It has been concluded1 that all the interfacial steps involved proceed so rapidly at steelmaking temperatures that transport of the solutes, present in the metal, become the important rate controlling factors provided nucleation phenomena are not restrictive. The O-Ag system was chosen for the investigation into gas bubble-molten metal interactions due to the relatively high solubility of oxygen that enables rates of oxygen transfer to be measured from changes in bubble volume. Other advantages of this system include the absence of a stable oxide phase at an oxygen pressure of 1 atm and the relatively low melting point of the metal which permits the use of a metallic container, providing that it is resistant to oxidation. In those metallurgical processes where bubbles have an important influence, bubble volumes are usually greater than 5 cm3. For this reason the present study relates specifically to single large bubbles of oxygen rising in silver. These bubbles adopt the characteristic spherical cap shape similar to that shown in Fig. 1 for a 30 cc bubble rising in water. After an initial investigation to determine the velocities of inert (nitrogen) bubbles rising in molten silver, experiments were carried out with oxygen and the rates of mass transfer between the oxygen bubbles and the silver were measured. EXPERIMENTAL Apparatus. The apparatus, Fig. 2, for containing molten silver, was constructed from "Nimonic 75" Alloy (75 pet Ni, 20 pet Cr, 5 pet Fe, Mn) and provided for the release of single bubbles from an hemispherical cup, situated at the bottom of the column. The cup was turned by translating the rotation of the drive shaft through 90 deg. This was accomplished by the use of a bevelled gear system, and a smooth drive was provided by the lubricating action of the silver on the gears. Since reliable high temperature seals at 1000°C were found to be impracticable, the filling and drive shaft tubes were extended outside the 3.5 kw resistance wire tube furnace, where connections were made using easily accessible O-ring seals. The apparatus remained gas tight to the atmosphere at pressure differentials far in excess of those used. The filling tube was connected via a small bore tube to the differential pressure transducer. Gas could be bubbled into the inverted cup from two i-in. tubes which passed down the inside of the column to preheat the gas. The temperature of the silver was maintained at 1020°C during all experiments. Measurement of Bubble Volume. In order to calculate mass transfer rates, it was necessary to obtain a continuous record of the bubble's volume during its passage through the column of molten silver. The method adopted for measuring the bubble volume involved closing off the top gas space to the atmosphere prior to each experiment, and recording the variation in gage pressure of this space during the formation and rise of the bubble. Since any change in bubble volume results in an equal change in top space volume, Boyles Gas Law may be applied (for isothermal con-

Jan 1, 1970

By E. Martinez

Samples of chrysocolla, a hydrated copper silicate, from several sources were submitted to differential thermal analysis (DTA) and thermal gravimetric analysis (TGA). Pure samples of chrysocolla are difficult to obtain, but comparison of the thermograms revealed that certain reactions occurred in all the samples and it is believed that these are due to chrysocolla. Endothermic reactions occurred at 50' to 175°C, 350° to 650°C, and 980° to 1100°C each of which caused a weight loss. The first was due to loss of absorbed water, the second to a dehydroxyla-tion, and the last to conversion of cupric oxide to cuprous oxide. In addition, two exotherms were detected at 685° to 695°C and 935° to 950°C. Infrared spectra of heated samples indicated the exotherms were due to changes in the Si-O bonds leading to the formation of cristobalite. The results suggest that thermoanalysis may be a more sensitive and reliable method for detection and identification of chrysocolla than X-ray diffraction, infrared spectroscopy, or optical techniques. The recovery of copper from oxide ores has been the subject of much research in recent years. One of the principal oxide copper minerals is chrysocolla, a hydrated copper silicate. The information available indicates that it has widely varying properties depending on the origin of the sample. Chrysocolla usually is found associated with cuprite, malachite, azurite, and native copper. Most of these other minerals are recoverable by present day flotation practice, but chrysocolla is lost in the tailings.1,2 Reagent combinations that are successful in laboratory chrysocolla flotation with ore from one source have been found to be ineffective with another. 3 The copper segregation process offers an altemative to beneficiation of oxide copper ores.4'5 The process is of particular interest in processing ores that cannot be treated by conventional hydrometal-lurgical methods because of high acid consumption.6 Fuller understanding of the properties of chryso- colla may prove of value in the search for improvements in both the flotation and segregation processes. Chrysocolla samples from Arizona, Nevada, Chile, Australia, and South Africa were studied by differential thermal analysis (DTA) and thermal gravimetric analysis (TGA). In addition, a sample from Miami, Ariz., was submitted to X-ray diffraction, infrared spectrophotometry, and surface area determination. EQUlPMENT Differential thermal analysis (DTA) detects, amplifies, and records exothermic-endothermic reactions occurring in a sample as its temperature is raised at a constant rate, usually 10°C per minute. A unit made by the Robert L. Stone Co. was used in this study. The tests can be run if desired with a gas streaming through the sample. A thermobalance records weight losses or gains in a sample as its temperature is raised at a uniform rate. The gravimetric analyses (TGA) were run on a Chevenard thermobalance converted electronically for graphic recording. A heating rate of 5°C per minute up to 1100°C was used in these tests. A Perkin Elmer Infrared Spectrophotometer, Model 221, was used with sodium chloride optics obtaining IR spectra in the 2 to 15 region. A pressed pellet technique with potassium bromide was used in preparing the samples. DESCRIPTION OF SAMPLES Chrysocolla is found in the oxidation zones of copper deposits commonly associated with malachite, azurite, and limonite. It is described as varying in composition and in color from bluish green to brown or black. Inclusions of other minerals are usual so chemical analysis of chrysocolla samples may be suspect. However, it is considered by many to be a solid solution of CuO, SiO2 and H2O with a general formula of CuO.SiO2.2H2O or 2CuO.2SiO2. 3H20. Chukhrov7 has described a sample from the Urals as CU3,5(OH)2 (A1Si3) O10.nH2O and stated that chrysocolla is a montmorillonite-type mineral. On the basis of X-ray analyses, DTA, and infrared spectra of chrysocolla from the Inspiration Mine, Ariz., Sun8 concluded that there was no substantial evidence to classify it as a montmorillonite mineral. Chrysocolla samples from many sources throughout the world were used in this investigation. The following is a brief description of each:

Jan 1, 1963

By William G. Pariseau, H. Douglas Dahl

Recent subsidence legislation indicates that mining engineers would be welt advised to be able to predict and control surface damage caused by mine subsidence. To date, such an ability is practically nonexistent. Model analysis is suggested as one of the alternative paths available which might yield fruitful results. Similitude requirements developed for a self-loaded body in static or quasi-static equilibrium indicate that complete similitude without centrifuging is an impracticability. However, a pilot experimental study which used a simplifying assumption to correctly model mine subsidence has produced results in qualitative agreement with field observations. The purpose of this paper is to present a discussion of the various approaches that can be taken in the study of mine subsidence phenomena. Particular attention is focused upon the rational selection and use of laboratory models. Broadly interpreted, mine subsidence is the deformation of the rock mass enclosing a mine. Depending upon a number of factors, the movement of the subsiding rock mass may disrupt gas and water lines or other buried utilities, damage surface structures such as buildings and bridges, dislocate streams, roads, and rail lines, aggravate acid mine drainage and fire problems, and generally mar the landscape. It is clearly a problem that no mine manager can safely ignore. It is also a problem that will grow with the general population increase. In the following discussion, a summary review of past and present approaches to subsidence studies is given. The possibilities of duplicating subsidence phenomena in laboratory models are examined, and an analysis of a particular type of model is presented. Some preliminary results obtained from a model of the particular type analyzed are then discussed. REVIEW OF PREVIOUS WORK Historically, subsidence investigations have been empirical studies in the field and laboratory or theoretical analyses of mathematically idealized media. Empirical and theoretical work in the United States has generally lagged behind investigations abroad. In the United States, field studies are mostly pre-World War 11. These are summarized in the Mining Engineer's Handbook. ' Field studies in Europe are more recent and more extensive. Those made in Great Britain are summarized in the Subsidence Engineers Handbook2 and represent observations made at 157 different collieries. Such studies by themselves are of limited usefulness as are all empirical studies. One can never be certain that conditions at one mine will be similar enough to those at another to warrant the drawing of like conclusions. European subsidence formulas rely heavily upon the "angle of draw" and "critical area" concepts. The angle of draw is defined as the angle between a vertical line through the face, and another line extending from the face to the surface at the point where movement is zero. The critical area is defined in relation to the least extraction necessary to produce maximum subsidence. Fig. 1 illustrates the angle of draw and critical area concepts. First and second "limits of influence" are also shown. The angle of draw and associated critical area concept are obviously not well defined, being dependent upon the accuracy of the surface survey. In Great Britain, the angle of draw has increased through the years from about 26 to 35°. In the United States, zero and negative angles of draw have been reported. In the authors' opinion, these purely geometrical concepts represent an oversimplification of subsidence phenomena and their use, in the United States at least, should be discouraged. Empirical observations of laboratory models containing layers of earth, sand, clay, and plaster were made by Fayol (cited by Peele) as early as 1885. An outgrowth of his work was the "dome theory," a verbal description of what is assumed to occur in subsiding rock masses. The dome theory has since fallen into disrepute. Theoretical analyses worthy of the name treat a subsiding rock mass as a deformable body. In these analyses, the actual rock mass is replaced by an idealized material that deforms according to a simple stress-strain relationship. The stress equations of equilibrium expressing the Newtonian laws of mechanical action and the geometry of strain furnish additional equations that must be satisfied. A loading criterion-generally understood, and in some cases stated explicitly-completes the theory.

Jan 1, 1969

By J. D. Ridge

The geologic setting and mineral relationships of seven European massive sulfide deposits that more or less conform to the bedding of the largely noncal-careous sedimentary rocks and/or bedded volcanics in which they are found are considered here. These orebodies consist largely of massive beds or lenses of sulfides usually surrounded by halos of disseminated sulfides and distorted by tectonic activity. The formations containing these deposits have been metamorphosed in varying degrees at times subsequent to their lithification. The ore-forming process is thought to be essentially volcanic, with the ore constituents being brought to the shallow-water site of deposition through tectonic fissures from magma chambers at depth as gases or relatively concentrated hydrother-mal solutions. Certain European ore deposits of base metal sulfide have previously been considered to be of hydro-thermal or magmatic origin, but today a number of European mining geologists consider them to be syngenetically produced. In an effort to provide American geologists with some idea of the reasons behind this change in thought, the geological settings of seven of these deposits have been studied. These are: Ldkken, Meggen, Rammelsberg, Ergani-Maden, Outokumpu, Boliden and Roros. These deposits lie in bedded rocks that have undergone metamorphism from causes not universally agreed upon; most of the formations were originally shales, and may have been intercalated with limey and occasionally quartzitic beds, volcanic tuff, agglomerate, extrusive lavas and usually basic intrusives. Deposits of the conformable type, however, are not confined to these rock types but may be in calcareous and associated igneous rocks or almost entirely in volcanics. These deposits may be closely associated in space with igneous rocks that, again, are usually basic types. Although the ages of the enclosing rocks range from mid-Precambrian (Boliden and Outokumpu) to Eocene (Ergani-Maden), the bulk of them are Paleozoic, with two (Meggen, and eammelsberg) being upper middle Devonian and two (LØkken and RØros) being Cambro-Ordovician. Geographically, two are in West Germany, four in Scandanavia and one in Turkey. Of the seven deposits, six are mined for copper, with three of these also producing zinc, and two lead; one is mined for zinc and minor lead. In the discussions of the seven conformable deposits that follow, I have attempted to present as uniform a treatment as their varying characters will permit. For each deposit, I have considered the stratigraphy of the area, its major structural characteristics, the form of the orebodies, their mineral content, and the origin of the ore. In the last of these subdivisions, I have presented only the viewpoint of those who believe the ores to have been formed by syngenetic processes, processes that went on at the same time as those which produced the beds that enclose the ores but that are not, in the deposits in question, thought to have been sedimentary in the strict sense of the term. The materials of which these orebodies are composed, it is suggested, did actually collect by falling through sea water to the floor of that portion of the sea in which they accumulated. The ore constituents, however, are believed by a considerable number of European geologists to have been added to the sea water from intratelluric sources, probably igneous magma chambers, as exhalations — hydrothermal solutions or volcanic gases. The effect of the encounter with sea water on these ejected gases or water-rich vapors was to precipitate their potentially solid constituents with great rapidity; they were deposited so quickly, in fact, that the amounj of normally accumulated mechanical or chemical sediment deposited over the same period of time was essentially negligible. The ores formed in this manner, however, are generally interbedded with normal sediments or with lava flows, or with any combination of these two types of rock-forming materials. Such departures as these deposits may have from their original mineral content and attitude are thought to be directly related to the degree of dynamic or static metamorphism that they may have undergone after their accumulation. I have not attempted here to present alternate hypotheses to that of so-called exhalative sedimentation although, of course, such exist and, in my

Jan 1, 1963

By E. T. Hayes, A. H. Roberson, M. H. Davies

R. F. Dornagala and D. J. McPherson (Armour Research Foundation, Chicago)—I should like to compliment the authors for a workmanlike job in determining the partial phase diagram of a system comprised of two rnetals which are certainly not easy to work with. We are completing work at Armour Research Foundation on an Atomic Energy Commission-sponsored project for the determination of eight zirconium binary diagrams. Work on the Zr-Cr system has been completed and should be published within the next year. For our work, Westinghouse Grade 3 iodide crystal bar served as the zirconium melting stock. Johnson-Matthey, electrolytic chromium, specially treated for oxygen removal, was employed. The overall constitution of the system determined at Armour Research Foundation is in very good agreement with the present work. We found a eutectic at 18 pct Cr and 1280 °C, somewhat lower than the value reported. This temperature was confirmed by thermal analysis, incipient melting studies, and regular isothermal anneals. The eutectoid was located close to 1 pct Cr and 835°C by metallographic analysis of annealed specimens. Maximum solubility of chromium in /S zirconium was 4.5 pct at the eutectic temperature. Chromium solubility in a zirconium was less than 0.28 pct at all temperatures. We found the compound at 53 pct to melt around 1700°C, with an open maximum, but determined its crystal structure to be hexagonal close-packed (MgZn, type). The lattice parameters were in excellent agreement with those determined by Wallbaum in 1942. The diagrams are in substantial agreement, and .part of the differences are undoubtedly due to the use of different zirconium melting stock. M. K. McQuillan (Birmingham, England)—I read this paper with a great deal of interest, as it covered the same field as some work of my own.' There are a number of points in the present paper on which I would like to comment. First, I should say that I, too, used zirconium prepared by magnesium reduction of the tetrachloride and electrolytically prepared chromium, and melted the alloys in a Kroll-type arc furnace. The purity of my alloys should, therefore, be comparable with the purity of those of the present authors, and any differences in our observations would not be expected to be attributable to this cause. The differences between my observations and theirs concern the presence of the eutectic, the temperature of the eutectoid, and the melting point of the compound. I would be very much interested in any further evidence the authors may have for the occurrence of the eutectic at 1380°C. During the course of my work I noted that a number of my alloys containing 60 to 90 pct Zr melted at about 1400 °C, and for a time assumed that a eutectic occurred at this temperature as described in the paper. On further investigation, however, I found that the structures of the as-melted alloys could not be made to fit in with this interpretation of the system. If a eutectic exists in this region of the system it would be expected that the as-melted alloys would show the usual type of cast structure, i.e., dendrites of the compound plus eutectic. This, however, does not occur, as may be seen from Fig. 9. The compound seen there is not dendritic in form, and the remaining material is by no means certainly eutectic. It may be argued that a compound such as ZrCrl would not form dendrites but would tend to crystallize in geometric shapes. In this case, however, I have evidence to the contrary, as on the chromium side of the compound, where a eutectic occurs at about 1545"C, the compound formed from the liquid takes on a conventional dendritic form, and the eutectic is observed in the interdendritic spaces in the usual way. There is no reason to suppose that the compound would behave differently in an alloy lying on the zirconium side of the compound composition if a eutectic existed there too.

Jan 1, 1953

By J. E. Drury, W. M. Byers, E. J. Lynch

Measurements made with starch ~~~~s indicate that the Presence of starch serves to depress the streaming potential of a clay mud system. Measurements with pure starch slurries show that the addition of NaCl or CaO reduces the streaming potential significantly. The addition of NaOH, however, causes only a minor reduction in potential even when there are large changes in mud resistivity. INTRODUCTION In their excellent study of the streaming potential, Hill and Anderson' proposed that the presence of conductive solids within the filter medium will reduce the generated potential. This theory was demonstrated with measurements on shaly sandstone cores having various "b" factors; the cores with the higher negative b factors showed markedly lower potentials. (The factor b was originally defined by Hill and Milburn2 in an expression relating the resistivity of a shaly sandstone to the resistivity of the interstitial water: log F, = log F,, + b (log 100R,)'. 'he factor b, therefore, is a measure of the contribution of the conductive solids to the total conductivity of the sample. It has been found experimentally to be directly related to the amount of chemically exchangeable ion per unit pore volume.) In the logical extension of this hypothesis to the streaming potential created by filtration through mud cakes, they suggested that the presence of nonconductive starch in a drilling mud would have the opposite effect; i.e., it would cause the streaming POtential to be increased. The high streaming potentials that they observed with lime muds were attributed to this cause. A cross-plot of some of their results which are relevant to this discussion is given in Fig. 1. The lime-mud curves and untreated-mud curve are taken from curves given in their paper. The gyp-mud line was estimated from their statement that the measured streaming potential for gyp muds in the range of 1.5 to 2.0 ohm-m was approximately 18 mv/1,000 psi. These gyp-mud potentials were the lowest that they reported for any of the bentonitic-clay muds, and were the only ones which were less than the untreated-mud potentials. This very low streaming potential of gyp muds has also been observed in field studies.' By way of comparison, a U. of Texas publication4 gives the approxi-ate compositions for lime and gyp muds shown in Table 1. These materials are added to a bentonitic-clay mud base. It can be seen that both of these muds contain significant amounts of calcium salts and that the gyp mud has the higher concentration of starch. It would appear from this and from the data shown in Fig. 1 that starch may well be the cause of a streaming-potential reduction, rather than a potential increase. EXPERIMENTAL A series of streaming-potential experiments has been performed using a cell of a design similar to that reported by Wyllie.5 Calomel electrodes were used in both the mud slurry and the filtrate. Pressure in the cell was generated with high-pressure nitrogen. The primary objective of the investigation was to determine the effect of starch on the potential. Five different slurries were made which ranged in composition from untreated ben-tonitic mud (Baroid Aquagel) to a pure starch suspension (Baroid Im-permex). The intermediate slurries were prepared by mixing together a 9-lb/bbl clay mud with a 12-lb/bbl starch suspension in the ratios 1:3, 1:1 and 3:1. When starch was used alone, it was necessary to use an 18-Ib/bbl mixture, since leaner mixtures would not form a suitable filter cake. The clay mud used in the experiments was aged for three months before use. In addition to this series of measurements on the starch-clay mud mixtures, other experiments were performed to determine the effect on the potential of the absolute starch and Aquagel concentration, and the effect of adding various chemicals. RESULTS The effect of starch on the streaming potential is shown clcarly in Fig 2. Increasing percentages of starch resulted in n continually decreasing

By D. R. Bomberger, M. Deul

An automatic microscope has been developed to measure the size and populations of macerals and minerals in fine coal particles. Differentiations are made on the basis of reflectance. This study is concerned with the size distribution of pyrite inclusions. Most fine coal cleaning processes do not remove pyrite as completely as a straight density separation. Consideration of the pyrite size distribution is suggested as a more accurate method of predicting sulfur reduction by a cleaning process. Analyses of float-sink results and Deister Table operation in terms of pyrite particle sizes are made. Other potential applications of automatic microscopy are also discussed. In the study of coal cleaning by pseudo-gravity methods (tables, cyclones, hydrotators, etc.), it is customary to express the deficiency of the process relative to float-sink measurements in some form of "percent efficiency". These have been calculated in many different ways in order to provide a means of extrapolation of test data to untested coal feeds. This works quite well with coarse coal (here defined as larger than one-eighth in.). Large, heavy pieces of refuse are rejected rather thoroughly by many cleaning processes, and the efficiencies relative to float-sink results approach 100%. In coarse coals, the difference in the sizes of fine pyrite is masked by the averaging effect of the large coal envelopes. The existence and fate of fine pyrite is often hidden in the larger numbers representing coarse (and easily removed) pyrite. There are cases where it is desirable to subject fine coal (here defined as smaller than one-eighth in.) to cleaning processes. This is true of naturally occurring fie coal streams and in cases where comminution followed by cleaning is necessary to provide the quality desired. It is in this area that the use of process efficiency relative to float sink fails. Percent efficiencies decline to very low figures, and equivalent separation densities become a matter for conjecture. The net result is that an attempt to estimate product quality from float-sink data and a process efficiency figure often results in large errors. This work represents a new approach to the problem by observing the fate of pyrite particles, grouped by sizes, in a cleaning process. Examples are given which relate pyrite size measurements to float-sink washability and to a Deister Table operation. EXPERIMENTAL WORK The automatic microscope used here has been previously described.' Briefly, it is an instrument which measures the diam of particles (as defined by a range of reflectance) exposed on a polished specimen. The instrument scans a sample briquet, measures diam of exposed pyrite inclusions and records the data by size intervals. Preparation of the briquet is critical, due to the automatic nature of the process. The principal requirement is for an optically flat surface, so that focus will be maintained as the motorized stage moves the specimen under the lens. The various substances present must be polished to the same level in spite of the wide difference in hardness between coal substance and minerals. The polishing method must not pluck out small grains, which might be rather loosely held by surrounding coal. The procedure below was successful in producing all of these results. The coal sample (8 mesh or finer) was riffled (a micro vibrating riffle is essential) to obtain 15 g. One volume of Lucite powder (thermosetting plastic mounting medium) was mixed with three volumes of coal and mixed thoroughly. A briquet was formed using a cylindrical die (1 1/4 in. diam) at 3000 lb per in.* pressure and 150°C. Preparation of the optical surface was accomplished on automatic polishing equipment, according to the following schedule: 1) Grinding: 3 stages, using successively fine Carborundum grits of 180, 320 and 600 mesh. 2) Rough polishing: 2 stages, using 3µ alumina on cast iron, followed by 1µ alumina on lead. 3) Fine polishing: 2 stages, using 0.5µ alumina on napless broadcloth over bronze, followed by 0.1µ alumina on silk filament cloth over bronze. Raw data were corrected for the fact that the chords

Jan 1, 1964

By J. T. Norton, J. G. McMullin

The ternary system of gold-silver-copper is characterized by a solid solubility gap and a two phase region in which copper-poor and silver-poor phases coexist. At about 30 pct gold, the two phases become mutually soluble at temperatures below the melting temperature. As the gold content is increased, the solubility temperature of the alloys decreases until at about 80 pct gold, the two phases are soluble down to the lowest temperature at which the alloys will recrystallize. Although the general form of the two phase region is known, its boundaries do not seem to have been investigated extensively. In an X ray diffraction study, Masing and Kloiberl have outlined the boundaries of this two phase field at 400 and 750°C. Using only microscopic techniques, Pickus and Pickus2 determined a vertical section of the ternary diagram showing the 14 kt alloys (58.3 pct gold). These two reports are riot in complete agreement. It has been shown3 that some of the ternary alloys are susceptible to age hardening and that the hardening is caused by the separation of a homogeneous alloy into two phases at the aging temperature. While the gold-copper binary system is an outstanding example of super lattice formation, Hultgren4 has shown that a few per cent of silver added to gold-copper destroys the tendency for ordering. Because of the age hardening possibilities of these alloys, it seemed advisable to investigate the boundaries of the two phase field more in detail using an X ray diffraction method, so as to permit a better understanding of the aging phenomena and enable predictions as to the behavior of other alloys to be made. This is especially true for the 18 kt alloys (75.0 pct Au) at the lower temperatures since they are known to exhibit age hardening. Twelve ternary alloys were prepared having the compositions shown in Table 1 and graphically in Fig 1. The gold used was fine gold bars supplied by Handy and Harmon. The silver was a bar of high purity silver from the U. S. Bureau of Standards. The copper was a bar of vacuum-treated, high conductivity copper from the National Research Corporation. The pure metals in the form of powder were weighed out in proper proportions and melted in graphite in a high frequency induction vacuum furnace. They were heated to 1100°C and slowly cooled. The ingots were then removed from the crucible, inverted, returned to the crucible and remelted. This remelting procedure was intended to reduce segregation in the ingots. After remelting, the ingots were checked for weight loss. The weight loss in each ten gram ingot was held to less than 25 mg. The remelted ingots were cold rolled and then given a homogenizing heat treatment of 16 hr at 760°C to remove any remaining segregation. Powder specimens were prepared by cutting the ingots with a fine file, one half the required amount of powder being taken from each end of the ingots. When the X ray diffraction pattern showed any difference in lattice constant between the ends of the ingot, the ingot was remelted and given an additional homogenization treatment. All powder samples were sealed in evacuated pyrex tubes for heat treatment. Ordinary pyrex proved satisfactory for temperatures up to 650°C but above that temperature it was necessary to use a special high temperature pyrex glass. Annealing at temperatures below 500°C was done in a salt bath whereas for temperatures of 500°C and above an electric muffle furnace was used. In both furnaces the temperature control was ± 5°C. In all annealing treatments samples of cold worked powder were placed in a furnace which was already at temperature. In this manner the specimens recrystallized directly to the equilibrium structure for that temperature. Time at temperature was selected so as to allow complete recrystallization, but very little grain growth. Specimens were quenched from the annealing temperatures by breaking the pyrex tubes in cold water. X ray diffraction photograms were made of all the heat treated powders using copper radiation and a Phragmen

Jan 1, 1950