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By James K. Gluck, William E. Galloway, Gary E. Smith, John P. Morton, Christopher D. Henry

INTRODUCTION Surface mining and in situ leaching of uranium have the potential to alter ground-water quality around mines and leach sites. Of particular concern is the fate of uranium and its associated trace elements: molybdenum, arsenic, and selenium. We wish to under- stand the natural processes that control trace element concentrations in ground water and how these processes will influence dispersion of the elements from a mineralized zone, both naturally and during and after mining or restoration. For example, it is commonly recognized that the trace elements are soluble in oxidizing ground water but are insoluble, and can be precipitated, in reducing ground water. Thus oxidizing, metal-bearing water leaving a deposit could re- enter reduced ground, causing the water to be re- reduced and the trace elements to be, reprecipitated. In a sense, this is recreating the original mineralization process. To accomplish the above goals, we have (1) examined the theoretical controls of concentrations based on the available geochemical and thermodynamic data, (2) determined the major ion composition and oxidation-reduction status of Oakville waters because of the influence of these factors on trace element solubility, and (3) determined trace element concentrations and distribution in Oakville ground water. The last approach is used to evaluate how well actual behavior follows predicted behavior. This report focuses on two elements, uranium and molybdenum, because they exemplify the results obtained. The report also is restricted to a regional study of Oakville ground water. Results of more de- tailed study in and around major uranium districts in the Oakville and much of the raw data that support the conclusions in this report are presented in Galloway, Henry and Smith (1980). This report is part of that larger study, which concerned the depositional systems, hydrology, and geochemistry of the Oakville. The U.S. Environmental Protection Agency funded the study, under grant numbers R-805357-01 and R-805357-02. Theoretical controls were determined by reviewing the available literature on aqueous chemistry and behavior of uranium and molybdenum. To aid in under- standing water chemistry, Oakville water analyses were run through a modified version of the computer model WATEQF (Plumer, Jones, and Truesdell, 1976). WATEQF calculates speciation of dissolved ions and determines saturation with respect to a variety of minerals. In the discussion below, ion activity products (IAP) are compared with the equilibrium constant (KT) for various reactions and mineral products. Values of log IAP/KT near zero indicate that the water is in equilibrium with a mineral. Values less than -1 indicate considerable undersaturation and values greater than +1 indicate oversaturation. Galloway, Henry, and Smith (1980) give a more complete discussion of the application of this approach to Oakville water chemistry. Eh-pH diagrams have been constructed or adapted from the literature to predict what form -- dissolved ion or stable mineral species -- uranium and molybdenum assume under various conditions. Construction of the diagrams has followed procedures described by Garrels and Christ (1965). This approach is particularly appropriate because the solubility of the elements is Eh-dependent, and Eh varies greatly within the Oakville aquifer. A number of assumptions or approximations are inherent in the use of Eh-pH diagrams and chemical models such as WATEQF and in the interpretation of water chemistry in general. Both Eh-pH diagrams and chemical modeling rely entirely upon available thermo- dynamic data, including free energies of formation and dissociation constants for various reactions. These values are known to varying degrees of accuracy. Most major ions and minerals are relatively well control- led; however, data for trace metals are much poorer. Thermodynamic data are not available for some minerals, and for other minerals, two or more divergent values exist. By necessity, we have relied on the judgment of others to evaluate thermodynamic data. Calculations by WATEQF and constructions of Eh-pH diagrams are based on an assumption of equi1ibrium. Equilibrium may not be comnon in low-temperature aqueous environments; at best, ground-water composi tion may be in a state of dynamic equilibrium, continuously changing due to changes in environmental conditions. Eh-pH diagrams show what phases are stable at equilibrium under given conditions; they do not prove that the phases actually exist. Many minerals persist or form metastably under conditions outside their equilibrium stability field. The kinetics of reactions, which cannot be evaluated here, are important in determining what phases occur. Kinetics may be less of a problem for ground water that travels and evolves slowly through a semihomogeneous matrix than for many other natural systems. Eh-pH diagrams show equilibrium fields only of phases included. They do not indicate anything about stability relative to phases not included in the diagram. WATEQF, obviously, cannot calculate the degree of saturation of a mineral not included in the program or for which the appropriate ions were not analyzed. Thus, a mineral that was not considered may be the most stable phase under a given set of conditions and may control the solubility of a trace element. Also, this study is limited exclusively to in- organic compounds. Organic material is known to be an

Jan 1, 1980

By J. Jr. Hudy

The objective of this investigation of the Cendrex was to determine the applicability of the X-ray instrument for the measurement of the ash content of coal. Developed by the Dutch State Mines, this instrument is designed to provide ash analysis of any desired coal product with only a 5-minute lag between sample collection and analytical result. The unit could, with limit controls, be used to feed back signals to preset the separating gravity of coal washers, control the ratio of various coals needed to produce an acceptable blend, and permit the sorting of a washed product into two qualities, one which is below and the other which is above a prescribed ash content. This unit can also be used discontinuously for rapid determination of samples of coals taken in the usual manner.

Jan 7, 1968

By John Gross

THE deductions drawn in crushing and grinding operations have heretofore been based on a separation of the products into various sizes. A crushed product may be sized by sieving, by elutriation, and by aid of the microscope. To estimate the surface of each size the relation of the surface to the estimated average diameter must be assumed. Such a relation, owing to the irregularity of the particles, may involve two assumptions: First, a factor to convert average diameter to surface for one particular size; and second, a variation in the factor as the diameter of the particle changes. Obviously a surface measurement in which such assumptions and estimates are involved is questionable. In the first paper of this series1 a method has been given by which an accurate measure of surface of quartz can be obtained from its dissolution rate. By the use of this method, surface measurements have been made on a series of sieve sizes of crushed quartz, the results of which are given and discussed in this paper.

Jan 1, 1928

THE CHAIRMAN (G. H. CLEVENGER, Stanford University, Cal.).¬I would like to ask Mr. Pyne if he has had any experience inn the use of chromite as refractory under conditions that are highly reducing? I am reminded of an experience I once had with an electric furnace. I imagined that chromite would form a splendid lining, but it soon disappeared; hence it seems probable that, under highly reducing conditions at a high temperature, chromite is a very poor refractory. F. R. PYNE.-In copper smelting the atmosphere is generally neutral, or slightly oxidizing; we do not use highly reducing atmospheres at all, not even in the matting furnace. You can take the chromite brick and treat it as you would an iron ore, obtaining ferro-chrome very readily, from which the copper will separate. We have done this; in fact, at one time we considered installing a small electric furnace for the production of ferro-chrome. FOREST RUTHERFORD, New York, N. Y.-During the time I was general superintendent at the smelter of the Copper Queen Consolidated Mining Co., at Douglas, Ariz., a great many experiments were made on the furnaces and settlers with different kinds of brick, and I agree with Mr. Pyne's statements about chrome brick. Their power to absorb metals is very great, and as they cannot be smelted at any temperatures obtainable in a copper furnace, to get rid of the bats and extract the metal from them is quite a problem. We finally got down to using chrome brick only for lining the settlers, out of which we often got a life of upwards of 2 years, and for lining the blast-furnace bottoms, for the reason that chrome brick can be heated and wet, or wet after being heated, without going to pieces, whereas under these conditions magnesite brick will break down very rapidly. We also used a layer of chrome brick above and below an 18-in. band of magnesite brick put on the slag line of the reverberatories, in order to separate the magnesite from the silica brick, fearing that they would slag each other and let the wall drop. The idea worked, but became unnecessary on account of a change made in the method of feeding the furnaces. Chronic brick will not stand up under pressure so well as a good Grecian or Austrian magnesite brick, on account of the poorer bonding properties of the materials from which the chrome brick is made.

Jan 4, 1918

By Michael R. Cartwright

The Gold Acres outcrop was located by Lee Lakin in 1922, according to Mr. H. W. Treweek. There was no activity, however, until 1935, when prospect drifts and pits penetrated the deposit. It was then drilled by the Willow Creek Mining Company. Beginning in the late 1930s and continuing to the late 1940s more than 150 churn drill holes were drilled in the Gold Acres area. From this drilling came what is now known as the London Extension pit. Only oxidized ore amenable to cyanide vat leaching was mined during this time. Our records indicated that this period of mining removed some 1.4 Mt (1.5 million st) of ore at an average grade of 0.006 kg/ t (0.2 oz per st). Union Pacific and Newmont Mining Company worked in the area prior to acquisition by the Cortez Joint Venture. Union Pacific drilled a number of core holes in the area. The unoxidized nature of the ore, small tonnage, and low grade undoubtedly prevented mining at this time. From these indications of mineralization shown by previous companies, the Cortez Joint Venture developed and mined 2 Mt (2.4 million st) at 0.005 kg/t (0.15 oz per st) in the Gold Acres pit. This pit is located immediately southwest of the older London Extension pit. Cortez Gold Mines has continued to drill to the west and south of these pits along the downdip continuation of the former ore bodies. The downdip extension is unoxidized and more metallurgically difficult than the normal Carlin type ores, but, more than 2.4 Mt (2.7 million st) have been outlined. It depends now upon the gold price and milling costs to turn this mineralized area into an ore body. A possible lesson to be learned from this deposit is that continued mining success depends upon an ongoing adequately funded exploration-development-metallurgical research program. These three disciplines must always be present to locate the mineralization and to turn this mineralization into ore. [ ]

Jan 1, 1985

By MARCELS CHLUMBER

BY the term making an "electrical log" the authors designate an operation conceived for the purpose of determining electrically the characters of formations traversed in drilling, the determination being carried out by means of measuring the electrical resistivities of the rocks along the uncased portions of drill-holes. As in the case of an ordinary core record, this process connotes a geological studs of the strata, and for that reason it is given a similar designation. The paper is divided into three parts, of which the first deals with the resistivities of rocks in general, since it is through this electrical parameter that they are to be characterized. The second deals with the technique, and the third with the description of practical applications of the electrical logs.

Jan 1, 1929

By P. P. Gregory

Natural petroleum gas occurring in the oil-bearing reservoirs is found to exist either as free gas associated with the oil and/or in solution in the oil. In some virgin fields practically no free gas is encountered under the reservoir conditions of pressure and temperature, although in other fields a considerable section of the "pay" horizon is occupied by free gas. In other words, a given oil field may or may not have a gas cap before the exploitation takes place. However, when the reservoir pressure is reduced to a point below the critical saturation pressure by withdrawals of fluids from the producing formation, the gas dissolved in the oil inevitably begins to come out of solution and becomes free gas. Under the controlled methods of production and drilling, a portion of this gas is produced with the oil to the surface and a portion of it remains within the reservoir to accumulate at higher structural levels toward which it migrates by virtue of its low specific gravity. The rate of growth of a gas cap in a given structure depends primarily upon the rate of decline in the reservoir pressure. If the rate of pressure decline is rapid, the gas cap likewise will grow rapidly. On the other hand, shrinkage in the gas-cap area was noted in some fields in which reservoir pressures wereincreasing. Determination of Gas-oil Contact and Thickness of Gas Cap The gas-oil contact can be conveniently located in the process of drilling a well and by electrical logging. However, very little can be found in the petroleum literature concerning methods of predetermining gas-oil contacts in producing reservoirs. Therefore, the writer feels justified in describing briefly a simple, workable, and inexpensive method of determining gas-oil contacts and outlining the limits of gas-cap areas in a field where such knowledge may be essential for efficient production and development operations. The method involves the determination of the following data: (I) Structural data, such as the depth or elevation of the top' of "pay" horizon; (2) reservoir pressures; (3) tubing and casing pressures at the well head; (4) static oil-pressure gradient; (5) static gas-pressure gradient. These data can be secured with a minimum of expense, inasmuch as the

Jan 1, 1938

By Wilbur I. Duvall, Wilson Blake

The microseismic method of detecting instability in underground mines was developed by the U.S. Bureau of Mines (USBM) in the early 1940's. ,3 The method relies on the fact that as rock is stressed, strain energy is stored in the rock. Accompanying the buildup of strain energy are small-scale displacement adjustments that release small amounts of seismic and acoustic energy. These small-scale disturbances, which can be detected with the aid of special geophysical equipment, are called micro-seisims or self-gene rated rock noises. It was further determined that as failure of rock is approached, the rate at which rock noises are generated increases. Thus, by monitoring a rock structure at intervals and plotting rock noise rates vs. time, a semi quantitative estimate of the behavior and stability of the structure can be made. Since sufficient use of the microseismic method is still being made by various mining and construction companies, USBM undertook a comprehensive review of the method and a study of the fundamental properties of rock noises. As all prior work on rock noises has been done with resonant-type geophones, which prevented any analysis of their vibration records, it was necessary to develop the instrumentation and field techniques in order that their properties could be investigated, such as their frequency spectrum and absorption characteristics, and to determine if both P and S-waves are generated by a rock noise. The aim of this program is the design of microseismic instrumentation which can be better utilized as an engineering tool than the presently available microseismic equipment. This new design, based on the basic properties of rock noises, should allow better utilization of these phenomena in the study and location of zones of incipient instability in both underground and open-pit mines. EXPERIMENTAL PROCEDURE To study the waveform of rock noises, it was necessary to develop a microseismic system with a broad bandwidth. To achieve high sensitivity and broad frequency response, commercial ceramic accelerometers were used. The present broad-band microseismic system consists of accelerometers as geophones, low-noise preamplifiers, high-gain amplifiers, and an FM magnetic tape recorder. This seven-channel system has a flat frequency response from 20 to 10,000 Hz, a noise level of less than 2.0 kv, and a dynamic range (including manual set attenuation) of greater than 100 db; it can detect signals with acceleration levels as low as 2 ug. The entire system is solid state and hence battery operated and portable (Fig. 1) Analysis procedures consist of playing back the 30-in-per-sec (ips) magnetic tape recordings at 1 7/8 ips to expand the time scale of a recorded rock noise event and then recording this on a high-speed direct-writing oscillograph. The oscilIographic records are then digitized and run through Fourier integral analysis computer programs to determine the frequency spectrum of a rock noise event. The oscillographic records are also examined visually to determine if both P and S-waves can be recognized in a rock noise waveform. Broad-band microseismic recordings have been made at field sites in a wide variety of rock types and in both underground and open-pit mines. Sites include the Kimbley Pit, Ruth, Nev.; the Galena Mine, Wallace, Idaho; the Colony Development Mine. Grand Valley, Colo.; the Cliff Shaft Mine, Ishpeming, Mich; and the White Pine Mine, White Pine, Mich. DATA AND DISCUSSION Analyses of the recorded data have shown that rock noise frequencies are very broad. Fig. 2 and 3 show typical rock noise events and their frequency spectrums. In addition, it is evident from these figures that the wave form of a rock noise is very complex. The wide frequency variation, 50 to 7500 Hz, is due to many variables; the effect of travel distance is the only one examined in this study. The higher frequency components of the wave are rapidly absorbed with distance or increasing travel time. Fig. 4 shows the change in waveform resulting from an additional travel distance of 195 ft. From these data, it is apparent that a resonant-type microseismic geophone cannot respond to all frequencies generated by a rock noise, and in spite of the fact that the tuned geophone is more sensitive at resonance, a geophone with less sensitivity but broader band width is much more effective in detecting rock noises. In addition, a study of broad-band microseismic records shows that both P and S-wave arrivals are easily detected, as shown in Fig. 5. All records analyzed to date show that most of the energy is in the S portion of the wave; hence, microseismic geophones should be well

Jan 1, 1970

By ir. H. Eraly

The allocation of miners to teams, and of teams to production faces, is complicated by the high degree of absenteism of miners in Belgium. Therefore, the exact knowledge of who is actually present at the beginning of a shift and of the exact skills of those present, enables the foremen and mine captains to constitute their teams before all men go down into the mine in the most effective way possible. This paper describes the system of attendance recording and of displays which the foremen use to constitute their teams and/or to interrogate the personnel data base in order to do so. It shows how the foremen dialogue with the computer, to change the function of a miner within a team, to another team, or the function of a team as a whole. The implementation of the system, data bases, and data communication equipment and procedures, is described. The benefits obtained are presented for each level of the company: foremen and team supervisors, engineers, mine management.

Jan 1, 1977

By Haim H. Chiswik, Ralph Hultgren

In recent years considerable attention has been devoted to the development of new commercial uses for silver, chiefly because of lowered prices and large stocks of the metal. This has led to increased interest in the phase diagrams of silver alloys. The silver-lead diagram is reported' to be of the simple eutectie type, but no measurements of the solubility of lead in silver have been made. The solubility of silver in lead has been estimated2 from diffusion experiments and resistance measurements to vary with temperature from 0.09 to 0.18 atomic per cent (0.05 to 0.10 weight per cent). Silver-rich silver-lead alloys have recently been recommended as high-strength bearing metals3 The silver-bismuth diagram is similar.' The solubility of bismuth in silver. has been estimated to be about 5.5 weight per cent on the basis of X-ray work.4 Matthiessen6 found a solubility of silver in bismuth from 0.25 to 0.50 per cent by conductivity measurements. Silver and thallium form the same type of diagram,' with no data on their mutual miscibilities. We have studied the first two of these diagrams by X-ray methods, verifying their main features and determining the solubilities of lead and bismuth in silver at several temperatures. We also determined the solubility of thallium in silver at one temperature. The solubilities of silver in lead and in bismuth were found to be too low to be detectable. Materials and Methods Mallinckrodt precipitated silver, analytical reagent, was used. Maximum impurities listed on the label were: chloride, 0.005 per cent; copper, 0.001; iron, 0.002; other heavy metals (as Pb), 0.002; and sulphate (SO³), 0.05. The lattice constant was found to be a0 = 4.0782 $., in good agreement with the value of Jette and Foote,6 a0 = 4.0779 A., for

Jan 1, 1940

By Ralph Hultgren, Haim H. Chiswik

In recent years considerable attention has been devoted to the development of new commercial uses for silver, chiefly because of lowered prices and large stocks of the metal. This has led to increased interest in the phase diagrams of silver alloys. The silver-lead diagram is reported' to be of the simple eutectie type, but no measurements of the solubility of lead in silver have been made. The solubility of silver in lead has been estimated2 from diffusion experiments and resistance measurements to vary with temperature from 0.09 to 0.18 atomic per cent (0.05 to 0.10 weight per cent). Silver-rich silver-lead alloys have recently been recommended as high-strength bearing metals3 The silver-bismuth diagram is similar.' The solubility of bismuth in silver. has been estimated to be about 5.5 weight per cent on the basis of X-ray work.4 Matthiessen6 found a solubility of silver in bismuth from 0.25 to 0.50 per cent by conductivity measurements. Silver and thallium form the same type of diagram,' with no data on their mutual miscibilities. We have studied the first two of these diagrams by X-ray methods, verifying their main features and determining the solubilities of lead and bismuth in silver at several temperatures. We also determined the solubility of thallium in silver at one temperature. The solubilities of silver in lead and in bismuth were found to be too low to be detectable. Materials and Methods Mallinckrodt precipitated silver, analytical reagent, was used. Maximum impurities listed on the label were: chloride, 0.005 per cent; copper, 0.001; iron, 0.002; other heavy metals (as Pb), 0.002; and sulphate (SO³), 0.05. The lattice constant was found to be a0 = 4.0782 $., in good agreement with the value of Jette and Foote,6 a0 = 4.0779 A., for

Jan 1, 1940

By John J. Strohl, Henry J. Schwellenbach

This paper relates the results obtained by decreasing the size of feed to a rod mill screen circuit. As would be expected, added production was gained and a finer grind with no tonnage loss was made possible.

Jan 12, 1950

By B. C. Raynes

IN the early part of 1952, under the auspices of the U. S. Atomic Energy Commission, Horizons Inc. undertook an investigation dealing with the preparation of high purity thorium metal in order to develop an economically competitive production process for this metal based on a recovery of the metal by a fused salt electrolysis, since a survey of the literature of thorium chemistry indicated that electrolytic methods had not received much attention, despite the consideration that electrochemical production methods often offer attractive commercial potentialities. Thorium metal has been prepared by methods which fall into four general categories: 1) reduction of halides or double halides; 2) reduction of the oxide; 3) thermal decomposition of halides; and 4) electrolytic methods. Some of the important results obtained by various investigators since about 1900 in recorded attempts to prepare pure thorium metal are summarized in Table I. A bibliography of pertinent literature is included in this paper. Thorium is strongly electropositive and possesses a great affinity for oxygen and nitrogen. As a result the prospects for the production of high purity thorium from aqueous media or oxygen bearing compounds are remote. The most promising and profitable area of investigation for production of thorium metal lies in fused salt electrolysis. Thorium has been produced previously by this technique from halide salts in fused alkali chloride eutectic mixtures. Until recently, however, the lack of known large uses for thorium has inhibited the investigation of these methods. The basic problem in an investigation into fused salt production methods for thorium is to develop a suitable fused salt system for the economic preparation of thorium. The first portion of the work in these laboratories was a small scale investigation of the electrolysis of potassium thorium fluoride, KThF5, under a variety of conditions. High purity thorium was prepared in this manner, but the process did not appear to offer the simplest and most attractive continuous commercial operation. The work reported here relates to an all-chloride system employing thorium chloride as the cell feed. ThCL4 was produced as an anhydrous material stabilized in molten sodium chloride. This product, further diluted in NaCl, was subjected to electrolysis. The electrolytic process has been studied in cells capable of holding up to 50 lb total salt charge. Ductile, pure thorium metal has been reproducibly obtained in this operation. Considerable experimentation was carried out in the preparation of ThCL as a cell feed free from moisture, oxides, and other impurities. Thorium was cathodically deposited as a coarsely crystalline powder interspersed with residual bath salts. Aqueous procedures for separating and recovering the metal were developed. The thorium metal powder obtained has been evaluated with respect to its hardness, chemical purity, and certain other physical properties. Preparation of ThC1,—Thorium chloride, and the chlorides of some other metals (aluminum, beryllium, tantalum, zirconium, etc.) cannot be obtained from aqueous solution by direct heating and evaporation. Evaporation and heating of a solution of thorium chloride yields a hydrated salt or partially hydrated salt, and finally Tho,. Anhydrous thorium chloride is obtained by forming a hydrated ammonium chloride complex salt in acidified water solution, dehydrating this compound, and finally decomposing the double salt and subliming the ammonium chloride component. Various methods for the preparation of anhydrous thorium chloride, in accordance with this concept, were investigated as indicated in Table I1 from hydrated thorium chloride (ThCl, . 3H2O), and from thorium oxycarbonate (ThOCO,). In the method found most satisfactory for this work, thorium oxycarbonate was dissolved in an excess of concentrated HC1 to give a clear yellow solution. At least 2 mol NH,Cl were added to the solution per mol of contained thorium. Ammonium thorium chloride hydrate was crystallized from solution by cooling and saturation with HC1. The resultant complex, (NH,Cl),ThCl;xH,O, was dehydrated by evaporation at 130° to 150°C and thoroughly dried at about 250°C. The dried ammanium thorium chloride was then mixed with sodium chloride in proportions to form NaThCL or to produce a ThCL4-NaCl mixture with a given thorium content. The ammonium chloride was sublimed off at temperatures above 500°C in an inert atmosphere furnace to give an anhydrous chloride source electrolyte, essentially free of Tho, and of NKC1.

Jan 1, 1958

Ahrenholz, Herman William, Jr., Student, Lehigh Univ Bethlehem, Pa. '35 Allen, Carl A., Student, Colorado School of Mines Golden, Colo. '35 Allen, Paul W., Student, Mass. Inst. of Tech Cambridge, Mass. '35 Allen, R. M., Jr., Student, Virginia Polytechnic Inst., "G" Co Blacasburg, Va. '35 Amberger, K. H., Student, Michigan College of Min. & Tech Houghton, Mich. '35 Andersen, Burton Lee, Student, School of Mines, Univ. of Washington Seattle, Wash. '35 Anderson, Joseph S., Student, Univ. of Texas El Paso, Tex. '35 Anderson, R. C., Student, Univ. of Washington Seattle, Wash. '35 Ansel, Gerhard 627 Clyde St., Pittsburgh, Pa. '34 Anutta, Frederick P., Student, Michigan College of Min. & Tech Houghton, Mich. '35 Apsouri, Constantin N., Graduate Student, Univ. of Arizona Tucson, Ariz. '35 Arakelian, Haig Mark, Student, Mass. Inst. of Tech Cambridge, Mass. '34 Archer, George K 1420 Court Pl., Denver, Colo. '34 Argall, George O., Jr., K. E. House Golden, Colo. '35 Argiielles, Alfredo, Student, Univ. of Texas El Paso, Tex. '35 Atwater, Ralph, Student, South Dakota School of Mines Rapid City, S. D. '35 Austin, Robert B., Miner, Page Mine, Federal Min. & Smelt. CoSpokane, Wash. '34

Jan 1, 1934

By F. A. Veer, W. G. Burgers, B. H. Kolster

Starting-- from Cu-Si diffusion couples a study of diffusion in the intermetallic compound Cu3Si of the Cu-Si system has been made. Mmker experiments showed copper to be the diffusing element. From the rate of growth of the Cu3Si phase diffusion coefficients were derived. The activation energy for diffusion is 18.6 kcal per mole. The couples show some interesting microscopic features, for which a tentative explanation is given. THE synthesis of dimethyldichlorosilane, (CH3)2SiC12, an important compound in the manufacture of methyl-silicones, takes place at the surface of a thin Cu3Si layer deposited on a mass of silicon particles."' By passing CH3C1 vapor at about 350°C, silicon atoms are consumed from Cu3Si in forming the volatile silane molecules, thus leaving copper atoms at the surface. It is well-known that copper acts as a poison for the above-mentioned reaction by catalyzing the dissociation of methylchloride.' However, no poisonous effect is observed, at least not before most of the silicon from the particles is converted into silane.3 This would be understandable, if either the copper atoms diffuse through the Cu3Si deposit to the underlying silicon or silicon atoms diffuse in the reverse direction to the copper, both processes resulting in the formation of new Cu3Si and so ensuring the proceeding of the reaction. In this paper experiments are described, demonstrating copper to be the diffusing element. Also a very low activation energy for the diffusion is observed. EXPERIMENTAL The silicon used contained 1 ppm Mg and 1 ppm Cu; the copper was spectroscopically pure (Fe: 2 ppm; Ag, Mg, Si: 1 ppm). The copper and silicon samples were prepared in the form of blocks of approximately 10 by 10 by 5 mm with two parallel sides by spark-machining. The blocks were ground on emery paper (grit 600), etched (copper with nitric acid, silicon with a 4:l nitric acid:hydrofluoric acid mixture), and cleaned with alcohol. As the brittleness of the silicon did not allow a welding procedure to prepare the diffusion couples, the copper and silicon blocks were pressed together in a steel clamp. The pressure exerted by the clamp brought about contact between the parts of the couple and so ensured proceeding of the diffusion. The couples were heated in a vacuum furnace (about 10"5 Torr). The temperature was stabilized within 1 pct. After a heat treatment a section parallel to the direction of diffusion was examined in the microscope and in the X-ray scanning microanalyzer. To determine whether copper or silicon is the diffusing element marker experiments were carried out using tungsten wires with a 20-p diam. EXPERIMENTAL RESULTS Figs. 1, 2, 3, and 4 give micrographs of diffusion zones of Cu/Si couples. Analysis by the electron mi-croprobe of the Cu/Si samples after a definite heat treatment revealed the existence of only one intermetallic phase as can be seen from the line scan shown in Fig. 5. From the X-ray diffraction pattern it could be deduced that this phase was CU 3 Si.4 Even when diffusion zones of considerable width (up to 600 p) were obtained, no other phases occurring in the Cu-Si system could be detected, neither by the electron microprobe nor by X-ray diffraction analysis. The optical anisotropy of the Cu3Si phase made it possible to observe the columnar shape of the crystal-

Jan 1, 1969

By Robert Isaac Williams

The Questa mine is located in northern New Mexico on the western flank of the Sangre de Cristo Mountains about 75 miles north of Santa Fe and ranges in elevation from 6,800 to 10,000 ft. GEOLOGY The rocks of the area are Precambrian metamorphic rocks covered by Tertiary extrusive andesites and rhyolites and intruded by Tertiary granitic rocks. These Tertiary intrusives are localized in an east-west belt about 20 miles long and 2 miles wide, extending from Questa to Red River. The Questa orebody is associated with a north-trending aplite intrusive about 3/4 mile wide and 1 3/4 miles long. In the area of mineralization, the metasomatism of aplite has produced a mottled porphyritic rock. This hybrid rock has caused much of the controversy about the Questa mine intrusive. The orebody is essentially monomineralic and consists of numerous closely spaced molybdenite veins varying in thickness from ' 'paint" to 3 in. and occurring in both the andesites and the intrusive. In the intrusive the veins are often siliceous. Common alteration minerals associated with the molybdenite ore vary with the original composition of the rock. The alteration of the aplite has produced phenocrysts of orthoclase, albite, oligoclase and biotite; veins of quartz, orthoclase, and biotite; and graphic myrmekitic intergrowths of feldspars and quartz. In many places near the contact, the andesite is indistinguishable from the metasomatized aplite. The dominant alteration in andesite, however, is the development of fine-grained biotite with apatite, rutile, and sphene.

Jan 1, 1969

By G. L. F. Powell, L. M. Hogan

Samples of silver and Ag-O alloy, 0.12 wl pet, have been undercooled to a maximum of 250°C by melting in a slag of commercial soda-lime glass. Grain refinement occurred in undercooled silver samples whet the degree of undercooling exceeded a critical value which varied from 153° to 175°C, depending on the melting conditions. In under cooled Ag-0 samples, the grain structure was fine and equiaxed at degrees of undercooling larger than 50oC. The grain refinement in both silver and Ag-0 alloy samples was the result of recrystallization during or immediately following freezing. When the oxygen content was increased, the degree of undercooling at which recrys-tallization occurred decreased. INVESTIGATIONS of the grain structure of strongly undercooled melts of nickel and cobalt1-4 have revealed a change in room-temperature grain size as a function of undercooling. At large degrees of undercooling the grain size was fine, but samples undercooled by smaller amounts exhibited a much coarser grain structure. The reported undercooling at which this grain size transition occurred in nickel varied between 140° and 175'C undercooling. Walker1 attributed this grain size change to an enhanced nuclea-tion rate. Cavitation at a melt-solid interface was con sidered to generate a high-pressure wave. This, in turn, produced nucleation in the liquid as a result of an elevated freezing point increasing the undercooling in the melt. A similar grain size transition was observed in undercooled silver between 133° and 153°C undercooling.5 The grain size transition in undercooled silver was found to be dependent on oxygen con tent. More recently, the authors5 showed that a simila transition occurred in an undercooled Cu-O alloy, =0.08 pet, but not in oxygen-free copper undercooled more than 200°C. The transition was attributed to recrystallization of the solidified grains after freezing; the greater the degree of undercooling, the more complete the recrystallization. In view of this effect of oxygen content on grain size transition, additional undercooling experiments were carried out with silver. This paper reports the results of these studies on silver and Ag-O alloys undercooled more than 50°C EXPERIMENTAL 1) Materials. The silver was supplied by Matthey Garrett Pty., Ltd., as fine granulate, silver mini' mum 99.9 pet, and contained the trace impurities shown in Table I. The silver originated from two different refineries resulting in the difference in impurity content shown in Table I. However, the variation in composition had no discernible effect on the undercooling behavior. Samples of the silver were melted in an open-ended, vertical, cylindrical resistance furnace, wound with Kantha] wire, the temperature of which was adjusted by means of a variable transformer, 2) Melting and Undercooling. Bulk samples of silver were undercooled by preoxidation and removal of oxidized impurities in a glass slag, as previously described,5 but special precautions were necessary to allow comparison between oxygen-free silver and a Ag-O alloy. Samples free of oxygen were prepared by first melting weights of granulate varying from 200 to 400 g in clean vitreous silica crucibles in air for approximately 15 min. A sample was frozen and a complete glass cover formed over the top surface by adding granulated glass rod. The sample was then melted and frozen several times until no oxygen bubbles appeared in the glass slag. Subsequent thermal analysis indicated that the oxygen content was negligible. The glass acted as an efficient barrier to absorption of oxygen from the air. Ag-O alloys were prepared by melting silver in silica crucibles with only a partial cover of glass, so that the top surface of the melt was in contact with air. The silver was held molten in air for several hours at 1000° to 1050°C, in the expectation that the oxygen in solution would reach equilibrium with atmospheric oxygen. At T - 1000°C the equilibrium oxygen content was calculated as 0.12 wt pet O, using Sieverts law and Eq, [l], derived by Mizikar et a!.7 from the data of Sieverts and Hagenacker8 for 1 atm of oxygen:

Jan 1, 1970

By Joseph B. Darby, Paul A. Beck

IN isothermal sections of several ternary systems, the a-phase was found1 to extend in the form of a relatively narrow elongated field, connecting the U-phases that are present in the adjoining binary systems. This was interpreted in accordance with the conception that the U-phase is an electron compound and the ternary U-phase fields were shown in several systems' to extend approximately in the direction of constant average d-shell electron vacancy number per atom. ' However, in the various isothermal sections of the Fe-Cr-Mo system" the ternary a-phase field was

Jan 1, 1958

By N. Malakouti, R. H. Whipp, O. A. Kuby, R. M. Smailer

A detailed description of the development of the FIOR process (Brown, Campbell, and Saxon, 1966) and, subsequently, other technical papers related to the operation and start up of the FIOR plant (Violetta, 1975; Whipp, 1980) are available in the technical literature. The Fluidized Iron Ore Reduction (FIOR) process plant constructed in the Matanzas region of Venezuela represents the first commercial application of this technology. The FIOR process was developed by Exxon Co. during the 1950s and 1960s. The facility in Venezuela was designed and constructed by Davy McKee, with plant start-up in 1976. While there is a minority government ownership in the company, FIOR de Venezuela operates as a private sector company with the majority of ownership being private capital. The FIOR process is well suited to utilize the naturally occurring iron ore fines of the Cerro Bolivar and San Isidro iron ore deposits located less than 100 km (62 miles) south of the plant site. Availability of natural gas within 150 km (93 miles) to the north, and a location bordering on the confluence of the Caroni and the Orinoco Rivers makes for an ideal geographic site. Feed stock to the FIOR plant consists of naturally occurring iron ore fines from these ore bodies, which are screened to -6mm (-0.2 in.) prior to drying in the ore preparation plant. A simplified flow plan is shown in [Fig. 1]. The dried ore is then transferred to the top of a structure containing four fluid-bed reactors located above one another so the mineral may flow from one reactor to the next by gravity. A reducing gas containing 90% hydrogen is made by steam reforming of natural gas, a CO shift

Jan 1, 1983

By E. L. Spain

The deposits described in this paper occur over much of Wayne County and in the southeast portion of Hardin County, Tennessee, and in the northeast and northwest portions of Mississippi and Alabama respectively. The presence of tripoli in this region has been known for some time and descriptions of various occurrences in Tennessee have been made by Jewelll and Miser2, while Hilgard3, Lowe4 and Logan5 have treated the deposits that occur in the adjacent portions of Alabama and Mississippi, but there has not been a 'general survey of the entire field summarizing completely the geology of the deposits with respect to their origin and stratigraphic relationships. During 1934, while engaged in surveys of mineral resources through this region for the Tennessee Valley Authority, the writer collected data with this in mind, and has assembled them in this report. He is indebted to H. S. Rankin and N. A. Rose, of the Tennessee Valley Authority Geology Division, for field assistance. Location of Tripoli Deposits Fig. 1 shows the locations of deposits of tripoli in a long belt that extends from northeast Wayne County southwestward into northwest Alabama and thence passes into Mississippi, where the formations carrying it are finally covered by Cretaceous sand and gravel of the Mississippian Embayment. Occasional deposits occur also in the southeastern corner of Hardin County, Tennessee. While tripoli is found at nearly all points along this axis where the related formations are exposed, the largest deposits are grouped about three different centers. Waynesboro-Collinwood District.—In the area between Waynesboro and Collinwood, in Wayne County, Tennessee, tripoli of various grades outcrops in the valley of Green River and in tributary valleys on either side. This district is roughly 12 miles long in a northeast-southwest direction and has a maximum width of 5 miles at its northern end. Exposures are found in road cuts, highway chert pits, in the beds of some of the streams, and on hillsides. The greatest number of high-grade

Jan 1, 1938