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By Edmund C. Pechin

THE writer approaches this subject with a great deal of diffidence —first, because it is utterly impossible to treat it satisfactorily within the limits of a paper, and, secondly, because the larger development is of so comparatively a recent date as to make authoritative data on some interesting points unavailable. For over one hundred years small charcoal-fnrnaces have been in existence, at widely scattered points, making a few tons of iron daily, and then gradually increasing to a daily output of, say 10 to 12 tons, as the market widened. With the exhaustion of local supplies of wood, inaccessibility to market, and sharp competition, bringing lower prices, many were compelled from time to time to make temporary stops, and finally to cease altogether. During the first half of the century there were at different times in operation between 75 and 90 charcoal furnaces. The last Directory of the Iron and Steel Works of the United States (1890) gives 19 as the number of charcoal-stacks in Virginia. Of these several are cold, and, it is

Jan 1, 1891

By W. H. Emmons

MANY mineral veins occupy faults, and movements on certain warped fault planes have resulted in openings. On normal faults the [ ] steeper parts have the widest openings, and on reverse faults the flatter parts have the widest openings. Theoretically the width of the opening is the sine of the angle of deflection times the amount of movement on the fault plane, but actually the widths of some of the openings are probably less because of readjustments of walls along joints or of other readjustments. The first treatment of the subject seems to have been in a book on mineral veins by John Leithart, published in Newcastle, England, in 1838. Later the subject was treated in various texts published in Germany, in England, and elsewhere. The subject was not given much prominence in the earlier American literature on economic geology, but has interested several workers in that field in the past decade. In this paper examples of districts showing ore shoots on warped faults, with relations noted, are described. Fault veins of the three depth classes of veins are noted. Many epithermal veins are in normal faults, and commonly the larger ore shoots are in their steeper portions. Many mesothermal veins are in reverse faults and many others are in normal faults. The flatter parts of veins in reverse faults are commonly wider than the steeper parts, although they are not always as rich as the steeper segments of the veins. There are not many hypothermal veins in faults of measured displacement.

Jan 1, 1943

By J. A. Herrick

For a long time, especially in Europe, heavy pieces of forging, such as cannon, armor plates, marine shafting, etc., have been steadily augmented in size, more particularly since steel has been substituted for wrought iron. To keep pace with these forgings several very large hammers have been, from time to time, erected. The most powerful and thoroughly appointed of all now in operation is that designed and built by Messrs. Schneider & Co. at their' works at Creusot, and it is the design of this communication to give to the members of the Institute a concise description of this remarkable piece of mechanism, which I have taken from an article published in the Annales Industrielles. This hammer is rated nominally at 80-tons power, but its capacity is, in reality, far greater, as will be seen by the comparative figures given later. The complete plant, comprising the hammer, the cranes, the furnaces, and the building which shelters the whole, is distin-

Jan 1, 1880

By C. H. Gerould

I would like to take a moment to consider our polystyrene-silica replica technique, which was developed at the Dow Chemical Co. and which was mentioned in the paper just given by Mr. Thielsch. He stated that he feared that our replica technique would cause difficulty due to deformation of the metal as a result of the application of pressure during the molding process. We at the Dow have never had any reason to suspect that any deformation of the metal was occurring during the molding process. Our procedure has been to heat the polystyrene to a temperature of 160°C. before applying any pressure, at which temperature the polystyrene is a viscous liquid. By so doing the pressure of the polystyrene against the metal is essentially hydraulic and is therefore applied equally in all directions, which we feel should not cause deformation. Our work using this replica technique has brought forth several indications that deformation of the specimen is negligible. These indications are: I. Direct comparisons have been made between the light and electron microscopes when studying a specific spot on a metal surface. These "same spot" studies were obtained by first taking micrographs at high magnification, with a light microscope, of a specific structure that could be readily recog-

Jan 1, 1947

By H. E. Wilborg

This chapter deals with those sands employed by the foundries for the manufacture of cores and molds used in the casting of such common metals as steel, gray iron, ductile iron, aluminum-based alloys, and copper-based alloys. Most metal is cast in "green sand" molds in which the sand mixture, consisting primarily of silica, clay, and water, forms a plastic material. This plastic material is rammed around a pattern in a split box called a flask, then the box is separated, the pattern is withdrawn, and the metal poured. These green sand molds are broken apart when the metal has solidified. The sand is then remixed and a new mold made for the next casting. To a lesser extent silica sand is mixed with resins or oils and, after forming, the mixture is hardened either by heat or chemical reaction. In any case, the foundry mold or core is used just once before being broken up and remixed for manufacturing another core or mold. By far the greatest consumption in the foundry is of those types of sand high in silica, low in clay (under 0.5%) and occurring in numerous locations thoughout the United States.

Jan 1, 1975

By J. Charles Miller

THE expansion of facilities for rapid transportation of perishables by train, truck and airplane has necessitated consideration of refrigerants of a minimum weight and volume per pound of cooling and has stimulated the use of solid carbon dioxide commercially. The gas probably has not had wide application in the past in air-cooling equipment for mines, theaters or buildings, owing to its thermodynamic properties, as will be deduced from examination of Table 2. However, consumption of the liquid in carbonating beverages remains a dominant factor. In addition to these uses, carbon dioxide is employed to a limited degree as an explo-sive in the liquid form, as a freezing agent in plumbing, in laboratories for low-temperature work, and in the manufacture of golf balls.

Jan 1, 1936

By M. C. Lavine, H. C. Gatos, R. S. Mroczkowski

The structure of GaAs-Ge heterojunctions prepared by a back-melting process was studied by X-rav diffraction, melallographic, and electron-micro-analyzer techniques. The boundary region between the GaAs and the germanium was found to consist of a four-layered band. A discontinuity between the two inner bands was brought about by solidification occurring simultaneously from the GaAs and the germanium side. The junction material OH either side of the central discotinuity was found to have grown as a single Crystal with the orientation of the parent substrate. It was found essential to determine the GaAs-Ge phase diagram. This was accomplished by a series of alloys containing 0 to 40 wt pet GaAs. Over this range the diagram is a simple eutectic with the eutectic point at 74 wt pet Ge and 845 C. The limiting- solubility of Coils in germanium was found to bc less than 5 wt pet. The Kossel divergent-beam X-ray technique was used to study orientation relationships across the boundary lager. A great deal of effort has been recently expended on the electrical properties of heterojunctions. Little attention, however, has been given to the metallurgical variables which may be of importance in the formation of the junctions. The present work was undertaken to investigate some of the more pertinent metallurgical aspects of interface-alloyed GaAs-Ge heterojunctions. Such parameters as solidification processes, composition gradients, orientation effects, and the accommodation of crystal structures have been the objects of study in this program. EXPERIMENTAL PROCEDURES Phase Diagram. The phase diagram of the GaAs-Ge pseudobinary system was determined by means of cooling curves. A Bridgeman furnace was employed with the center section maintained at 1200°C and the upper section at 800°C. Melts varying from 0 to 40 at. pct in GaAs content were used. Each charge was incapsulated under a two-thirds atmosphere of argon in a carbon-coated quartz tube. Five min in the furnace hot zone provided rapid melting and homogenization. The capsule was then removed to the cooler portion of the furnace. Cooling times were of the order of 3 min. The resulting homogeneous microstructure indicated that equilibrium conditions were obtained by this procedure. Formation of Heterojunctions. Rectangular parallelepiped single-crystal samples were cut with the large faces of either the (l00), (110), or (111) orientation. The remaining four surfaces were also cut to specific orientations to permit accurate relative orientation of the GaAs-Ge pairs. The

Jan 1, 1965

By Howard Reiss, C. S. Fuller

A theoretical and experimental study has been made of those interactions between holes and electrons which influence the solubilities of donors and acceptors in semiconductors. The major portion of the work concerns the solubility of lithium in silicon doped to varying degrees with boron. This solubility increases with increasing boron content in a manner predicted by theory and exhibits the expected temperature dependence. A qualitative experiment in germanium is described which demonstrates, in accordance with theory, that doping with a donor decreases the solubility of another donor. SEVERAL authors have discussed the possibility that holes and electrons behave like chemical entities and influence the solubilities of ionized impurities, Wagner was the first to invoke this concept in connection with his studies on nonstoichio-metric oxides. He used it again in explaining the solubility of hydrogen in molten binary alloys. In a theoretical paper,' Reiss drew attention to the fact that solutions of impurities in semiconductors

Jan 1, 1957

By R. S. Shoemaker, F. W. McQuiston

CARLIN GOLD MINING COMPANY 1974 Operating Data to October MINE LOCATION: 40 miles from Elko, Nevada ORE DESCRIPTION: Gold with minor amounts of mercury occurring in siltstone and carboniferous limey shales. TYPE OF MINE: Open pit ORE HAULAGE TO MILL: By trucks up to a distance of 12 mi1es MILLING CAPACITY: 2500 tons per day ORE GRADE: 0.20 oz per ton oxide ore 0.25 oz per ton carbon type ore PRODUCTS: Gold bullion 993 fineness, by product quicksilver RECOVERIES: Oxide ore 887'0 Carbon ore 83% POWER FOR GRINDING: 7 Kwh/T POWER, other than grinding: 14 Kwh/T WATER SUPPLY: Pumped from wells 2- 112 miles through 13,000 ft of 8" buried pipe 6 ft underground. Consumption 0.60 tons of new water per ton of mill feed. TAILINGS: By 10" woodstave pipe a distance of 2500 ft to mine waste filled dam. RUNNING TIME: 10 ft x 10 ft mill on oxide ore, 98% 7 ft x 8 ft mill on carbon ore, 937'0 Principal causes of lost time, power outages and problems of feeding gaseous chlorine to carbon ore agitators. LABOR, TONSIMAN SHIFT: See detailed data sheet ILL BUILDING DESCRIPTION: Framed structural steel with sandwich type walls of marine plywood, then packaged pre - fabricated insulation and outer sheeting of galvanized corrugated steel.

Jan 1, 1975

By B. W. Howlett, M. B. Bever, Somnath Misra

The heats of Formation of the compounds Sb2Se3, Bi2Se3, Sb2Te3, and Bi2Te3 and the heats of solution of tellurium and selenium in liquid bismuth have been measured in a liquid metal solution calorimeter. The heat capacities near the melting point, the heats of fusion, and the melting points of the two tellurides have been measured in a constant temperature gradient calorimeter. The thermo-dynamic quantities are interpreted in relation to the stability of the compounds and the nature of the solid-liquid transition. THE selenides and tellurides of several elements of Group VB of the periodic system are of interest because of their electronic properties. The compounds Sb2Se3, Bi2Se3, Sb2Te3, and Bi2Te3 are semi- conductors; they also have gained prominence in the fields of thermoelectricity and photoconductivity. However, little is known about their thermody-namic properties. As part of a research program on the thermo-dynamic properties of intermetallic compounds, the heats of formation of the compounds Sb2Se3, Bi2Se3, Sb2Te3, and Bi2Te3 were measured in a liquid metal solution calorimeter. The heat capacities near the melting point, the heats of fusion, and the melting points of the two tellurides were measured in a constant temperature gradient calorimeter. The results, in addition to their intrinsic interest as thermodynamic quantities, contribute to an understanding of the stability of the compounds and the nature of the solid-liquid transition. 1) EXPERIMENTAL 1.1) Materials. Samples of the compounds SbzSe3 and Bi2Se3 were prepared by melting the elements in stoichiometric proportions in evacuated Vycor capsules followed by quenchinn in water. They- were then annealed in vacuum for 12 hr at 550°C. A sample of Sb2Te3, consisting mainly of one large grain, supplied by the Lincoln Laboratory,

Jan 1, 1964

By J. D. H. Strickland, K. J. Jackson

IN previous papers' ' details were given of the constructlon and use of an apparatus to study the rate of chlorine consumption and the rate of sul- fate and sulfur production when dilute aqueous chlorine solutions were allowed to react with pyrite and galena in acid solutions at or near room temperature. The reaction with pyrite was very rapid, and hence entirely transport-controlled in its kinetics, and produced only ferric and sulfate ions. The behavior of galena was much more complex and was studied in some detail. Sulfur monochloride could be detected as a reaction product and both

Jan 1, 1959

By W. O. Philbrook, R. H. Spitzer, F. S. Manning

A generalized mathematical model has been developed to describe the kinetics of the gaseous, topo-chemical reduction of porous hematite spheres. Gas-solid reduction is permitted at each of three advancing interfaces and is controlled by a complex series-parallel sequence of chemical and transport steps. Despite the fact that transport resistances are significant to the advance of each interface, little deviation from linear advance is predicted for the first 98 pct of reduction. Calculations to predict the movement of magnetite /wustite interface by a solid-state diffusion mechanism have been incorporated into the earlier dense-pellet model.' The porous-pellet model is found to give a better description than the dense-pellet one for McKewan's measurements2 of interface movements in dense polycrystalline hematite reduced in hydrogen-water vapor mixtures. THIS paper reports a continuation of work"3" directed toward the better understanding of gas-solid reactions and the development of mathematical models that may be helpful in the design or control of ore-reduction processes. Laboratory studies of the reduction of single oxide samples in tube furnaces normally employ an abundant excess of pure reducing gas. Reduction may appear to be adequately described by a model assuming gas-solid reaction solely at the iron/wustite interface.''' However, when iron ore is reduced in either a fixed bed or an efficiently operated counter-current column, there are portions of the bed where the partially spent gas is no longer capable of reducing wustite to iron. Nevertheless, the formation of the intermediate reaction products, wustite or magnetite, can and does continue. In order to account for this aspect of the reduction of beds of particles, three semiempirical mathematical models were devised.' One of these was for the limiting case of completely dense particles, and two alternatives were provided for porous particles. For purposes of the analysis, a dense pellet was defined as one in which the wustite and magnetite layers were impervious to the reducing gas when the atmosphere was capable of forming iron. In a porous pellet, the intermediate product layers were assumed to be sufficiently permeable to allow reducing gas to penetrate beyond the iron/wustite interface to form wustite and magnetite by removal of oxygen as a gaseous product rather than by a solid-state redfiction mechanism. Further progress required a better understanding of the reaction of the individual particles with the gas stream. A comprehensive mathematical treatment was developed' to describe the continually changing interplay of transport and reaction steps

Jan 1, 1967

By L. F. Marek, G. W. King, A. Bogrow

THE purpose of this paper is to present the data and some interpretation of the results of a laboratory study of the reduction of iron ore and the deposition of carbon from the reducing gas mixtures in such reductions. One major object of the study was to determine the effect of gas pressures on these chemical processes. Effort was made to approximate the conditions of temperature, gas composition, linear and mass gas velocities, pressure range, and extent of reduction prevailing in commercial blast furnaces. The results show that the reduction of Fe203 proceeds by two steps, largely consecutive under the conditions used herein: reduction of Fe203 to FeO, and reduction Of FeO to Fe. Unless the gas has a CO/CO2 ratio greater than 2.1 only the first step occurs under these conditions (850°C) but the following generalizations apply to either step or to the combination. The rate of reduction of relatively fine ore particles at any time is proportional to the mass rate of supply of CO (provided some of it is thermodynamically available) the rate therefore is proportional to the linear velocity at constant pressure, or to the pressure at constant linear velocity. Thus, the rate of reduction may be increased without increase in linear velocity f the reducing gas by increasing the mass velocity of the gas and increasing the pressure correspondingly to avoid any increase in the linear velocity. The rate "constants"-i.e., the efficiency of conversion of the "available" CO supplied-is not actually constant but decreases as the reduction proceeds, and is a function only of the state of the ore; i.e., of the amount of reduction already accomplished and hence of the amount of CO passed. The particle size Of ore used in nearly all the experiments was relatively small (8 to 14-mesh). The rate of reduction in run 16 with 3 to 8-mesh ore particles is within experimental error the same as with the finer ore. Although this would indicate an absence of effect due to particle size in this range of ore particles, it is desirable to have more data on other ore sizes and on ore of different densities before arriving at any generalizations on this point. Although it is possible to extend the analysis of these results to consideration of the more detailed kinetics and mechanism of iron oxide reduction, such extension is beyond the scope of the present paper. From the experiments on carbon deposition, it was evident that if carbon deposition is increased at all by the application of pressures up to 10 psi ga., such increase appears to be less than the experimental and analytical error. It appears safe to conclude that at top pressures on the order

Jan 1, 1947

By Henry E. Wood

In my opinion, the concentration of minerals by flotation is the most interesting problem in ore-dressing, and will command eventually far more consideration than it has at present. For many ores it furnishes a complete method of concentration absolutely independent of specific gravity, and thus simplifies the milling of many difficult combinations. Not having to recognize the influence of specific gravity, we are also able to dispense with some of the complications resulting from classifying-conditions. Where flotation cannot be used for a complete separation of the minerals from the gangue, it will be found, in nearly all cases, to save those portions which are generally lost by reason of their fine state of division. For this reason, it should be looked upon mainly as an aid to general concentration, although there are many ores so well adapted to flotation that more than 90 per cent. of the valuable metals can be recovered from them in one operation by this process. In presenting the results of my investigations in flotation, I have endeavored to theorize as little as possible. That side of the subject has been extensively discussed by others. My earliest work with flotation was done in 1895, when I used various oils, grease, soap, etc., with results that were remarkable. I did not realize then that with water alone equally good separations could be made. Up to 1906, my endeavors were confined to attempts to keep the concentrates on the tables well wetted and away from exposure to the air. In common with others, I observed that when there mas any obstruction in the wash-water on the table of sufficient size to divert the water to either side, the concentrates collected, and, on exposure to the air, would promptly float away. This convinced me that the sulphides were all good "swimmers," and that if,

Jan 1, 1913

By David H. Browne

The use of coal-dust fired reverberatory furnaces, or indeed of rever-beratory furnaces of any description, was for the Canadian Copper Co. a matter of necessity, and not of choice. For 20 years smelting had been done in blast furnaces alone, and with the Herreshoff furnaces used prior to 1904 there was no trouble in treating fine ores. But little flue dust was produced, and this, following the time-honored custom, was wetted down and put back with the charge. Whether the flue dust really smelted, or whether it was worn out by being chased around in a circle, was a problem that troubled no one. With the installation of modern blast furnaces and high-pressure blowing engines, in 1904, flue dust commenced to assert itself. Evidently more dust was made than could be smelted, but so many vital. problems engaged our attention at that time that this minor question was pushed to one side. In 1906, the details of blast-furnace smelting and the conversion of matte had been worked out to a satisfactory conclusion, and the ever-increasing piles of flue dust and fine ore on the stock yard demanded serious consideration. Numerous experiments in sintering, briquetting, mixing with converter slag, forming blocks of flue dust with green-ore fines and cement, and so on, were undertaken. None of these showed much promise. Our problem was still further complicated by the question of treating converter slag. The ore was basic, the slag was not needed as a furnace flux, and it was felt that under these conditions the old method of pouring slag in molds and resmelting in the blast furnace was an unnecessary expense. If the converter slag could be settled in basic-lined reverberatory furnaces, in which at the same time flue dust and green-ore fines could be smelted, two problems might thus be solved. Reverberatory practice with our ores was, however, an unknown factor. As carried on in the West, on siliceous ores and concentrates, at least 25 per cent. of fuel was required, and even this ratio depended greatly

Jan 1, 1915

By M. A. Childers

Recent work with controlled laboratory tests.' field experience and a new analytical approach indicate that casing centralization, pipe movement and relative rheological properties between the mud and cement (yield point and density) are the three controlling factors in successfu1 primary cementing of dual casing. Turbulent flow has been demonstrated to be unnecessary under the severe displace ment conditions of parallel dual strings of casing. Simultaneous reciprocation of dual casing in directionally drilled boreholes is highly dependent on centralization and on the rapid initiation of pipe movement once the casing has been run to total depth. Successful cementing of 30 out of 32 dual, 3%-in casing wells substantiated these conclusions. A review of 15 dual, 3 1/2-in. casing wells completed prior to the adoption of these principles disclosed only one success. Mathematical and graphical techniques permit the engineer to analyze and anticipate the success or failure of a cementing operation. Standoff, mud displacement and reciprocation can be analyzed mathematically and planned in deep, directional or straight boreholes by review of annular geometry, relative rheological properties between the mud and cement, and forces caused by caring weight, functional drag and differential sticking. Introduction The objective in primary cementing is to displace the drilling fluid with cement that will bond to the formation and casing to prevent communication through the annulus. The predominant cause of failure appears to be channels of gelled mud that remain in the annulus after cementing.1 '* Past investigations have noted many procedures that could improve the displacement process.2-' These procedures include centralization, chemical preflushes, mechanical mud cake removers, controlled flow rates in certain regimes, pipe movement an1 control of mud and cement properties. Not until recently have the effects of many of these procedures been isolated so that their individual importance could be determined. In a recent paper,' a comprehensive and analytical laboratory study of various factors controlling the displacement process concluded that there are three major factors in obtaining complete mud displacement by the cement slurry. 1. Good relative rheological properties between the mud and cement. The cement should be heavier and have a yield point and plastic viscosity higher than the mud being displaced. Buoyancy forces often can dominate the displacement process. 2. High degree of standoff or centralization. The more centered the casing, the greater the likelihood of complete mud displacement and removal. 3. Pipe movement obtained by rotation or reciprocation. Often unfavorable rheological properties between the mud and cement, and poor standoff can be compensated by pipe movement. This work demonstrates the compatibility of the latter concepts with field results extended to the more severe dual casing displacement process. Early Experience With Dual 3'/t-In. Primary Cementing Early slim casing completions in the West Delta Block 73 field, offshore Louisiana, included 17 dual 3%-in., 3 single 3% -in. and 1 dual 2% -in. casing installations. Table I provides data on these earlier wells. Usually, common Class A cement was placed across the pay zone and 12 percent gel cement was placed to a height of 500 ft above the highest productive sand. Centralizers (6%-in. OD maximum expansion) were placed two or three per joint on both casing strings from total depth through the completion intervals and at least one per joint for the remainder of the cement sheath. A number of techniques and procedures were attempted to improve cementing success. Casing was run simultaneously or separately with a number of mud conditioning and circulating techniques. Mechanical aids such as cement bonders, slmiding sleeves, turbulizers and various sizes and strengths of centralizers were used. Common and gel cements were mixed with fresh or sea water with a number of different additives to control retardation and dispersion. Cements were thinned and mixed at high rates to try to induce turbulent flow in the annulus. On one well the "slow flow" method was used." Perforating was accomplished with a jet orienting gun. Unsuccessful cement jobs were indicated by production of extraneous fluids or by pressure communication between zones. On test, five wells flowed water, four flowed sand and six had pressure communication with the other string or the 10%-in. casing. A total of 25 remedial squeeze ce-

Jan 1, 1969

By Cyril Stanley Smith, Earl W. Palmer

STRIP of any of the metals used for deep drawing operations occasionally yields cups that are defective because of a rim that varies in height around the cup in a wave-like manner Some such defects are traceable to tools or other press factors, but when the protuberances formed (usually four in number on brass and other copper alloys) are symmetrically disposed with respect to the rolling direction of the strip, they are invariably attributable to the metal The effect is known as "caring" and the protuberances are called "ears" Other terms frequently heard are "tips," "scallops," and "corners " It is recognized that the effect is most commonly a result of a directional crystal structure produced by rolling and annealing operations in the manufacture of the metal strip Numerous papers dealing with various aspects of the caring effect have appeared in the literature, those listed in the references' being especially interesting and valuable An investigation of the factors influencing caring of brass cups has been in progress in the laboratories of the American Brass Co for several years, and it was thought desirable to make some of the results generally available in summarized form The present paper discusses many factors that do and do not contribute to ear formation In addition, a section is devoted to methods of minimizing the caring tendency of brass sheet by proper selection of the cold-rolling and annealing schedule by which it is produced In the space available, it is impossible to quote detailed experimental procedures and numerical results However, the authors make no statement that they do not believe to be properly substantiated, either by experimental evidence obtained under laboratory conditions or by experience in the actual production of deep-drawing brass in the brass mill MECHANISM OF EAR FORMATION It must be clearly understood that the formation on cups of symmetrical ears, four or more in number, is attributable solely to the strip metal, and results from the strip having different deformation characteristics in different directions The tools used in the drawing process, or the type and completeness of lubrication of the strip, have nothing to do with the problem of ears, although they do, of course, greatly affect the "drawing quality" of the strip and the general appearance of the cup A single tip may be drawn up on the rim of a cup because of misalignment of the tools, or because the gauge of metal varies from side to side of the strip The two-ear form that sometimes appears is also traceable to gauge variations However, the four-ear and six-ear symmetrical forms that we are concerned with here are caused by factors inherent in the structure of the metal itself

Jan 1, 1942

By A. A. Smith, J. S. Smart, A. J. Phillips

The preparation of a sufficient quantity of high-purity copper for extensive laboratory use in the study of impurity effects has been an integral part of a research program in progress at the Central Research Laboratory of the American Smelting and Refining Co. for the past several years. Initially the degree of purity desired was that necessary to meet two essential requirements for experimental accuracy: (I) no impurity was to be present in the copper in an amount capable of producing a detectable effect on the properties to be studied, (2) even the minor changes in propertties caused by the addition of extremely small amounts of individual elements were to be measured without significant interference from contaminants. In the course of the investigation, evidence has accumulated to justify the conclusion that this copper is of exceptional purity; in fact, no impurity can be detected by any chemical method or spectrographic technique known to the authors. The present paper describes the method of production of the copper and presents some of its properties. Preparation oF High-purity Copper The elimination of impurities from commercial electrolytic copper is accomplished by a three-step purification process. The first operation consists of an electrolysis through a purified CuSO4-H2SO4 electrolyte using bagged anodes, low current density (5 amp. per sq. ft.) and low tem- perature (25°C max.). The electrolyte is prepared from commercial Cu2SO4 and is purified by heating the solution and adding I gram Fe as Fe2(SO4)3 to each 100 grams dissolved copper; sufficient hydrated oxide of copper, prepared from Cu2SO4 and NaOH, is supplied to precipitate Fe(OH)3, which carries down arsenic, antimony, tin, selenium, tellurium and other minor constituents. Silver and remaining traces of lead are removed by addition of Na2S to the acidified filtrate, which is then reatered after standing hot overnight. The cold solution is made up to 30 grams per liter Cu and 150 grams per liter H2SO4 and introduced without addition agents into the electrolytic system, which consists of a double row of hard-rubber battery boxes with the inside webbing and partitions removed, arranged in seven steps of ascending height. Electrolyte is uniformly supplied to the two highest cells by glass siphons operating from a constant-level reservoir, and flows by gravity through the bank of seven cells, entering each at the bottom and leaving at the top. Glass air lifts continuously supply the returning liquid to the constant-level reservoir for recirculation. Each cell contains three 4 3/4 by 4 3/8 by 1-in anodes cast from high-quality electrolytic wirebar copper, various lots of which have been used with equal success. The anodes are pinned to sheet copper hangars shaped to prevent crawl of the electrolyte to the multiple-wired bus bars—which would result in fouling of the contacts—-and hang inside wool flannel bags stretched over open wood frames. The deposit

Jan 1, 1941

By A. J. Phillips, A. A. Smith, J. S. Smart

The preparation of a sufficient quantity of high-purity copper for extensive laboratory use in the study of impurity effects has been an integral part of a research program in progress at the Central Research Laboratory of the American Smelting and Refining Co. for the past several years. Initially the degree of purity desired was that necessary to meet two essential requirements for experimental accuracy: (I) no impurity was to be present in the copper in an amount capable of producing a detectable effect on the properties to be studied, (2) even the minor changes in propertties caused by the addition of extremely small amounts of individual elements were to be measured without significant interference from contaminants. In the course of the investigation, evidence has accumulated to justify the conclusion that this copper is of exceptional purity; in fact, no impurity can be detected by any chemical method or spectrographic technique known to the authors. The present paper describes the method of production of the copper and presents some of its properties. Preparation oF High-purity Copper The elimination of impurities from commercial electrolytic copper is accomplished by a three-step purification process. The first operation consists of an electrolysis through a purified CuSO4-H2SO4 electrolyte using bagged anodes, low current density (5 amp. per sq. ft.) and low tem- perature (25°C max.). The electrolyte is prepared from commercial Cu2SO4 and is purified by heating the solution and adding I gram Fe as Fe2(SO4)3 to each 100 grams dissolved copper; sufficient hydrated oxide of copper, prepared from Cu2SO4 and NaOH, is supplied to precipitate Fe(OH)3, which carries down arsenic, antimony, tin, selenium, tellurium and other minor constituents. Silver and remaining traces of lead are removed by addition of Na2S to the acidified filtrate, which is then reatered after standing hot overnight. The cold solution is made up to 30 grams per liter Cu and 150 grams per liter H2SO4 and introduced without addition agents into the electrolytic system, which consists of a double row of hard-rubber battery boxes with the inside webbing and partitions removed, arranged in seven steps of ascending height. Electrolyte is uniformly supplied to the two highest cells by glass siphons operating from a constant-level reservoir, and flows by gravity through the bank of seven cells, entering each at the bottom and leaving at the top. Glass air lifts continuously supply the returning liquid to the constant-level reservoir for recirculation. Each cell contains three 4 3/4 by 4 3/8 by 1-in anodes cast from high-quality electrolytic wirebar copper, various lots of which have been used with equal success. The anodes are pinned to sheet copper hangars shaped to prevent crawl of the electrolyte to the multiple-wired bus bars—which would result in fouling of the contacts—-and hang inside wool flannel bags stretched over open wood frames. The deposit

Jan 1, 1941

By W. C. Ellis, E. S. Greiner, M. E. Fine

C. H. Samans and W. R. Ham (Chicago, Ill., and Dix-field, Maine, respectively)-—For several years we have been studying transitions of this basic type in metals, alloys, glasses, etc. Usually, however, they are not so clearly marked as those which the authors have found, and hence are much more difficult to determine accurately. Since our studies indicate that most of them occur virtually unchanged (as far as temperature is concerned) regardless of the form in which the element appears, we believe that they are a characteristic of the atom. Specifically, we believe that there is an additional rotational degree of freedom possessed by the nucleus which has not been considered heretofore. This nuclear rotation is made up of several components, each related to the several quantum shells of electrons. In chromium there are four of these shells and hence four separate series of characteristic transition temperatures. The lowest temperature at which any transition occurs, based on the present state of our computations, is 125°K, 4° higher than the authors' value of 121°K. A convergence of this series, we believe, shows up at the higher temperature of 2085 °K, surprisingly close to the transformation temperature of 2103°K recently announced by N. J. Grant of M.I.T. for a body-centered to face-centered transformation in chromium. Likewise, our computations indicate a temperature of 311°K for the second transition temperature, reported by the authors as 310 °K. A convergence of this series, we believe, shows up at a higher temperature as the melting point at 2163°K. Although our work on these series must, in a sense, still be regarded as empirical, since we do not understand fully as yet just what the series mean, it is based on a reasonably firm picture. The individual constants, from which the various series are computed for each element, comes directly from the X-ray K absorption limit. Furthermore, the same basic method has accounted for transformation and melting temperatures in about 50 of the chemical elements, which is all we have tried thus far. In many cases the only known transformation is the melting point, but in others the occurrence of transformations or other transitions, equally as well marked as those of the authors, has been pointed out by others. These observations have assisted us greatly. Consequently we were very pleased to see the authors' excellent work in finding these two transitions in chromium. With these confirming data, our picture of this element is clarified considerably, so we expect that at least some of our work can be published in the near future. R. C. Ruder (E. I. du Pont de Nemours & Cu., Wilmington, Del.)—The authors' interpretation of these transitions in terms of 3d to 4s electronic structure transitions is most interesting. It would be interesting to have additional experimental evidence of such transitions from the temperature dependence of the Hall coefficient in the neighborhood of the property changes discussed in this paper. Simple theory15 suggests the Hall coefficient as a measure of the free electron (or s electron) concentration per unit volume. It has been shown that for paramagnetic'" and ferromagnetic1? metals the simple theory is in fact too simple. However, the existence of a discontinuity in the Hall coefficient would provide information which should aid both in our understanding of these transitions and the significance of the Hall coefficient in these metals. It was rather surprising that no significant paramagnetic effects were observed. In this connection the recent work of McGuire and Kriessman18 is cited. They measured the magnetic susceptibility of chromium from 20" to 1460 °C. They also observed no large change in the susceptibility although there might be a change in slope in the vicinity of the 40 °C transition. The existence of these 3d to 4s electronic transitions has been discussed in connection with the paramagnetic susceptibility behavior of nickel and nickel alloys.'"-" Assuming a correspondence principle between classical and quantum mechanical paramagnetic theory and using classical theory to calculate the effective Bohr magneton number from the Curie constant for substances obeying the Curie-Weiss law," it is found that the effective magneton number is a function of temperature. The process of calculation involves the inverse of the differential of the 1/x4 vs. temperature curve so that good and numerous data are necessary to obtain significant results. The data of Fallot23 show a discontinuous increase of about 12 pct in the effective magneton number between 850" and 900 oC, followed by a continuous increase up to the melting point. The data of Sucksmith and Pearce24 show a possible 8 pct increase. The older data of Terry25 and Weiss and Foex26 show a continuous increase. It is possible that small amounts of impurity atoms change these electronic transitions significantly. Fallot's23 data on a nickel alloy with 4.5 atomic pct Fe indicate that the discontinuity occurs around 1300 °C. Systematic investigation of the transition metals for transitions of this nature should provide information which would be very valuable for our understanding of these metals. The absence of antiferromagnetic structures in chromium has been shown by Shull27 using neutron diffraction techniques. M. E. Fine, E. S. Greiner, and W. C. Ellis (authors' reply)—The remarks by Drs. Samans and Ham are certainly very interesting, in particular those pertaining to the close agreement between the theoretically calculated values for transition temperatures in chromium and the experimental values reported by a number of investigators. This is a remarkable achievement and we shall look forward to a more detailed presentation of the method followed in their calculations. We do not believe that the transition in pure chromium near 40 °C remains temperature invariant with alloying, as was reported by Samans and Ham for a number of the substances that they studied. We have not done any work with alloys but base our belief on the results of earlier studies in which less pure chromium was included and considerably lower transition temperatures were observed. The transition tempera-

Jan 1, 1952