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By M. C. Udy, F. W. Boulger

AN incomplete phase diagram for the U-Ti systern was determined earlier 1 and more recently, a tentative diagram was presented for the uranium-rich end of the system.' In the present re-examination of the whole system of U-Ti alloys, high purity materials were used. Melting stock for the alloys was high purity uranium, containing about 0.09 pct C as the only appreciable impurity, and high purity iodide-process titanium purchased from New Jersey Zinc Co. Both metals were cold rolled to about 1/6 in. thickness, sheared to about I/' in. squares, and cleaned by pickling. The alloys were arc melted under a helium atmosphere in a water-cooled copper crucible. A thoriated-tungsten electrode was used. The furnace chamber was evacuated, then flushed with helium, prior to each melting. It was finally filled with stagnant helium at one atmosphere pressure. Each alloy was remelted three times after the original melting, to insure homogeneity. The alloy button was turned bottom side up before each re-melting operation. Some 22 alloys were examined. Their compositions were spaced at appropriate intervals between 100 pct Ti and 100 pct U. Analyses were made on chips taken after fabrication. The major contaminant was carbon, which varied from 0.03 to 0.08 pct. It appeared in the microstructure as titanium carbide. Alloy compositions were calculated to a carbon-free basis for consideration on the diagram. Tungsten and copper, possible contaminants from the melting operation, were generally less than 100 parts per million each. Fabrication All alloys were forged and rolled to bars approximately V8 in. square. They were clad either in SAE 1020 steel or in a 5 pct Cr-3 pct Al-Ti-base alloy, depending on the fabrication temperature. A temperature of 1800°F (980°C) was used for alloys near the compound composition. This necessitated using the titanium-base alloy, since iron reacts with titanium at this temperature, producing a low melting alloy. Other alloys were fabricated at 1450°F (790°C), using steel jackets. No iron-titanium reaction occurred at this temperature. The jackets were welded in place in an argon atmosphere. Those alloys sheathed in steel were declad and then reclad between rolling and forging operations. On the other hand, those clad with the titanium alloy were cut to a roughly rectangular shape prior to clading and were then carried through both the forging and rolling operations without opening. Those alloys near the compound composition were found to be cracked when the clading was removed. The cracked materials had been plastically deformed, however, and at least some of the cracking had OCcurred during cooling. Heat Treatment The rolled bars, after being declad and shaped to remove surface contamination, were all given an homogenizing treatment of 160 hr at 2000°F. (Samples were taken for analysis following the declading and shaping operations.) All were heat treated at the same time in one furnace, but each was sealed in a purified argon atmosphere in an individual Vycor glass tube. Argon pressure was such that it was approximately atmospheric at temperature. One end of each tube contained titanium chips and this end was heated to 1200°F (650°C) for 10 min prior to the heat treatment. This purged the atmosphere of residual reactive gases. The balance of the tube was warmed during the purge to liberate adsorbed moisture and gases, which also reacted with the hot chips. The bars were furnace cooled from the homogenization treatment. Specimens of each alloy were water quenched after 2 hr heating at 1000°, 1200°, 1400°, 1600°, 1800°, and 2000°F (540°, 650°, 760°, 870°, 980°, and 1095°C). In addition, some were treated at intermediate temperatures of 1300°, 1500°, and 1700°F (705", 815", and 925°C) and at 2150°F (1175°C). Specimens, about '/s in. cubes, were cut from the bars, sealed in individual Vycor tubes, and heat treated as described. All specimens heat treated at the same temperature were processed together. Samples were quenched by breaking the Vycor tube rapidly under water. Metallographic Examination Specimens were mounted in bakelite and ground wet on 180 grit paper held on a 1750 rpm disk. They were then ground wet by hand, using 240, 400, and 600 grit papers. The rough grinding was continued long enough to get well below the surface. Specimens were mounted separately because of the variation in the rate of etching between alloys. The specimens were polished with rouge on a 4 in., 1725 rpm wheel covered with Miracloth. Alloys on the titanium side of the compound composition were etched with a solution of 2 pct hydrofluoric acid in water saturated with oxalic acid. A few crystals of ferric nitrate were added as a bright -ener. Specimens were immersed 5 sec, polished to remove the etch, then re-etched. With the higher titanium alloys, it was often necessary to start the etch on the polishing wheel, because of the formation of a passive film. In some instances, a plain 2 pct hydrofluoric etch was satisfactory. For the alloys on the uranium side of the compound, a distinction between the compound and the uranium phase developed after standing a short time in air. This could be hastened by the application of heat, such as obtained by placing the specimen on a radiator. A deep etch was necessary to develop details in the uranium-rich phase, such as the Widmanstaetten pattern sometimes obtained by quenching y uranium. A 2 pct hydrofluoric acid solution was used for this deep etching.

Jan 1, 1955

By Malcolm V. Lowry

At Balmat in northern New York State, the St. Joseph Lead Co.'s 2100-tpd zinc mining and milling operation is utilizing a unique thickener in conjunction with conventional crushing, grinding and flotation methods. From 1930 through 1962, zinc concentrates went directly from flotation to the filtering, drying and loading facilities, all of which had to operate 24 hr per day. Wide fluctuations in tonnage also had to be accommodated due to variations in the grade of ore. Many problems were thus encountered in filtering and drying, but the cost of installing a conventional, large diameter thickener could never be justified. In 1963, after thorough investigation, an unconventional thickener that is unusual in several respects was installed at Balmat. The tank depth is 16 ft instead of the normal 8 ft. The rakes are raised and lowered by having the main drive gear located on a movable platform. Automatic controls are programmed to raise the drive platform and rakes during one shift of storage. During the next two shifts of withdrawal, the controls are programmed to lower the drive platform and rakes.

Jan 5, 1966

Papers published by the Institute are issued in a variety of forms MINING TECHNOLOGY, issued every other month, contains the TECHNICAL PUBLICATIONS on Metal Mining, Minerals Beneficiation (milling and concentration), Industrial Minerals (nonmetallic) and Mining Geology, Mining Administration, and Geophysics papers relating to Metal Mining (A, B, H, I, K, L ) METALS TECHNOLOGY, issued eight times a year, contains the TECHNICAL PUBLICATIONS of the Iron and Steel Division and the Institute of Metals Division, and once or twice during the year those on Non-ferrous Metallurgy (reduction and refining of nonferrous metals) (C, E, and D ) PETROLEUM TECHNOLOGY, issued every other month, contains the TECHNICAL PUBLICATIONS of the Petroleum Division, together with Geophysics papers relating to -the finding of Petroleum (G, L ) COAL TECHNOLOGY, issued four times a year, contains the TECHNICAL PUBLICATIONS of the Coal Division (F ) MINERAL INDUSTRY EDUCATION DIVISION papers appear in a TECHNOLOGY according to classification of subject matter DISCUSSIONS appear in the respective TECHNOLOGY as available MINING AND METALLURGY is the monthly magazine, which contains papers of general interest and news of the membership

Jan 1, 1952

By K. U. Snowden, J. N. Greenwood

CRACKS which form in lead exposed to fluctuating stress frequently follow a rectangular pattern. It is well known that under ordinary atmospheric conditions these cracks are intercrystalline. On the other hand after fabrication the crystal grains in lead are in general irregular polygons. The observed facts appear to be mutually contradictory. Re-examination of some lead failures has confirmed that the rectangular cracks are intercrystal- line. It follows therefore that under fluctuating stress some of the grains lose their irregular outlines and become approximately regular polygons of cubic type. G. R. Gohn and W. C. Ellis* suggest that this is due to recrystallization during the life of the part, in such a way that the new grain boundaries are aligned at 45 deg to the longitudinal strain prior to the formation of the fatigue crack. Experiments at Baillieu Laboratory—Some recent experiments carried out in the Baillieu Laboratory in conjunction with the Broken Hill Associated Smelters have thrown some light on this transition. A test piece of pure lead was polished chemically

Jan 1, 1959

By David White

THE environmental conditions under which coals are deposited are revealed by the stratigraphy of the coal basins and coal beds and by the details of the structure and the physical constitution of the coals themselves. THE LAND SURFACE Generally Low Relief or Base Level In the Paleozoic coal fields, which have longest been worked, are most important, and are best known, we find relations, in general, as follows A post-Mississippian uplift with, in most cases, very moderate deformation, followed by erosion by which the uplifted regions, especially the bolder of the new topography, were largely worn down, while the older and less deformed regions were more or less extensively base leveled. Base leveling of most of the region continued as the deposition of coal measures proceeded. Consequently, in most coal fields the Pennsylvanian, or upper Carboniferous, lies unconformably on the Mississippian or on older formations. There are but few regions in which sedimentation is seen to have been apparently continuous from the Mississippian into the Pennsylvanian ("Coal Measures").

Jan 1, 1925

By Charles M. Cooley

THE continual improvements in. the two extremes of the drilling, unit, the drill and bit, have prompted critical examination of the drill steel, the weak link of this drilling unit. Obviously, little is to be gained from the betterment of the drill and bit if the drill steel which transmits the force needed for drilling from the machine to the bit cannot stand long hard service. The technology of the bit has advanced from the integral type to steel detachables, thence to the tungsten carbide insert. The carbide insert is the most significant advance in the bit, bringing it to the level of a machine tool with its performance records under constant surveillance. Long steel changes have become advantageous because the carbide bit will drill greater footages without replacement than did the steel bit: The development of the tungsten carbide insert opened new fields of endeavor in drilling with percussion drills here- to fore known, but limited by the steel bit. After the introduction of the tungsten carbide bit, drill manufacturers began promotion of long feed shells, lighter drifters and stopers, and easily handled auxiliary equipment. Ultimately this promotion of better equipment was intended to increase the bit-against-rock time of the drill shift. Advantages of the uninterrupted drilling period of a long steel change and faster setup time of lighter drill machines are lost when the shank fails in the machine, rod failure requires continual changing, or the bit breaks off in the hole. The quest for reduced

Jan 1, 1952

By Stanley D. Michaelson, Ben. H. Slothower

The depletion of most high-grade ore reserves coupled with growing demands for metals and fuels has made it necessary to bring into production increasingly lower grade deposits. Improvements in technology have made lower grade ores economically recoverable in spite of major increases in labor and material costs and the initial investments required to open new mines and build their metallurgical and service plants. To remain competitive, managements of mining companies must keep abreast of and exploit these often complex technical developments. The proper application of these improvements in technology requires extensive and detailed study. In addition, managements of mining and other industries are becoming more deeply involved in public affairs and the myriad of other nontechnical problems common to all industries. These involvements, plus the demands of evaluating technological developments as well as the necessary work related to the routine administration of operations, have required mining managements to delegate additional study and review functions to staff services. To help overcome the problems involved in adopting the best technologies, managements have generally expanded their engineering and research staff services. Integrated, base-metal-producing companies, having open pits, concentrators, smelters, and refineries, are generally more research and engineering oriented than are most smaller mining companies and quarries. However, mining methods for even the simplest open pits and quarries are improving rapidly, and installations of these improvements are essential to combat increasing costs. Because of this, the managements of smaller operations may also require enhanced engineering staff services to realize the potential benefits.

Jan 1, 1968

By Frank Harwood Riddle

Products made from the ores of the sillimanite group, and synthetic substitutes for them, have unique properties, and service tests prove that they are playing, and will continue to play, a major part in improvements in metallurgical processes. Also, they are examples of how comparatively useless, rare, or "museum" minerals have been made available in commercial quantities. Until research developed uses for them, the minerals had been observed only in small, scattered masses, or crystals. Improvements in ceramic processes and compositions have come about very gradually. In the last 10 or 15 years, several outstanding developments have been made. Of greatest interest to the mining and metallurgical engineers are those affecting the composition, necessitating the mining of new minerals, and improvements in ceramic products used in metallurgical processes. Sillimanite and Mullite Sillimanite (Al2O3.SiO2), then known as Fibrolite, according to Dana,' was first reported in 1792. In 1796, cyanite (Al2O3.SiO2) was first described.2 In 1873, Behrens published results of his microscopic study8 of porcelain. He showed that it contained what appeared to be crystals, which dissolved less readily than quartz and glass in hydrofluoric acid. Hussak4 described the presence of needlelike crystals as occurring in some instances in small amounts in certain porcelains. In 1908, Plenske and Zoellner both studied porcelain structure.5 Plenske observed that "sillimanite" might be present in masses of exceedingly minute grains which apparently were amorphous. Zoellner advanced the theory that the needlelike crystals were formed by a molecular change in the clay,

Jan 1, 1932

By Herbert H. Kellogg

Graphs representing the standard free-energy of formation as a function of temperature for 21 fluorides are presented, along with estimated values for the standard free-energy of formation of 20 atedadditional fluorides. A few of the many possible uses of these data in metallurgical calculations are discussed, including the fluorination of oxides, sulphides, metallurgicaland chlorides, and the reduction of metal fluorides. RECENT papers which have presented free-energy data for oxides, sulphides, chlorides, carbonates, sulphates, and silicates in the form of free energy vs. temperature plots,1-5 have found important uses in teaching and metallurgical development work. This method of presentation of thermo-dynamic data serves to make available in readily usable form thermodynamic constants which are scattered throughout the literature, and to show by graphical means the stability relations which exist between the compounds of a given type. It is certainly desirable to have these free-energy-temperature diagrams for as many types of compounds as are of present or potential use in metallurgical processes. Thus, even though there are but few uses of metallic fluorides in extractive metallurgy today, the potential uses of fluorine processes are of great importance and serve as the principal justification of this paper. Recent developments in the production of fluoro-carbons have resulted in vastly improved methods for the production and handling of fluorine and corrosive fluorides, with consequent reduction in costs.".' The extractive metallurgist should no longer overlook possible fluorine processes when development of a new process for a relatively high unit-price metal is being considered. In a previous paperv he author outlined in some detail the importance and use of free-energy data in metallurgical calculations and also discussed the properties of a standard free-energy vs. temperature diagram. The same method of presentation is adopted in this paper, and the reader is referred to the earlier work for explanations of the use of free-energy data. Thermodynamic Data This paper presents standard free-energy vs. temperature diagrams, Figs. 1 and 2, for those fluorides for which the major thermodynamic constants are known. In the calculations of the standard free-energy of formation (AGO), values of the enthalpy of formation at 298°K (?Ho,) were taken from "Selected Values of Thermodynamic Constants"8 most of the values of standard entropy at 298°K (S°298) were taken from "Selected Values"," but in a few cases the values given by Kelley9 ere preferred; data for the Phase changes came from "selected Values" and several of Kellley's publics- tions;0-12 and most of the specific-heat data were taken from Kelley.l0 The appendix gives a detailed list of the sources of the data. As explained in an earlier paper,6 he accuracy of some of the standard free-energy relationships is not high. An error of +1 kcal at 1000°C is expected in most of the curves of Figs. 1 and 2. The error may be as high as +3 kcal in some of the curves. Rather than attempt to estimate the reliability of each curve, the source of the data used is reported in the appendix, and the reader may compare these data with newer values as they become available. Figs. 1 and 2 fail to show values for the fluorides of many important metals. In most cases this is because the entropy of the metallic fluoride is unknown. For preliminary calculations it is often useful to have available the best estimate of an unknown datum, rather than no information at all. With this in mind, Table I lists estimated standard free-energy values for a number of important metallic fluorides not included in Figs. 1 and 2. The values reported in Table I were, calculated by Brewer et al.13 and are based on estimated entropy values. The estimated uncertainty of the values for each fluoride were calculated from the uncertainty values given by Brewer1' for ?H°, and the entropy function.

Jan 1, 1952

By R. Al-Hussainy, P. B. Crawford, H. J. Ramey

The effect of variations of pressure-dependent viscosity and gas law deviation factor on the flow of real gases through porous media has been considered. A rigorous gas flow equation was developed which is a second order, non-linear partial differential equation with variable coeficients. This equation was reduced by a change of variable to a form similar to the diffusivity equation, but with potential-dependent diffusivity. The change of variable can be used as a new pseudo-pressure for gas flow which replaces pressure or pressure-squared as currently applied to gas flow. Substitution of the real gas pseudo-pressure has a nrtmber of important consequences. First, second degree pressure gradient terms which have commonly been neglected under the assumption that the pressure gradient is small everywhere in the flow system, are rigorously handled. Omission of second degree terms leads to verious errors in estimated pressure distributions for tight formations. Second, flow equations in terms of the real gas pseudo-pressure do not contain viscosity or gas law deviation factors, and thus avoid the need for selection of an average pressure to evaluate physical properties. Third, the real gas pseudo-pressure can be determined numerically in term of pseudo-reduced pressures and temperatures from existing physical property correlations to provide generally useful information. The real gas pseudo-pressure was determined by numerical integration and is presented in both tabular and graphical form in this paper. Finally, production of real gas can be correlated in terms of the real gas pseudo-pressure and shown to be similar to liquid flow as described by diffusivity equation solutions. Applications of the real gas pseudo-pressnre to radial flow systems under transient, steady-state or approximate pseudo-steady-state injection or production have been considered. Superposition of the linearized real gas flow solutions to generate variable rate performance was investigated and found satisfactory. This provides justification for pressure build-up testing. It is believed that the concept of the real gas pseudo-pressure will lead to improved interpretation of results of current gas well testing procedures, both steady and unsteady-state in nature, and improved forecasting of gas production. INTRODUCTION In recent years a considerable effort has been directed to the theory of isothermal flow of gases through porous media. The present state of knowledge is far from being fully developed. The difficulty lies in the non-linearity of partial differential equations which describe both real and ideal gas flow. Solutions which are available are approximate analytical solutions, graphical solutions, analogue solutions and numerical solutions. The earliest attempt to solve this problem involved the method of successions of steady states proposed by Muskat.' Approximate analytical solutions' were obtained by linearizing the flow equation for ideal gas to yield a diffusivity-type equation. Such solutions, though widely used and easy to apply to engineering problems, are of limited value bemuse of idealized assumptions and restrictions imposed upon the flow equation. The validity of linearized equations and the conditions under which their solutions apply have not been fully discussed in the literature. Approximate solutions are those of Heatherington et al.. MacRobertsl and Janicek and Katz.' A graphical solution of the linearized equation was given by Cornell and Katz. Also, by using the mean value of the time derivative in the flow equation, Rowan and Clegg' gave several simple approximate solutions. All the solutions were obtained assuming small pressure gradients and constant gas properties. Variation of gas properties with pressure has been neglected because of analytic difficulties. even in approximate analytic solutions. Green and Wilts8 used an electrical network for simulating one-dimensional flow of an ideal gas. Numerical methods using finite difference equations and digital computing techniques have been used extensively for solving both ideal and real gas equations. Aronofsky and Jenkins"I " and Bruce et al.11 gave numerical solutions for linear and radial gas flow. Douglas et al." gave a solution for a square drainage area. Aronofsky 13 included the effect of slippage on ideal gas flow. The most important contribution to the theory of flow of ideal gases through porous media was the conclusion reached by Aronofsky and Jenkins" that solutions for the liquid flow case'" could be used to generate approximate solutions for constant rate production of ideal gases. An equation describing the flow of real gases has been solved for special cases by a number of investigators using numerical methods. Aronofsky and Ferris 10 onsidered linear flow, while Aronofsky and Porter 17 considered radial gas flow. Gas properties were permitted to vary as linear functions of pressure. Recently, CarteP 18 proposed an empirical correlation by which gas well behavior can be estimated from solutions of the diffusivity equation using instantaneour values of pressure-dependent gas

Jan 1, 1967

By Fred S. Mulock

THE principal operating and producing properties covered by the Western Operations of the United States Smelting Refining and Mining Company are the U. S. and Lark mine in the Bingham district of Utah, the Bayard department in the Central mining district of New Mexico, the Midvale mill and smelter near Salt Lake City, the lead refinery of its subsidiary, U. S. S. Lead Refinery, Inc., at East Chicago, Ind., and the coal operations of its subsidiary, United States Fuel Company, at Hiawatha, Utah. Operations of lesser importance at this time are conducted either on company account or by lessees in the Centennial, Bullion Beck, and Eagle and Blue Bell mines in the Tintic district of Utah, the Hidden Treasure and Ophir mines in the Ophir district of Utah, and the White Knob mine in Custer County, Idaho. The Richmond-Eureka Mining Company, in which the Company owns a controlling interest, has leased its properties near Eureka, Nev., to the Eureka Corporation Limited. The Gold-road property at Goldroad, Ariz., has been shut down since 1942, and due to high costs of labor and supplies, consideration is now being given to removal of all surface and underground improvements. The mine and mill im¬provements at the Sunnyside property in Colorado, recently purchased by the Sunbank Corporation, a subsidiary of the Company, are now being dismantled.

Jan 1, 1948

By Earl Oliver

SEVERAL notable papers, and free discussion on many controversial subjects, marked the various sessions of the Petroleum Division at the annual meeting. The Division first convened on Tuesday afternoon, Feb. 16, and wound up with a dinner and technical meeting on Thursday night. H. C. Fowler presided at the opening session, which was devoted to problems of engineering research and production engineering. Joseph Chalmers abstracted his paper on the flow of air and gas through porous media, in the preparation of which E. L Rawlins and D. B. Talia-ferro contributed. G. H. Fancher told how much he and his associates at Pennsylvania State College were interested in this field, and described the problems they had met in conducting test work. He made a plea for standardization of testing methods. Mr. Fowler then read an abstract of written discussion by Professor Barb, which was followed by discussion by Dr. Fancher and Mr. Chalmers of technical points in connection with the Chalmers' paper. H. H. Hill abstracted written discussion from Messrs. Wilde and Moore, of the Humble company. The second paper, by K. B. Nowels, on computing pressure drop in the pipe of flowing oil wells, was abstracted by the author. Messrs. Blair Smith, G. W. Coggeshall, and I. I. Gardescu participated in the discussion, and the chairman abstracted written discussion prepared by Mr. Rawlins. Most of this had to do with the viscosity of gas¬oil mixtures, on which subject Mr. Nowels said there was great need of accurate technical information.

Jan 1, 1932

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

Numerous investigations of the effects of the various impurities common to commercial coppers have been published, and the data have found wide use in industry. Naturally, emphasis has been placed on the oxygen-bearing coppers of the tough-pitch variety, but need is now evident for data covering the oxygen-free condition as well. Furthermore, relatively few of the important reactions between oxygen and the various impurities are well understood, and often the data at hand are not applicable to the low concentrations encountered in commercial coppers. This paper presents the changes in conductivity and softening temperature derived from individual additions of the group VIII triad, iron, cobalt and nickel, to high-purity copper, and constitutes a portion of the copper-research program being conducted at the Central Research Laboratory of the American Smelting and Refining Co. The method of preparation of high-purity copper and its alloys in either the oxygen-free or oxygen-bearing form has been described previous1y.l The purity of this material, and the methods developed to produce it, provide the means for direct investigation of the very low concentration range in which the various impurities generally exist in commercial coppers. The usual necessity for extrapolation to this range using the results obtained from higher concentrations, and the interfering effects of extraneous impurities, are thus simultaneously circumvented. Since previously published data have adequately presented the effects of higher concentrations of iron, cobalt and nickel, the present investigation has been confined to the composition range o to 0.05 per cent. All alloys were initially prepared in the form of oxygen-free continuous cast rod, the weighed alloying additions in suitable form being charged with the pure copper to the continuous casting crucible. The best of the available high-purity alloying materials were used, and spectrographic analyses confirmed the absence of interfering elements from the alloys formed. Each series was compounded in the direction of increasing concentration, starting with pure copper in a new crucible and finishing with the 0.05 per cent alloy. Composition was closely controlled by adding the alloying element in the form of a carefully compounded and analyzed master alloy rendered uniform by continuous casting. The accuracy of this method of synihesis was proved by chemical analysis of the more concentrated alloys, and, accordingly, there is every reason to credit the stated composition of the very dilute alloys in the range where chemical analysis becomes highly uncertain. Oxygen-free samples for measurements of conductivity and softening temperature Were obtained by drawing the continuous cast rod to wire of 0.08I-in. diameter. employing a number of intermediate anneals to refine the grain structure. The

Jan 1, 1942

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

NUMEROUS investigations of the effects of the various impurities common to commercial coppers have been published, and the data have found wide use in industry. Naturally, emphasis has been placed on the oxygen-bearing coppers of the tough-pitch variety, but need is now evident for data covering the oxygen-free condition as well. Furthermore, relatively few of the important reactions between oxygen and the various impurities are well understood, and often the data at hand are not applicable to the low concentrations encountered in commercial coppers. This paper presents the changes in conductivity and softening temperature derived from individual additions of the group VIII triad, iron, cobalt and nickel, to high-purity copper, and constitutes a portion of the copper-research program being conducted at the Central Research Laboratory of the American Smelting and Refining Co. The method of preparation of high-purity copper and its alloys in either the oxygen-free or oxygen-bearing form has been described previously.1 The purity of this material, and the methods developed to produce it, provide the means for direct investigation of the very low concentration range in which the various impurities generally exist in commercial coppers. The usual necessity for extrapolation to this range using the results obtained from higher concentrations, and the interfering effects of extraneous impurities, are thus simultaneously circumvented. Since previously published data have adequately presented the effects of higher concentrations of iron, cobalt and nickel, the present investigation has been confined to the composition range 0 to 0.05 per cent. All alloys were initially prepared in the form of oxygen-free continuous cast rod, the weighed alloying additions in suitable form being charged with the pure copper to the continuous casting crucible. The best of the available high-purity alloying materials were used, and spectrographic analyses confirmed the absence of interfering elements from the alloys formed. Each series was compounded in the direction of increasing concentration, starting with pure copper in a new crucible and finishing with the 0.05 per cent alloy. Composition was closely controlled by adding the alloying element in the form of a carefully compounded and analyzed master alloy rendered uniform by continuous casting. The accuracy of this method of synthesis was proved by chemical analysis of the more concentrated alloys, and, accordingly, there is every reason to credit the stated composition of the very dilute alloys in the range where chemical analysis becomes highly uncertain. Oxygen-free samples for measurements of conductivity and softening temperature were obtained by drawing the continuous cast rod to wire of 0.081-in. diameter, employing a number of intermediate anneals to refine the grain structure. The

Jan 1, 1942

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

Numerous investigations of the effects of the various impurities common to commercial coppers have been published, and the data have found wide use in industry. Naturally, emphasis has been placed on the oxygen-bearing coppers of the tough-pitch variety, but need is now evident for data covering the oxygen-free condition as well. Furthermore, relatively few of the important reactions between oxygen and the various impurities are well understood, and often the data at hand are not applicable to the low concentrations encountered in commercial coppers. This paper presents the changes in conductivity and softening temperature derived from individual additions of the group VIII triad, iron, cobalt and nickel, to high-purity copper, and constitutes a portion of the copper-research program being conducted at the Central Research Laboratory of the American Smelting and Refining Co. The method of preparation of high-purity copper and its alloys in either the oxygen-free or oxygen-bearing form has been described previous1y.l The purity of this material, and the methods developed to produce it, provide the means for direct investigation of the very low concentration range in which the various impurities generally exist in commercial coppers. The usual necessity for extrapolation to this range using the results obtained from higher concentrations, and the interfering effects of extraneous impurities, are thus simultaneously circumvented. Since previously published data have adequately presented the effects of higher concentrations of iron, cobalt and nickel, the present investigation has been confined to the composition range o to 0.05 per cent. All alloys were initially prepared in the form of oxygen-free continuous cast rod, the weighed alloying additions in suitable form being charged with the pure copper to the continuous casting crucible. The best of the available high-purity alloying materials were used, and spectrographic analyses confirmed the absence of interfering elements from the alloys formed. Each series was compounded in the direction of increasing concentration, starting with pure copper in a new crucible and finishing with the 0.05 per cent alloy. Composition was closely controlled by adding the alloying element in the form of a carefully compounded and analyzed master alloy rendered uniform by continuous casting. The accuracy of this method of synihesis was proved by chemical analysis of the more concentrated alloys, and, accordingly, there is every reason to credit the stated composition of the very dilute alloys in the range where chemical analysis becomes highly uncertain. Oxygen-free samples for measurements of conductivity and softening temperature Were obtained by drawing the continuous cast rod to wire of 0.08I-in. diameter. employing a number of intermediate anneals to refine the grain structure. The

Jan 1, 1942

By Gareth Thomas

The analysis of Kikuchi pattersns of exct ovientalions from single cryslals and paired Kikuchi lines from single and overlapping crystals is shown to be useful and quanlitalve and is applied to Phase transfovnzcitions including ordering, spinodals, mavten-silic, and nuclealion and growth pyocesses. 112 pinciple, the analysis of exacl orientations enables the crystal system and the Bravais lattice of a crystal to he determined. The advantages of the davk-field imaging technigure for detecting vevy small precipitates are also described. ALTHOUGH Kikuchi electron-diffraction patterns were first observed nearly 40 years ago,' little systematic application seems to have been made of them, until fairly recently during electron microscopy, when their usefulness in contrast experimen and for determining exact orientations8'9 has been pointed out. With the availability of gonio-metric specimen tilting stages it has now become possible to make much wider use of diffraction patterns, particularly the Kikuchi pattern, which is the main subject of this paper. The treatment presented here is not exhaustive but it is hoped that it will stimulate more use of Kikuchi patterns during electron-microscopy investigations. The Kikuchi pattern is formed as a result of Bragg diffraction of the inelastically scattered electrons produced during the interaction of the beam and thick specimens, The important feature of these patterns is that they give an accurate representation of the symmetry of the crystal being investigated, so that it is possible to identify crystal systems and even the Bravais lattice. This means that new structures, e.g., formed in phase transformations, may be identified during normal electron microscopy, so that Kikuchi-pattern analyses considerably extend the uses of the electron microscope. Recent work has also shown that dark-field images are more informative than bright-field images, particularly, for observing small precipitates. The second part of this paper discusses some applications and advantages of dark-field imaging in studies of two-phase systems. 1) DIFFRACTION PATTERNS 1.1) Spot Patterns. Electron-diffraction spot patterns have their limitations because of the importance of the form factor on the intensities and shape of the reciprocal lattice points. Because of the extension of these points into relrods, reflections are possible over a large angular range (+5 deg) and the patterns from thin regions can be complicated because second-layer relrods intersect the reflecting sphere. Spot patterns can thus give only an approximate idea of the crystallography unless the foil is tilted into exact orientation. In this case the spot pattern is symmetrical, with equal numbers of spots on the positive and negative zone directions about the origin. Such cases are necessary for structural analyses and have been used recently to determine the crystal structure of the ordered Ta64C phase." Exact orientation means that the plane of the reciprocal lattice lies exactly normal to the incident beam as shown in Fig. 1(b). It should be noted that in exact orientations the angle of reflection is less than the exact Bragg angle 9 so that the reciprocal lattice points lie to the outside of the sphere, Fig. 1(b). This deviation is denoted by the parameter s and in the usual convention4 s is negative for exact orientations and, of course, zero at the exact reflecting position shown in Fig. l(a). In order to avoid secondary reflections from thickness relrods it is advantageous to work in thicker regions of foils. Diffraction from thick regions may also produce Kikuchi patterns and as dis-

Jan 1, 1965

By P. S. Roller

P. S. ROLLER,*College Park, Md.-The author introduces the idea of a grind limit, or lower size limit of the particles formed directly by grinding, and this is stipulated to be 0.70 micron. I wonder where all the particles come from that lie between the resolving power of the microscope and 0.7 micron, which are seen under a microscope in examining a sample of grind? There is also introduced the idea of excess fines; this is all right in itself but the author's quantitative definition seems to be virtually impossible to justify, and, moreover, is obscure. Just why E, the excess fines, should he defined as the distance between an F line and a y line is hard to follow, and just where the distance should be measured does not appear to be stated, as it should be since the F and y lines intersect and the distance between will depend upon where that distance is measured. The basis of the presentation is the relation of log weight against log size that was "discovered" by Schuhmann. While this relation is implied to fit, the only evidence that I can see is a slightly irregular line in Fig. x between 2 per cent and 18 per cent by weight and then a precipitous drop at 18 per cent away from any sort of straight line. Some of the conclusions are rather startling. It is stated that E, the excess fines, remains constant for all the comminution products of any particular material, except that it may decrease for some coarse crusher products. No reason is given for this assertion. One would, on the contrary, expect that excess fines, if such a concept is permissible, would generally vary with different conditions instead of being constant. Again, "as much net energy is required to reduce a ton of quartz to particles of the grind-limit diameter (namely, of course, 0.7 micron) by grinding as is required to melt the quartz." This would require many data to prove, but no proof is given; any consideration would reveal the impossibility of such a result. Still further, ore samples "ground to widely different sizes, and with different circulating loads and different size distributions or product, show the same production of new surface area per revolution of the mill, when this grind limit is used." This statement is confuted by ordinary experience, which teaches that grinding efficiency varies generally with the condition of material. For example, the cushioning effect of fines is widely accepted, while the inefficiency of a ball mill when the feed is too coarse is also well known. R. SCHUHMANN, JR.," Cambridge, Mass. Contrary to Mr. Bond's stand, there is a great deal of miscellaneous experimental evidence that comminution does not stop at around 0.7 micron, nor does it cease consuming energy at that point. Comminution is in fact recognized as an important method of producing colloids., Mechanical comminution methods were used by von Weimarn6 to produce colloidal dispersions of a variety of solids, including the minerals chalcocite, galena, hematite, stibnite. Utzino7 gives average particle sizes ranging from 0.02 to 0.09 micron for colloids produced by mechanical comminution of several crystalline solids. Andreasen and Berg' have ground

Jan 1, 1941

By P. S. Roller

P. S. ROLLER,* College Park, Md.-The author introduces the idea of a grind limit, or lower size limit of the particles formed directly by grinding, and this is stipulated to be 0.70 micron. I wonder where all the particles come from that lie between the resolving power of the microscope and 0.7 micron, which are seen under a microscope in examining a sample of grind? There is also introduced the idea of excess fines; this is all right in itself but the author's quantitative definition seems to be virtually impossible to justify, and, moreover, is obscure. Just why E, the excess fines, should be defined as the distance between an F line and a [?] line is hard to follow, and just where the distance should be measured does not appear to be stated, as it should be since the F and [?] lines intersect and the distance between will depend upon where that distance is measured. The basis of the presentation is the relation of log weight against log size that was "discovered" by Schuhmann. While this relation is implied to fit, the only evidence that I can see is a slightly irregular line in Fig. I between 2 per cent and 18 per cent by weight and then a precipitous drop at 18 per cent away from any sort of straight line. Some of the conclusions are rather startling. It is stated that E, the excess fines, remains constant for all the comminution products of any particular material, except that it may decrease for some coarse crusher products. No reason is given for this assertion. One would, on the contrary, expect that excess fines, if such a concept is permissible, would generally vary with different conditions instead of being constant. Again, "as much net energy is required to reduce a ton of quartz to particles of the grind-limit diameter (namely, of course, 0.7 micron) by grinding as is required to melt the quartz," This would require many data to prove, but no proof is given; any considera¬tion would reveal the impossibility of such a result. Still further, ore samples "ground to widely different sizes, and with different circulating loads and different size distributions or product, show the same production of new surface area per revolution of the mill, when this grind limit is used." This statement is confuted by ordinary experience, which teaches that grinding efficiency varies generally with the condition of material. For example, the cushioning effect of fines is widely accepted, while the inefficiency of a ball mill when the feed is too coarse is also well known. R. SCHUHMANN, JR.,* Cambridge, Mass.¬Contrary to Mr. Bond's stand, there is a great deal of miscellaneous experimental evidence that comminution does not stop at around 0.7 micron, nor does it cease consuming energy at that point. Comminution is in fact recognized as an important method of producing colloids.5 Mechanical comminution methods were used by von Weimarn6 to produce colloidal dispersions of a variety of solids, including the minerals chalcocite, galena, hematite, stibnite. Utzino7 gives average particle sizes ranging from 0.02 to 0.09 micron for colloids produced by mechanical comminution of several crystalline solids. Andreasen and Berg8 have ground

Jan 1, 1941

By P. S. Roller

P. S. ROLLER,* College Park, Md.-The author introduces the idea of a grind limit, or lower size limit of the particles formed directly by grinding, and this is stipulated to be 0.70 micron. I wonder where all the particles come from that lie between the resolving power of the microscope and 0.7 micron, which are seen under a microscope in examining a sample of grind? There is also introduced the idea of excess fines; this is all right in itself but the author's quantitative definition seems to be virtually impossible to justify, and, moreover, is obscure. Just why E, the excess fines, should be defined as the distance between an F line and a y line is hard to follow, and just where the distance should be measured does not appear to be stated, as it should be since the F and y lines intersect and the distance between will depend upon where that distance is measured. The basis of the presentation is the relation of log weight against log size that was "discovered" by Schuhmann. While this relation is implied to fit, the only evidence that I can see is a slightly irregular line in Fig. I between 2 per cent and 18 per cent by weight and then a precipitous drop at 18 per cent away from any sort of straight line. Some of the conclusions are rather startling, It is stated that E, the excess fines, remains constant for all the comminution products of any particular material, except that it may decrease for some coarse crusher products. No reason is given for this assertion. One would, on the contrary, expect that excess fines, if such a concept is permissible, would generally vary with different conditions instead of being constant. Again, "as much net energy is required to reduce a ton of quartz to particles of the grind-limit diameter (namely, of course, 0.7 micron) by grinding as is required to melt the quartz." This would require many data to prove, but no proof is given; any consideration would reveal the impossibility of such a result. Still further, ore samples "ground to widely different sizes, and with different circulating loads and different size distributions or product, show the same production of new surface area per revolution of the mill, when this grind limit is used." This statement is confuted by ordinary experience, which teaches that grinding efficiency varies generally with the condition of material. For example, the cushioning effect of fines is widely accepted, while the inefficiency of a ball mill when the feed is too coarse is also well known. R. SCHUHMANN, JR.,* Cambridge, Mass.-Contrary to Mr. Bond's stand, there is a great deal of miscellaneous experimental evidence that comminution does not stop at around 0.7 micron, nor does it cease consuming energy at that point. Comminution is in fact recognized as an important method of producing colloids.5 Mechanical comminution methods were used by von Weimarn6 to produce colloidal dispersions of a variety of solids, including the minerals chalcocite, galena, hematite, stibnite. Utzino7 gives average particle sizes ranging from 0.02 to 0.09 micron for colloids produced by mechanical comminution of several crystal-line solids. Andreasen and Berg8 have ground

Jan 1, 1941

By T. R. Ingraham

The thermal decomposition of cupric sulfate and of cupric oxysulfate has been examined by deter-mining the equilibrium gas pressure generated over each pure compound. The equilibrium data have been used to calculate the thermodynamic properties of both compounds, and the results have been combined with previously published data to establish a predominance-volume diagram for the Cu-S-O system over the normal range of roasting temperature and gas composition used in the treatment of copper minerals. Copper oxysulfate recrystal-lizes at 1100°K with an apparently irreversible en-dothermic heat requirement of 2.9 * 0.3 kcal per mole. WHEN mixed sulfide minerals containing copper are roasted, either of two procedures may be followed, depending on the nature of the other metals. In the first procedure, the roasting is controlled to produce a maximum amount of water-soluble copper sulfate which may be removed selectively from the water-insoluble compounds of the other metals. In the second, control is directed toward the production of water-soluble sulfates of the other metals and an insoluble salt of copper. Effective control of either of these processes would be enhanced by knowledge of the thermal stability of cupric sulfate and of cupric oxysulfate. In this paper, established data for the thermal stability of cuprous and cupric sulfide and of cuprous and cupric oxide will be combined with new data for the therma1 stability of cupric sulfate and cupric oxysulfate, to designate the volumes of stability of the significant compounds in the Cu-S-O system in the temperature range 750° to 950°K. EXPERIMENTAL Materials, Apparatus, and Procedure. The copper source material used in all experiments was Fisher Certified Reagent Grade "anhydrous" cupric sulfate, for which the following analysis was supplied by the manufacturer: chloride, 0.002 pct; alkalies and earths, 0.2 pct; insoluble, 0.002 pct; iron, 0.020 pct. Cupric oxysulfate was prepared from the normal sulfate by two procedures. In the first, equimolar quantities of cupric oxide (prepared by decomposition of the sulfate) and cupric sulfate were ground together and heated under vacuum in a sealed silica vessel at 800°C. This procedure was subject to failure because of explosion of the silica vessels due to the pressure of the final traces of water released from the sulfate on the initiation of its decomposition. The second procedure involved roasting the cupric sulfate, with frequent rabbling, in a muffle furnace at 725°C for a period of 48 hr. This produced an excellent product, which was confirmed as copper oxysulfate by X-ray and chemical analyses. The experimental technique used was that of measuring the total pressure exerted by the sulfur trioxide, sulfur dioxide, and oxygen produced by the following reactions: 2 CuS04 = cuo • CuSO4 + SO3 [1] cuo . CuSO4 = 2 cuo + SO3 [2] SO3= SO2 + 1/2 O2 [3] The apparatus used in the experiments has been described previously.1-3 Its main feature of a U-tube mercury manometer in which the mercury is protected from corrosion by enclosure in a flexible Pyrex bellows. Before beginning a run, the interior of the apparatus, including the bellows-manometer and all connecting tubing, was thoroughly washed with hydrochloric acid and distilled water to remove any

Jan 1, 1965