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By P. G. Shewmon, H. E. Collins

A study has been made to determine the sites at which sulfur adsorption occurs on copper surfaces. measurements were made of the relative torques, Ys, at the intersection of twin boundaries with surfaces near the three low-index orientations, i.e., (100), @lo), and 011), over a range of H2S/H2 ratios. HZS concerztvations j'ro~n 3 to 1500pp)n between 830" and 1050°C were used. It is concluded that sulfur adsorption occurved preferentially though not exclusively at edge sites near the (100) and (110) surfaces in the HzS range — 700 Ppm giving rise to negative torques near these orientations. Beyond this HzS range, adsorption occurred at all sites. Near the (111) surface, 7/y little with HzS concentration up to approxiwzately 75pptn. Above this range, the results indicate adsorption is occurring OH both terrace and edge sites. SCIENTIFIC interest in surfaces and their interactions with a gaseous environment dates back to the beginning of the 19th century. The scientific luminaries of that period—Faraday, Maxwell, Rayleigh, Dewar, and Gibbs—were already concerned about such processes. However, it has only been within the past several decades that adsorption on metal surfaces has been actively studied. This increased interest in adsorption has been brought about by the advent of new and improved experimental techniques and apparatus, e.g., ultrahigh vacuum, and field-emission and ion microscopes. However, most of the work done using these techniques has been carried out at low temperatures. When adsorption studies have been made at either low or high temperatures, they usually gave no indication of the particular surface orientations or type of sites on which adsorption was occurring. In the last few years, there have been a series of studies in which the surface tension, y,, and/or its derivative with respect to orientation, 7, have been studied as a function of orientation and atmosphere.'-7 Nearly all of the work on the relative torque,* ~/y, silver annealed in hydrogen and air.6 Recently Winterbottom and Gjostein" have used a modified and more accurate Mykurian method to determine the y plot of gold in hydrogen The only work in which T/~, has been measured over a range of chemical potentials for a given solute, p2, is that of Robertson and shewmon7 on the Cu-0 system. They measured T/Y, vs Po, (10"" to 10- l3 atm) at 1000°C in various mixtures of Hz0 and HZ. From this work they estimated the value of p2 at which one half of the surface sites are occupied with oxygen, pg, as being in the range 10- l6 to 10- l5 atm of oxygen. They also found that increasing Pa increased the magnitude of ~/y, near the (111) and (100) orientations. This indicates that oxygen is not adsorbed preferentially at step edges, but uniformly over all surface sites. In addition, they did one experiment on sulfur adsorption on copper surfaces, which indicated that sulfur adsorption decreases ~/y, near the (100) orientation, while not affecting ~/y, near the (111). This could be interpreted as indicating that sulfur adsorbs preferentially at step edges near the (100). In this paper the primary objective of the work has been to carry out a study of sulfur adsorption on copper surfaces over a range of temperatures and p,. In conjunction with this work, thermal grooving at grain boundaries has been examined as a method of determining the effect of sulfur adsorption on y,. METHODS Ideally, one would like to have information on the quantity of solute adsorbed on a surface and the types of sites at which it is absorbed as a function of p2. The total quantity adsorbed or the surface excess is given by the thermodynamic equation Thus data on the variation of y, with pz indicates the value of p2 at which adsorption becomes appreciable and the quantity adsorbed. The type of adsorption site is more difficult to deduce but information on this can be obtained from the variation of rz with 8, the angular deviation of the surface orientation. This is obtained from the thermodynamic equationlg Data on t and ys as functions of p2 have been obtained by the following methods. 1) Twin Boundary Grooving—By determining the effect of adsorption on the torque, 7, where T is the variation of surface energy, y,, with orientation, it is possible to obtain some indication as to the preferred sites of adsorption. Experimentally, the torque value measured is the relative torque, 7/ys The twin boundary grooving technique suggested by Mykura'' was used in this study to determine near the three low-index orientations— (loo), (110), and (111). Mykura's equation relates 7 /yS to measurements of the di-

Jan 1, 1967

By L. L. McDaniel

Copper smelters of various kinds have operated in the Morenci district since 1872, but all have been abandoned with the exception of the present Morenci Smelter of Phelps Dodge Corporation, which was completed in 1942. During the five-year period starting in 1937, the Morenci ore body was prepared for open pit mining, pilot mill test work was carried out, and a complete reduction works, of which the Smelter is a part, was designed and erected. Actual construction work on the Morenci Smelter was started in the fall of 1940, and warming up of the units began on April 1, 1942. Charging of the reverberatory furnaces commenced on April 18, 1942, and the first anode copper was produced on April 26, 1942. The smelter was originally designed to handle the production of the Morenci Concentrator on a 25,000 ton per day program, but by the time the smelter was in operation, plans were already underway to increase the smelter capacity to handle the production of the concentrator which was being enlarged to 45,000 tons a day capacity as a war-time necessity. This extension to the smelter was completed and the new units were put in operation toward the beginning of 1944. The original smelter consisted of a smelter crushing plant, bedding plant, two direct-smelting reverberatory furnaces with two waste-heat boilers on each furnace, three converters, an anode department, a stack, and all of the usual accessory smelting equipment. The extension consisted of increasing the bedding plant from three to five beds, the reverberatory department from two to four furnaces, and from four to eight waste-heat boilers, and the converter department from three to six converters. A third converter aisle crane was added and additions were made to the flue systems and conveyor systems throughout the smelter; but no change was made in the smelter crushing plant or the anode department, and the same stack was used for all additional Smelter units. A blister casting machine was installed at that time in the south end of the converter aisle to handle excess and emergency production above the capacity of the anode department and in 1947 a converter aisle skull breaker and a lime burning plant were added as the final units for a complete plant. The choice of direct smelting over calcine smelting for the Morenci Smelter was made after careful study by members of the Western organization of Phelps Dodge Corporation and after test runs on direct smelting of Morenci concentrate had been made at the Douglas Smelter of Phelps Dodge Corporation. The Morenci furnace charge is made up of comparatively high grade concentrate with no ores of smelting grade available and with only flux, a small amount of copper precipitate and the usual amount of smelter secondaries to be smelted with the concentrate. The simplicity of direct smelting for this charge and the large amount of waste-heat steam available from direct smelting operations were factors influencing the decision to adopt direct smelting for Morenci. The design of the Morenci Smelter and the type of units selected followed best experience at the Douglas Smelter of Phelps Dodge Corporation. A description of the original smelter before operations started was given in an article in the May 1942 issue of Mining and Metallurgy. The purpose of the present article is to describe the enlarged Morenci Smelter, with a discussion of metallurgy and operating practice and to show tabulations of operating and metallurgical results obtained. Because of beginning operations during the early years of World War 11, many problems caused by labor shortage were encountered, but no major difficulties developed in starting the new plant. However, because of labor shortage, full scale Smelter production was not reached until the fall of 1946. Fig 1 shows a general plan of the Morenci Reduction Works. The arrangement of the smelter equipment is shown in Fig 2, a sectional view of the smelter is shown in Fig 3, and the smelter flow sheet is shown in Fig 4. Metallurgy The metallurgy of direct smelting, being more or less fixed by the character of the charge, is not subject to the control available in calcine smelting. Slags may be modified by the addition of suitable fluxes, but the grade of the matte is determined almost entirely by the iron:copper ratio of the concentrate. The direct smelting operation involves distributing the wet concentrate along the sidewalls and in the bath of a reverberatory furnace by means of some suitable feeding device and raising the temperature of the charge so that first the moisture is driven off, then the first-atom sulphur is eliminated, and finally the sulphide portion of the charge melts and runs into the bath, carrying with it the non-sulphide portion which has been partially fluxed to form a suitable slag. The fusion of the non-sulphide portion is completed by contact with the irony converter slag which is regularly being poured into the reverberatory furnace. The smelting rate of the charge is influenced by the mineralogi-cal composition of the sulphide portion of the concentrate and by the composition and amount of the non-sulphide portion including the fluxes added. The copper in Morenci concentrate is chiefly in the form of chalcocite, intimately associated with pyrite, and non-sulphide content is very low so that

Jan 1, 1950

By N. J. Grant, Per Knudsen, J. T. Blucher

The fatigue behavior of three SAP alloys was studied in ternzs of strain rate and temperature, at high strains. The k values in the modified Manson-Coffin equation, Nk4 = C, were less than 0.5 under all test conditions, and change with strain amplitude for the lower-oxide alloys at about 2 pct strain. Lowest k values were near 0.25. Strain rate had no effect on life at 80 F, but had an increasingly greater effect with increasing temperature above 500". Life decreased with decreasing strain rate, above 500"F, and with increasing temperature. Ductility at fracture in a tension test was indicated to be an important factor in determining 1ife in these big+-strain tests with the SAP alloys. INEVITABLY, in the course of mechanical tests at elevated temperatures, particularly if significant time at temperature is involved, there are large changes in structure; these changes make it difficult to relate behavior patterns over ranges of temperature or strain rates at high temperatures. Such changes are to be expetted in low cycle fatigue at low strain rates and high temperatures. Accordingly, it was of great interest to examine the low cycle fatigue behavior of SAP / an aluminum oxide dispersion-strengthened aluminum, a type of alloy which had shown unusual structure stability to temperatures as high as 1000" to 1150°F and resisted recrys-tallization essentially to the melting temperature.'j3 Since the matrix is pure aluminum, there are no complications of averaging, agglomeration, or phase solution. It was also desirable to check the Manson-Coffin equation4?' for the SAP alloys, namely N~E~ = , where ep is the total plastic strain amplitude, k and C are constants, and N is the number of cycles to failure. Here, too, was an opportunity to check the roles of temperature and strain rate with a very stable material. Tavernelli and coffin6 had concluded that k had a value of about 0.5 for many alloys and C was equal to ~/2, where E is the fracture ductility determined from a static tension test. The results were obtained from low-temperature tests where creep and diffusion processes are unimportant. Manson7 found k = 0.6 fitted his data reasonably well; however, in later analyses of a large amount of low cycle fatigue data generated at room temperat~re@"~ he found k to vary from 0.6 for short lives to 0.21 for long-life fatigue tests. In the latter studies,89g Manson separated the total strain range into elastic and plastic components when he found that k was influenced by the nature of the strain. The use of EL (total strain) instead of EP (total plastic strain)4'5 makes a difference in the resultant k value. The ratio of changes with temperature, strain rate, and strain; further, there are the problems in the determination of the elastic strain. Based on these considerations, and the improved fit of points in a plot of by Wells and Sullivan,' is also utilized in these studies. Anderson and wahl,14 using commercial 1100 aluminum, and Blucher and Grant,15 using 99.99 pct pure aluminum, found an increase in life with increasing test temperature. Anderson and Wahl were the first to report low cycle fatigue results from SAP materials. With increasing temperature, the role of strain rate becomes more important. In this regard, care must be exercised to differentiate between frequency (wherein strain rate may vary from zero to a maximum in each cycle, sinusoidally, for example), and constant strain rate, as used in the present study, in a saw-tooth type cycle; in the latter case, the frequency is not specified but can easily be calculated from the strain and strain rate data. It has generally been found that life in low cycle fatigue tests decreases with decreasing frequency16 or with decreasing strain rate at elevated temperatures.15 Coffin,17 reviewing Eckel's work,16 also reported that k increased with decreasing frequency for acid lead, yielding values from 4.0 at a frequency fo 6.6 cycles Per day to 1-46 at a frequency of 7440 cycles per day; the value of k decreased to 0.58 at a frequency of 2.38 x lo6 cycles per day. EXPERIMENTAL PROCEDURE Three SAP alloys, of two nominal compositions, were tested. Alcoa supplied XAP 005 as 2-in.-diam extruded bar, of nominal composition A1-7 wt pct A1203. The Danish Atomic Energy Commission supplied SAP 930 (A1-7 wt ~ct Ala3) and SAP 865 (A1-13 wt pct Al&) manufactured by Swiss Aluminium Ltd., in the form Of $-in.-diam extruded rod. Metallographic comparison of the structures of XAP 005 and SAP 930 showed the former to have a more uniform oxide distribution. Button-head specimens were machined in the longitudinal direction of the bar with 0.4 in. gage length by 0.2 in. diameter, with a fillet radius of j-B in. After machining, the specimens were electropolished in a 1 to 4 mixture of perchloric acid to methanol to remove all machining marks. All test bars were in the as-extruded condition. The fatigue tests were performed on a hydraulically activated, axial strain machine, with complete reversal of strain.15 Test conditions were:

Jan 1, 1969

By EDWARHD HALSE

Discussion of the Paper of Dr. H. M. Chance, presented at the Lake Superior Meeting, September, 1904. EDWARD HALSE, Puerto Berrio, Colombia, So. Amer. (communication to the Secretary*) : The Taviche mining-district is generally known as a Taviches," being named from the two villages called respectively San Pedro Taviche and San Jeronimo Taviche. It is so called by José G. Aguilera, in his paper on the Geographical and Geological Distribution of the Mineral Deposits of Mexico;' and in published reports by the late N. W. Rudston Read ;2 and by Juan de Dios Villarello.3 The region is a large one, measuring about 24 miles long and 7 miles wide. Dr. Chance, in his interesting paper, tells us very little about the nature of the ores, and, with regard to the geology of the district, contents himself with observing that ? the country, as a rule, consists of eruptive rocks; and no evidences of sedimentary strata appear near the mines.? The latter part of the above statement is hardly correct. The formation is mainly eruptive, being hornblende-audesite of Tertiary age, which is limited on the east by the calcareous (Cretaceous) formation, and on the west by the Huronian rocks of Ocotlan. Limestone is seen close to the Santa Càtarina mine, at the northern end of the region. In the surface-working known as La Cueva, a little northeast of San Pedro, limestone forms the eastern wall of the deposit which consists of spots (moscas) of pyrargyrite in white opaque or transparent quartz. Ill one place the ore is associated with stibnite, and the quartz frequently exhibts a

Sep 1, 1905

By R. W. Shearman, F. Weston Starratt

A new center for mining and metallurgical research is developing at Sterling Forest, N. Y., under the auspices of Union Carbide Corp. Here is to be located the Union Carbide Nuclear and Ore Research Laboratories. In truth, history has repeated itself; the Sterling Forest area in the days of the Revolutionary War, and for many years thereafter, was the mining and metallurgical center of the US. For in these Ramapo hills along the New York-New Jersey border, iron ore was mined, pig lion was cast, and the weapons of war and the plowshares of peace were forged. Before embarking on an historical pilgrimage to yesteryear-a brief description of Sterling Forest. Located in Orange County, N. Y., near Tuxedo, immediately north of the New York-New Jersey State line, and just west of the Erie Railroad and the New York State Thruway, Sterling Forest is approximately 35 mi from New York City. Title was acquired in 1956 from the Harriman family by City Investing Co. Its President, Robert W. Dowling, has established himself as a city planner, having conceived such projects as Pittsburgh's Gateway Center and Philadelphia's Penn Center. A unique, self-contained community -is planned that will contain light industry and centers for research and engineering. Colonies of homes will be interspersed throughout the 20,000 acres of forest land, lakes, and rolling hills. Culture will not be neglected, for Sterling Forest will be the new home for the annual Empire State Music Festival The Sterling Forest Gardens, 125 acres of landscaped woodland and streams, will become the "world's largest permanent floral showplace" The Sterling Forest International Research Building was opened earlier this year, and designed to provide all facilities needed by small growth research companies. The first major company to acquire land to construct research buildings at Sterling Forest is Union Carbide. 1763 ... Discovery of iron ore In turning back the pages of history, a fascinating story can be told of special interest to the metallurgist, the mining engineer, and perhaps even the sociologist. For, where new communities are planned today, older communities had been born, matured, and died. In these hills had lived the. iron miners, the blacksmiths, the lumbermen, the masons, and the teamsters that had given America its start in heavy industry. This was the area where the forests were crisscrossed with many wood roads that brought logs to the charcoal pits, and iron ore to the furnaces. Men make history. Our story brings forth many names of men known as ironmasters, or as industrial leaders-Hasenclever, Faesch, Erskine, Townsend, Ryerson, Parrott, Cooper, Hewitt, Jay Cooke, and Harriman. The name Sterling is derived from a Scotch Lord, the Fifth Earl of Stirling (in its earlier spelling). Lord Stirling was one of seven Englishmen granted a patent of land in the Ramapo hills by Queen Anne in 1707, known as the Cheesecock Patent. He sent an agent, Cornelius Board, to America in 1730, with the express purpose of looking for copper deposits. While he found no copper in his travels up and down the Ramapo Valley, he did find iron ore in two localities: first, in the vicinity of what is now Ringwood, N. J.; second, five miles to the north. There he constructed a forge and furnace at the edge of a lake in 1736, naming the land Stirling Property, after his patron. In 1740, the Ogden family in Newark bought land from Board at Ringwood and began smelting of iron in 1741. The Ringwood story Soon, a genius in the person of Peter Hasenclever appeared on the scene. He was attracted by an advertisement in the New York Mercury for March 5, 1764, in which David Ogden of Newark offered

Jan 1, 1961

By W. A. Oates, J. A. Lambert, P. T. GaIIagher

Monte Carlo methods have been used to compute the arrangements of interstitial atoms dissolved in tetrahedral sites in bcc lattices. It is assumed that the presence of an interstitial atom "blocks " a certain number of neighboring sites and prevents their occupancy. Sites "blocked" by more than one filled site are allowed for. The computed values of. the mean occupation number (defined as the ratio of the total number of sites blocked to the number of solute atoms are used to calculate the configurational entropies of the solutions. These entropies are compared with those resulting from previous theoretical studies of this problem and also with available experin~ental data for the p Zr-H, Nb-H, V-H, and Ta-H systems. Evidence is also given that the "blocking" explanation of low limiting compositions in these systems, rather than this being due to initial limitations on the number of sites available, is probably correct. THE ideal partial configurational entropy of mixing of an interstitial solute in a metal is given by: where p is the number of interstitial sites per metal atom and Xi is the atomic fraction of the interstitial. For the bcc lattice. which we shall be concerned with in this paper, the interstitial positions are shown in Fig. 1. It can be seen that for the tetrahedral sites, p=6. whereas for the octahedral sites, p = 3. Different emphasis has been placed on the relative importance of energy and entropy effects in determining deviations from ideality in interstitial solid solutions. In some cases the same system, e.g., Fe-C, has been described by the contradictory regular and athermal solution models indicating that the enthalpy and entropy functions, derived from equilibrium data, are frequently not accu.rate enough to differentiate between these treatments. However, for certain metal-hydrogen solutions the equilibrium data is available over sufficiently wide ranges of temperature and composition to permit a reasonably accurate determination of the compositional variation of the heats and entropies. Hoch&apos; has attempted to interpret the results of interstitial solid solutions in terms of a regular solution model. In the case of the Ta-H system where 13 = 6, this model entails fitting the experimental relative partial entropies of solution, asH, to the equation: where ASgs is the relative partial excess entropy of solution of hydrogen. Hoch found that the results of Mallett and Koeh1 could be fitted to this equation with an approximately constant value of AF up to XH = 0.25. However, it is apparent from the solubility isotherms in this system which become asymptotic to the composition TaH that, since (Xh /6 - ~Xh ) becomes infinite only at TaH6, it is necessary that AS<&apos; tends to infinity at TaH. In other words, the low saturation composition of TaH, instead of the anticipated TaH,, eliminates the possibility of applying regular solution theory to such systems. Rather large negative excess configurational entropies must exist at higher hydrogen concentrations in order to explain the lower saturation values. To account for these low limiting compositions and excess entropies two distinctly different approaches have been followed. Rees and many others1-l2 have assumed that not all interstitial sites are crystallographically equivalent with respect to the interstitial addition; that is, in Eq. [I] p is less than the value anticipated from geometrical considerations. To describe, say, a bcc metal-hydrogen system with a limiting composition of MH by this approach one would consider that p = 1 in the first instance instead of p = 6.&apos;j3 In some cases, nonintegral values of B have been taken in order to improve the fit with the experimental data over limited ranges of composition. The other approach which has been used to explain the low saturation compositions is to assume that, although all sites are available for occupancy, strong repulsive interactions exist between the neighboring interstitial atoms, and hence occupancy of any site excludes or blocks a certain number of neighboring sites from being occupied. Earliest treatments of this concept considered the exclusion of an integral number, of nearest-neighbor sites from being occupied at all concentrations. In this case, the partial configurational entropy is given by: These early treatments failed to allow for the overlap of the blocked sites which will arise at all but the very lowest concentrations. More recently attempts have been made to calculate the effect of this decrease in the number of blocked sites on the configurational entropy. Using the quasichemical treatment of interstitial solid solutions as given by Lacher and assuming that an infinite repulsive interaction energy existed between the solute atoms. atom obtained an approximate configurational entropy applicable to the blocking with overlap case:

Jan 1, 1970

Separates of all the Technical Publications published in 1930 are available at Institute headquarters. All the papers are on file in public, university and technical libraries, and when so indicated in the list, may be found in the TRANSACTIONS. Copies of these papers have been mailed to those members of the Institute who are registered in Classes A-Mining Methods; B-Milling and Concentration; C-Iron and Steel Division; D-Non-ferrous Metallurgy; E-Institute of Metals Division; F-Coal Division; G-Petroleum Division; H-Non-metallic Minerals; I-Mining Geology; K-Mining Administration; L-Geophysical Prospecting, respectively. Other members may obtain copies by writing to the Secretary. Additional copies are sold at the rate of 1 cent per page; minimum charge, 25 cents. METAL MINING TECH¬ NICAL PUBLI- TITLE AUTHOR MEETING TRANS CATION VOLUME No. AND PAGE* 264-A.29. Quicksilver Industry in 1929. Im- L. H. Duschak San Francisco T30, 283, 312 provements in the Metallurgy of C. G. Maier and Oct., 1929 Quicksilver and Symposium on The others Present Status of the Quicksilver Industry (With Discussion) (37) 271-A.30 Observation on Ground Movement R. E. Palmer New York T30,168 and Subsidences at Rio Tinto Feb., 1930 Mines, Spain (20) 274-A.31 Development and Installation of the C. L. Berrien New York T30, 139, 166 Hawkesworth Detachable Bit (29) . Feb., 1930 276-A.32 Protective Measures Against Gas O. A. Glaeser New York T30, 129, 187 Hazards at United Verde Mine (11) Feb., 1930 287-A.33 Use and Cost of Compressed Air (12) R. S. Lewis New York Feb., 1930 314-A.34 Miami Copper Company Method of F. W. Maclennan New York T30, 39, 80 Mining Low-grade Orebody (44) Feb., 1930 319-A.35 How Human Beings Respond to W. J. McConnell New York Changing Atmospheric Conditions Feb., 1930 (9)

Jan 1, 1930

By G. Wakefield, A. H. Daane, D. H. Dennison, F. H. Spedding

Preparation of pure scandium metal was accomplished by calcium reduction of the fluoride by two methods; a low-temperatzdre alloy process and direct reduction with subsequent distillation of the product. The following properties were determined: melting point: 1181OK; boiling point (calculated): 3000°K; lattice constants at 298°K (hexagonal lattice): a = 3.308 * 0.001 A, c = 5.267 * 0.003A; calculated density at 298°K, g per cm3: 2,990 + 0.007; electrical resistivity, ohm-cm: 299°K, 66.6 ± 0.2 x 10 -6; 373oK, 77.4 * 0.2 x 10 -6; thermal coefficient at 299°K, ohm-cm per deg: 5.4 X x; heat of sublimation at 298°K, kcal pel- mole: 80.79. The vapor pressure was determined as a function of temperature between 1505o and 1748°K, with the data fitted to a straight line shielding the equation: Log Pmm = -1.718 X 104/ToK + 8.298. SCANDIUM, element number 21, was first discovered by Nilson in 1879 and was recognized as the Ekaboron as predicted by Mendeleff. As it is in group III of the periodic table, the general properties are a little like aluminum and also resemble quite closely the properties of yttrium and the rare-earth metals, in both the metallic and ionic form. Although the earth&apos;s crust contains approximately 5 ppm of scandium (the element is as abundant as arsenic and twice as abundant as boron) it generally occurs so widely distributed that it has earned the reputation of being very rare. The one exception to this is the mineral thortveitite, which has been found in Madagascar (20 pct Sc2O3) and in Norway (35 pct Sc2O3). Scandium also occurs in small but distinct amounts in uranium and rare-earth ores; the recent larger scale processing of these materials has made some scandium available from these sources. As with other naturally-occurring monoisotopic elements (except Be), scandium contains an odd number of protons and an even number of neutrons. Scandium metal was first prepared by Fischer and coworkers1 in 1937 by electrolysis of scandium chloride in a molten eutectic mixture of lithium and potassium chlorides, using molten zinc as a cathode and collector of the scandium metal produced. The zinc was removed from the Zn-2 pct Sc alloy by vacuum distillation, leaving a product reported to be 94 to 98 pct Sc, with the main impurities being iron and silicon. They reported a melting point of 1400° C for this material. Scandium has also been prepared by the reduction of scandium chloride with potassium metal in a glass apparatus by Bommer and Hohmann in 1941,&apos; resulting in a mixture of metal and potassium chloride; these workers did not isolate the metal proper, but the X-ray diffraction of the slag-metal mixture showed it to be hexagonal with a = 3.30A, c = 5.45A. petru3, 4 and coworkers have recently reported the preparation of the metal in a compact form by the reduction of either ScF3 or ScC13 with calcium metal and subsequent distillation of the product. This process probably yielded a metal of high purity, but they list no chemical analysis nor do they list any of the properties of their product. Previous related work in this Laboratory has been concerned with the production of yttrium and the rare-earth metals and the determination of their physical properties. Because of its similarity to these metals, scandium is being included in this study. PREPARATION OF SCANDIUM METAL The preparation of yttrium and the rare-earth metals may be accomplished by reduction of their fluorides with calcium metal in tantalum crucibles.5 This process leads to the introduction of tantalum (up to 0.5 pct) as an impurity in the higher melting rare earths, but since the tantalum occurs as dendrites, uncombined with the rare-earth metals, its presence is not objectionable in some cases. The preparation of scandium metal in this manner, however, was found to yield a product containing 2 to 5 pct Ta. To obtain a purer product, the following two methods were developed for the reduction of scandium fluoride with calcium metal: i) a low-temperature process utilizing zinc to form a low

Jan 1, 1961

By D. G. Westlake

THE structure observed in thin foils by transmission electron microscopy is not necessarily representative of the initial bulk material. We have shown that hydrogen, originally present in a specimen of vanadium, niobium, or tantalum, can be concentrated by the thinning operation used to prepare foils from the bulk materials.&apos; These foils exhibited domain walls indicative of a tetragonal distortion of the bcc unit cells, probably caused by ordering of the hydrogen in preferred interstitial sites. We believe this ordering does not occur at room temperature in the bulk material which contains less than 1 at. pct H. In a continued effort to prepare metal foils whose hydrogen concentrations remain constant during preparation, we have developed some new chemical and electrothinning techniques for vanadium. Each of the procedures presented in Table I produced foils that were thin enough for transmission electron microscopy. The experiments described below were performed to test the effect of each thinning procedure on hydro-

Jan 1, 1968

Jan 1, 1902

By Cyril S., Smith

THE phenomenon of air-hardening is well known in connection with special steels. It occurs when the rate of decomposition of austenite to marten- site is so retarded that it takes place on free cooling in air rather than on more rapid cooling in a quenching bath. If an air-hardening steel is quenched sufficiently rapidly it will remain in the soft austenitic state, while if it is cooled very slowly it will again become soft owing to growth of the carbide particles. It depends on a critical adjustment of the decomposition velocity and diffusion rate, and such alloys are rather rare, especially in the non-ferrous field. In carrying out some experiments on some copper- rich copper-cobalt alloys, the author found that these possess very marked air-hardening properties. The alloys are covered by a patent issued to M. G. Corson (1,723,022-1919), which states that an alloy containing between 2 and 5 per cent cobalt is hardened by simple quenching from above 850° C.

Jan 1, 1930

By B. J. Kochanowsky

To improve blasting methods it is necessary to know how the explosive force acts and how rock resists this force. Because of the tremendous power developed within milliseconds and the great number of other factors directly affecting the technical and economic results, an analysis of the fundamentals of blasting theory is difficult. But since the rules used for layout design and for calculations of size of explosive charges are based on theoretical assumptions, complete knowledge of blasting theory has great practical importance in mining. Analysis of Blasting Theory: It is interesting to note the opinion of blasting experts with respect to contemporary blasting theories. F. Stussi,&apos; Professor of the University of Zurich, stated: "We do not have enough experience yet to change our army engineering regulations in blasting and base it on new fundamentals. It is our duty to collect more practical data and to do more research in blasting to close this gap." K. H. Fraenkel,&apos; editor of the Manual on Rock Blasting published in 1953 in Sweden and written by well-known Swedish, German, Swiss, and French blasting and explosive experts, said: "To the best of our knowledge no suitable formulas for civil blasting work are to be found in the American, French or German literature."

Sep 1, 1955

By C. A. Eligwe, F. W. DeVries, A. E. Torma

This study is an investigation on using hydrogen peroxide for tank-leaching of uranium with sulfuric acid. The optimum sulfuric acid concentration was found to be 0.03 mole 11 -&apos;for a 25% pulp density suspension. The order of reaction with respect to sulfuric acid concentration was found to be ns0.75. The best results vith hydrogen peroxide were obtained at a 4.64 molar ratio of 6202 to U in the ore. The order of reaction was found to be zero with respect to hydrogen peroxide concentration. The theoretical maximum rate effect of Hz02 on uranium extraction was derived as Vm = 8.15 x mole &-&apos;min-&apos;. The highest rate experimentally attained was 8.09 x mole kL&apos;min-&apos;. It was found that the uranium extrac- tion was not affected by the pulp density up to the 50% used in this study. However, the final yieldswere significantly higher (over 90%) for leaches carried out in the presence of Hz02 than (less than 90%) for leaches carried out in the absence of H202. The reaction was found to follow a first order course with respect to substrate concentration (pulp density) regardless of the presence of H202. The effect of temperature was more explicit at moderate tempetatures (30 to 55 C) than at lower (10 C) or at higher (70 C) temperatures. At this latter temperature an almost complete extraction was realized even without H202. The apparent activation energies were found to be AEa = 2.68 kJ mole-&apos; in the absence of H202, 0.5 kJ mole-&apos;with Hz02 at 40 C to 70 C. and 4.72 kJ mole-&apos; with Hz02 at 10 C to 40 C. All these activation energy values suggested that the uranium extraction process is diffusion controlled regardless of the presence of H202. Further, the change in activation energy in the presence of Hz02 indicates the possibility of change in the reaction mechanisms at lower and higher temperatures.

Jan 1, 1980

By J. S. Aronofsky

The results of polentiometric model studies and numerical computations are described. The purpose of these studies was to determine the influence of the mobility ratio on flooding efficiencies during water encroachment in petroleum reservoirs, in systems of regular well geometry. The direct line drive well pattern having relative spacing distances of one and one-half to one was investigated for water to oil mobility ratios of 10. 1. and 0.1. The results of these studies indicate that the pattern Sweep efficiency i.; very dependent upon the mobility ratio. INTRODUCTION The almost universal occurrence of water in the immediate neighborhood of oil-hearing sands lends considerable emphasis to the desirability of having a rational analysis of water encroachment into petroleum reservoirs. This problem has 1)become increasingly important with the accelerated use of water injection for secondary recovery operations. The water encroachment problem has been studied from both the theoretical and experimental viewpoints by Muskat.&apos; He has formulated, in a precise manner, differential equations to express flow in a water encroachment system, and rigorous analytical solutions have been developed for the linear, radial, and spherical cases.&apos; However, it becomes exceedingly difficult to solve the encroachment problem rigorously for any general two-dimensional system in which the shape of the two-fluid interface is not immediately evident from the geometry of the system. The difficulty lies in the fart that a rigorous analytical solution requires that the shape of the two-fluid interface be known simultaneously with its instantaneous posititon and with the pressure distribution on both sides of the interface. Although this paper concerns the study of the two-fluid system of oil and water. the methods described in the paper are generally applicable to other systems of incompressible and immiscible fluids in which the displacing fluid sweep-the displaced fluid down to a residual value. In each region it is assumed there is only one mobile fluid and its mobility is constant throughout the region. The Same procedure. with minor alteration, is applicable for gas injection systems provided the assumption can be made that both the displaced and displacing gases can be described by steady state formulas. For the particular two-fluid problem considered in this paper, there is a relative permeability. K, and a viscosity. p. associated with the water zone, and a different permeability and viscosity associated with the oil zone. The K/p (mobility value associated with a particular volume element of the porous medium. at any instant of time. will depend upon whether the element is ahead of. or behind the advancing interface. It is assumed that all volume elements ahead of the interface are characterized by the K/p value for oil, while all the elements behind the interface are characterized by the K/p value for water. That is. the K/p value in the oil zone is constant throughout the oil zone. and the K/p value in the water zone is also constant but different from the value in the oil zone. The symbols are defined at the end of the paper. The well pattern chosen for initial study is the direct line drive; the swept-out area at breakthrough was determined by two different methods which are described in the section on theory. These are: 1. Potentiometric analyzer 2. Numerical computation The use of the potentiometric analyzer for studying water flooding problems is adequately described in the literature, particularly for cases where the mobility in the water zone is assumed equal to the mobility in the oil zone." &apos; 5

Jan 1, 1952

By R. W. Armstrong, P. C. Jindal

WE should like to point out that Hu and cline.1 in their study of the recrystallization of titanium, have obtained data which appear very important for accurately determining the dependence of hardness on grain size for this material. It has been proposed2,3 that the macrohardness. H. of a poly crystalline material should depend on its average grain diameter, l. in accordance with the relationship: H =H0 + kHl-1/2 [1] where Ho and kH are experimental constants. This relationship follows from the hardness dependence on yield stress or flow stress4 and. thence. the Hall-Petch stress-grain size relations.5&apos;6 Fig. 1 shows the Diamond Pyramid Hardness. Dph. values vs the reciprocal square root of the average diameter of the recrystallized grains, taken from the titanium data reported by Hu and Cline. The data in this figure give a linear relationship for the hardness over a wider range of grain diameters than anyone has previously measured. The data are not linear, for example. on an I-1 or l-1/3 scale. At the very large grain sizes the data are in reasonable agreement with measurements earlier reported by Holden, Ogden, and Jaffee.7 For the grain sizes smaller than 1 µ, which correspond in Fig. 1 to hardness values greater than 150, the material was reported as not being completely recrystallized and, therefore, these data appear less meaningful as far as the hardness dependence on grain size is concerned. However. it has been suggested by other investigators that deformed materials exhibit strengthening due to an effective grain size refinement even in the unrecrys-tallized condition.8-10 Also. Hu and Cline have shown that a change in texture occurs for titanium during the recrystallization process and. especially. following it. The influence of this texture change on the hardness-grain size relation would be expected to be less than that reflected in the unidirectional stress-strain behavior, even for an hcp material. because of the actual combined stress system which applies for the hardness test. For, at least, certain combined stresses, average values of the orientation factors should still occur in the stress-grain size analysis of a material exhibiting a preferred orientation.&apos; We previously suggested3 that the experimental constants. H0 and kH. from the Meyer hardness-grain size relation should be correlated with the Hall-Petch constants, uoy and ky.5,6 Our recent study" of the Hall-Petch relation and the hardness-grain size results which obtain for a number of polycrystalline materials shows that: The inequality [2] is explained by noting that the hardness should be correlated. perhaps, with the flow stress at some value of strain, as suggested by Dugdale,12 and. also, that the influence of strain on the Hall-Petch relation is to increase uo and not change k very much." Normally. Dph values and Brinell hardness values are nearly equivalent to each other and to the Meyer hardness number. For the case of titanium, then. the inequality [2] may be evaluated using the experimental values of ao = 8.0 kg per sq mm and ky = 1.3 kg per mm3/2 obtained from the experiment of Guard.6,13 Thus, (Ho/uo) = 12 and (kH/k3) = 1.3. This research has been supported at the University of Maryland through the Center of Materials Research by the Advanced Research Projects Agency of the U.S. Government.

Jan 1, 1969

Papers in Classes A-Metal Mining, B-Milling and Concentration, H-Industrial Minerals, and I-Mining Geology are distributed in MINING TECHNOLOGY, which is issued every Other month. Papers in Classes C-Iron and Steel Division, D-Nonferrous Metallurgy and E-Institute Of Metals Division are distributed in METALS TECHNOLOGY, which is issued twice quarterly. Papers in Class G-Petroleum Division are distributed in PETROLEUM TECHNOLOGY, which is issued every Other month. TECHNICAL PUBLICATIONS in Classes F-Coal Division, J-Mineral Industry Education Division, K-Mining Administration, and L-Geophysics, are issued as separate pamphlets. Contributions are papers that when printed Or mimeographed are available, but Only On request. All the TECHNICAL PUBLICATIONS Of the F, J, K Or L classes, the TECHNOLOGYS and the CONTRIBUTIONS issued in 1945 are available at Institute headquarters, unless Otherwise noted. They are also On file in many public, university and technical libraries and, when so indicated in the list, the papers may be found in the TRANSACTIONS. An Institute member is entitled to One copy Of any TECHNOLOGY, TECHNICAL PUBLICATION Of the F, J, K Or L classes, Or printed Or mimeographed CONTRIBUTION. Copies Of TECHNOLOGYS and TECHNICAL PUBLICATIONS Of the F, J, K Or L classes listed have been mailed to members Of the Institute according to their registration by classes. CONTRIBUTIONS will he sent upon request. A member may purchase an additional copy Of a TECHNICAL PUBLICATION Of the F, J, K Or L classes, a paper in a TECHNOLOGY, Or a CONTRIBUTION at One cent a page; minimum charge, 25¢.

Jan 1, 1946

By A. W. Gauger

WITHOUT QUESTION the Commonwealth of Pennsylvania contains the most remarkable coal deposits of the whole world. Within its borders ,are to be found excellent coals ranging in rank from the high volatile bituminous of the western part of &apos;the state through the low volatile or semi-bituminous of central Pennsylvania to that aristocrat of solid fuels, anthracite, found in the East. . . . But while other states and even the Federa1 Government have recognized the needs of the coal industry, Pennsylvania has not. Though bituminous coal represents one of the most important industries in the state, far more important in annual productive wealth than agriculture, for example, hundreds, of thousands of dollars have been spent on agricultural research whereas little or nothing has been spent on coal investigation.

Jan 1, 1932

By O. F. Kammerer, W. E. Miller, D. H. Gurinsky, J. Sadofsky, J. R. Weeks

Zirconium and titanium inhibit solution mass transfer of steels by liquid bismuth, mercury, and lead. It is shown that in bismuth and mercury, these adsorb on the surface of the steels and subsequently react with nitrogen and possibly carbon from the steels to form inert, adherent surface layers of ZrN, TiN, or TiN + Tic. Data are presented which describe the condition under which thase deposits form. These inhibitors decrease the solution rate of iron into bismuth, and require a higher supersaturation for precipitation of iron from bismuth. USE of the low-melting heavy metals (bismuth, lead, mercury, and their alloys) as coolants has been limited because solution mass transfer of steels occurs in these liquids; i. e., iron dissolves in the hot sections of the heat transfer circuit and deposits in the colder sections. The rate of solution of iron and the temperature coefficient of solubility are sufficiently great to cause complete or partial stoppage by the deposition in the coldest section of a closed circuit in finite time, even though the actual solubilities are extremely low. In the development of the mercury vapor turbine by the General Electric Co., Nerad and his associates1 discovered that the addition of as little as 1 ppm Ti or Zr to magnesium-deoxidized mercury reduced the mass transfer of ferrous alloys by mercury to a negligible amount. Reid2 reported that titanium was detected chemically on the surface of steels contacted with this mercury alloy in amounts varying from 2.0 to 2.6 mg per sq in., the greatest amount being found in the hottest portion of the circuit. Reid stated that the titanium forms the intermetallic compound Fe2Ti by reaction with iron on the surface of the steels. This compound was presumed to be highly insoluble in mercury. More recently, El-gert and Egan3 have reported a greater than 100-fold reduction in the rate of mass transfer of a 5 pet Cr steel by liquid bismuth upon the addition of titanium (in excess of 50 ppm) and magnesium (350 ppm) in the liquid metal, during experiments performed in thermal convection loops* over the temperature differential 700° to 615° C. Also, Shep-ard and his associates&apos; have reported that the addition of titanium to liquid bismuth and Pb-Bi eutec-tic produced a marked decrease in the rates of solution of both iron and chromium from type 410 steel capsules under static conditions. This inhibiting effect increased with repeated reuse of the capsules. Tests performed in this laboratory under carefully controlled conditions have shown that the addition of zirconium and magnesium, or titanium and magnesium, to liquid bismuth or lead greatly reduces the rate of mass transfer of chromium alloy steels and carbon steels in thermal convection loops with a maximum temperature of 550°C.5-9 The present paper will review the data obtained to date at this laboratory on the behavior of iron and steels in contact with liquid bismuth alloys containing titanium or zirconium, and will attempt to explain the role of the above additives in reducing solution mass transfer. Reaction between the Zirconium or Titanium Dissolved In Liquid Bismuth and an Iron or Steel Surface Reaction between Zirconium Dissolved in Bismuth and the Surface of Pure Iron-—A small pure iron crucible (analyzed by the supplier to contain 0.8 ppm N was contacted with bismuth containing approximately 0.1 pet Mg and varying amounts of a radioactive zirconium tracer. The crucible was then inverted at the temperature of contact. The thin residual layer of adherent bismuth was dissolved in cold, concentrated nitric acid. The crucible surface and the solidified bismuth were then analyzed for radioactive zirconium. An analysis of the activity loss on the crucible surface and the weight loss of the crucible during the nitric acid treatment showed that the acid treatment removed the zirconium that had originally been dissolved in the adherent bismuth, but not any zirconium that may have reacted with the crucible surface. The crucible was then pickled in warm aqua regia to remove all surface activity, hydrogen-fired at 600°C, and recontacted with a new liquid alloy. The results of the experiments contacted 1 hr at 450°C show, Fig. 1, a Langmuir-type adsorption with an adsorption free energy of approximately 17 keal per g atom Zr.5 This deposit was estimated to contain 1 atom of zirconium for each 7 to 8 iron atoms on the crucible surface, assuming a surface roughness factor of the pickled crucibles to be five. Increasing the temperature to 520°C caused consi-

Jan 1, 1959

By Henry Knox

AMIDST the tumult and the shouting of the times, there are perceptible certain tendencies, quiet though serious, to take stock of the situation with a view to putting our house in order, and of these none is more encouraging than the awakening, interest in the higher education, and especially in technical education. Various committees of the professional organizations have cast much light on the matter and have pointed the way to progress and reform, but their scope is necessarily restricted by the requirements of precision and any excursion beyond these bounds must be undertaken by the unfettered individual who is free to rush in where responsible committees fear to tread. A discussion of the bearing of the higher education on character scarcely lends itself to objective treatment and yet, fraught as it is with imponderables and abstractions, the theme cannot be escaped in any com-prehensive scheme of education. The question is being pressed with growing insist-ence, why these United States, relatively to Europe, are deficient in intellectual output, and the ready reply, "Because America is a new country and Americans are too intent on developing their natural resources," is too facile and too false to carry conviction.

Jan 12, 1922

By R. H. Jacoby, M. J. Rzasa

Experimental equilibrium vaporization ratios were obtained for nitrogen, methane, carbon dioxide, ethane, and hydrogen sulfide in natural gas-condensate systems. Two different overall mixture compositions were investigated over the pressure range 500 to 4,000 psia at 100°, 150°, and 200 °F. Partial phase diagrams of the mixtures were obtained; one of these showed a critical point at 204°F and 3,875 psia. These and earlier data&apos; were compared with the Kellogg correlation&apos; at! 100°F and 1,000 psia. INTRODUCTION The authors&apos; have presented equilibrium vaporization ratios for nitrogen, methane, carbon dioxide, ethane, and hydrogen sulfide in complex mixtures, such as natural gas-crude oil and natural gas-absorber oil. Since mixtures of the natural gas-condensate type also occur widely in petroleum reservoirs and often contain the non-hydrocarbons mentioned, it would be useful to have appropriate K data for calculating equilibrium vaporization conditions. Roland, Smith, and Kave-ler&apos; obtained K&apos;s for methane and the light hydrocarbons in gas-condensate mixtures; and Poettmann and Katz3 obtained K&apos;s for carbon dioxide in a gas-condensate system. The data presented in this paper extend this coverage to include K&apos;s for nitrogen and hydrogen sulfide and phase diagrams for the experimental mixtures. EXPERIMENTAL WORK The equipment and experimental procedure was essentially as described previously, except for analysis of the vapor samples. The vapor sample bombs were filled at the pressure and temperature of the run. Immediately after sampling, a portion of this sample was flushed from the bomb into a 650 cc glass bulb, filling it to near atmospheric pressure. The sample in the glass bulb was then analyzed by the mass spectrometer. Some checks were made on this analytical procedure to find the accuracy of measurement of the C + content of the vapor samples. The modifications tried were complete fractionation of the vapor sample and the use of several liquids (depropanized condensate and retrograde liquid from several vapor samples) as calibrating materials for the mass spectrometer. The results obtained from these various checks differed by about 10 per cent relative and this is believed to be the order of accuracy of the vapor C+ concentrations.

Jan 1, 1953