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By Didyk M. Marko, Vásquez Ñ. Gregorio

INTRODUCTION The Salvador Division of Codelco Chile is an important copper molybdenum production center, located 1,200 km north of Santiago and 124 km east of the Pacific Ocean, in the foothills of the Andes Range. El Salvador Mine produces by block caving 8,600,000 t of ore with a content of 1 .l0% Cu and 0.02% Mo, from a copper porphyry ore body. The geology of the ore body shows a great heterogeneity as to rocks, grade distribution, ore height and undercutting levels. This has resulted in a variety of designs for the productive units (blocks) and in the mineral handling systems. Up to now, 4 systems have been employed: grizzly and intermediate haulage; slusher drifts with intermediate ore pass and haulage; slusher drifts with scraper loading directly into trains; and, LHD. On the other hand there is a marked dispersion in the final results from each block mined out. We report here the conclusions reached after analyzing the data gathered on the mining of 163 depleted blocks, representing a total production of 102,000,000 t, with an undercut area of 340,000 sq m. The final results of each block, characterized in terms of tonnage and fine cop- per recovery, were studied as a function of a number of design, geological, and operational parameters. BASIC CONCEPTS Indices of Efficiency In order to evaluate the final result of each block, or group of blocks, the following indices of efficiency were defined : Tonnage Recovery (TR) . It is the ratio between the ore tonnage extracted and the in situ tonnage estimate for each block or group of blocks. Grade efficiency (E) . It is the ratio between the Cu mill feed grade and the in situ Cu grade estimate for each block or group of blocks. Grade efficiency is numerically equal to the ratio between fine copper recovery (FR) and tonnage recovery (TR) . Figure 1 shows the final results for 163 mined out blocks, in terms of tonnage and fine copper recovery. Different grade efficiencies are also indicated. The marked dispersion in the final results of mined out blocks must be stressed since it greatly incides in mine planning. It must be kept in mind that an eventual concentration of low overall efficiency in the blocks during a given period (e.g., one year) will make it necessary to bring into production new blocks over the standard development schedule. It is worth noting that the final results in the 163 mined out blocks corresponding to a production of 102,000,000 t of ore with a mill feed grade of 1.445% were obtained from an ore estimate of 93,000,000 t and a grade of 1.671% Cu, which represents 110% tonnage recovery and 86% grade efficiency. Parameters Studied The following parameters are considered in this study: Geological Parameters. These parameters depend exclusively on the geological and geotechnical features of the ore body. IN SITU GRADE: The initial estimate of the block grade. Four copper grade categories were considered : (a) lower than 1.3% ; (b) 1.3 to 1.6%; (c) 1.6 to 2.0%; (d) higher than 2.0%. The overall initial in situ estimate of the ore body was 1.6% Cu. IN SITU TONNAGE: Initial tonnage estimate of the block. Four categories are considered: (a) below 500,000 t; (b) 500,000 to 1,000,000 t (c) 1,000,000 to 1,500,000 t; (d) over 1,500,000 t. CONTACTS SLOPE: Since up to 4 rock types can be found in a block, resulting in a corresponding number of contacts, a horizontal con- tact was defined as that which forms an angle of less than 45" with the horizontal and a vertical contact that which forms an angle of more than 45" with the horizontal. GRADE DISTRIBUTION: As in rock types, horizontal and vertical grades were defined. ORE HEIGHT: The distance measured between the undercut level and the top of ore. Four categories are considered: (a) less than 60 m; (b) 60 to 100 m; (c) 100 to 150 m; (d)over 150 m

Jan 1, 1981

By T. L. Joseph, G. Bitsianes

THE layered structure of partially reduced iron ore was described in a previous paper.' Reduction by hydrogen was found to take place at well-defined interfaces between layers of the solid phases. In the present investigation, a detailed study was made of the wiistite phase that had formed during the partial reduction of a cylindrical compact of chemically pure hematite. An unusually wide band of wiistite permitted a rather detailed study of this phase. The specimen was made from Baker's C.P. hematite in the form of a cylinder 1.5 cm in diameter and 1.8 cm long. A dense ore structure with about 6 pct porosity was attained by heating the specimen in air at 1100°C for 3 hr. To confine reduction to the top surface, a ceramic coating was applied to the bottom and sides of the cylindrical compact. The specimen was then partially reduced in hydrogen at 850°C and subjected to a coordinated sequence of macro-, micro-, and X-ray examinations. A section of the partially reduced cylinder is shown in the macrograph, Fig. 1. Four layers consisting of metallic iron, wustite, magnetite, and unreduced hematite are clearly shown. The effort to force reduction to proceed downward in topochemi-cal fashion was only partly successful, as some reduction occurred along one side and bottom of the cylinder. A rather wide layer of dark wustite phase had formed, however, and permitted sampling for X-ray studies as indicated. To supplement previous work and to study the wustite layer in more detail, ten separate layers were removed for X-ray examination. Broad and diffuse patterns were obtained with the as-filed powders, especially with those of iron and wiistite, and the condition indicated a cold-working and variable composition effect within the respective layers. This condition was corrected by annealing the entire series of powders at an appropriate temperature. For the annealing treatment, the ten powder samples were wrapped in silver foil, sealed under vacuum in small quartz tubes, and heated at 750°C for 16 hr. The specimens were then drastically quenched in cold water to preserve the annealed condition. These annealed specimens were X-rayed in turn and the compiled patterns are shown in Fig. 2. The standard patterns for iron and its oxides have been interjected at appropriate positions for purposes of comparison and phase identification. All of the patterns obtained were clearcut and concise so that positive identifications could be made for all of the phases. The outermost layers A, B, and C were composed almost entirely of iron with a small amount of wiistite being detectable at the X-ray limit of phase detection. Layer D from the iron-wustite interface showed both of these phases. The next four layers E, F, G, and H were all in the dark phase band which had been tentatively identified as wustite by the macroexamination, Fig. 1. The diffraction data with their single-phase patterns of wiistite for these layers checked the visual evidence. Continuing the X-ray analyses after layer H, the macrograph (Fig. 1) shows that layer I came largely from the magnetite zone but included some fringes of the wiistite-magnetite interface. The diffraction pattern for the sample confirmed this observation. Layer J came from the unreduced core of the specimen and its diffraction pattern indicated a preponderance of hematite phase. The reduction behavior of synthetic compacts has thus been found to be similar to natural dense iron ore. The previous results were supplemented with measurements of the diffraction films and calculations of the respective unit parameters. These X-ray data are summarized in Table I and offer some interesting correlations as to the compositions of the various phases undergoing reduction. The iron layers that were analyzed gave lattice parameters close to that of pure iron at 2.8664A. Evidently this iron was present in layers A through D as a pure phase with little or no oxygen dissolved in its lattice. With the wiistite layers an entirely different situation prevailed in that there was a definite and

Jan 1, 1955

By G. L. Simard, D. J. Salley, J. Chupak

DITHIOPHOSPHATES and xanthates are the principal collectors for sulphide minerals, and consequently any knowledge of mineral-collector systems of this type is of value. In the present investigation an attempt was made to obtain information on the interaction of a typical dithiophosphate with galena. In carrying out this study, radioiso-topes, so much discussed in the past few years,', ' were extensively employed. By using radioactive dithiophosphate synthesized from radioactive phosphorus, a rapid and sensitive analytical procedure G. L. SIMARD is in the Research Division, Stamford Research Labs., American Cyanamid Co., Stamford, Conn.; J. CHUPAK, formerly in the Research Division, Stamford Research Labs., is now at Camp Detrick, Frederick, Md.; and D. J. SALLEY is in the Research Division, Stamford Research Labs. AlME New York Meeting, Feb. 1950. TP 2815 B. Discussion (2 copies) may be sent to Transactions AlME before April 30, 1950. Manuscript received Oct. 17, 1949. was at hand. This permitted determination of such important quantities as the rate of uptake of dithiophosphate by the mineral, the amount existing at equilibrium on the mineral surface and in the solution, and the desorption of the agent from the surface. Such measurements were possible even on single crystals of galena. In addition the exchange of dithiophosphate between the solution and the sorbed phase was examined, a matter which could be accomplished only by the use of isotopes. It is desired to point out at this time that throughout this paper the term "sorption" has been employed to designate the uptake of agent by mineral, without implication as to the nature of the process by which the uptake was accomplished. Experimental Materials: Galena: The galena was from the Tri-State district. For studies on ground mineral four preparations were used during the course of the investigation. These were prepared from selected large crystals by wet grinding in order to reduce surface oxidation. Alcohol was chosen as a convenient medium for this purpose. The ground mineral was then fractionated by sedimentation in alcohol, dried by evacuation, and stored in a nitrogen-filled desiccator. Data on the preparations are tabulated in table I. The size analysis indicated that the areas of the preparations were of comparable magnitude, even though the absolute values may be somewhat incorrect. Dithiophosphates: Nonradioactive dithiophbsphate (di-isopropyl or di-secondary butyl) was obtained by purification of a commercial product. An aqueous acid solution of the agent was extracted with petroleum ether, the ether layer dried, and the dithiophosphate precipitated as ammonium salt with anhydrous ammonia. Several repetitions of this process resulted in a nearly colorless, flaky product of good purity. (General formula (RO,)PSSNH,). Radioactive dithiophosphate was synthesized by heating radioactive elementary red phosphorus* • For early experiments (1943 to 1944), the elementary red phosphorus was obtained from the cyclotron group at the Crocker Radiation Laboratory of the University of California. Berkeley, through the courtesy of Dr. Joseph W. Hamilton. For more recent work (1946 to 1949). the elementary radioactive Phosphorus has been supplied by the Oak Ridge National Labarotories on allocation from the U. S. Atomic Energy Commission. with sulphur at 270" to 300°C to produce radioactive P,S,. The latter was then treated with the desired purified alcohol (isopropyl or secondary butyl) at 60" to 80°C to form the dithiophosphoric acid derivative. Purification was effected in the same manner as for the nonradioactive material. The effectiveness of the purification method was established by the isotopic dilution method." The same technique was used to show that only negligible decomposition of neutral or of carbonate solutions of the dithiophosphate took place over a period of a day; this was true whether or not galena was suspended in the solutions. Procedures: Radioactivity: The activity of a solution was obtained by counting with a small glass-jacketed, silvered Geiger counter, using a conventional scaling circuit.' Crystals and other solids were counted under a bell-shaped, mica-window counter tube. Sufficient counts were made so that the probable error of counting was of the order of +I-3 pct. The specific activity in terms of counts per minute

Jan 1, 1951

By J. Chupak, D. J. Salley, G. L. Simard

DITHIOPHOSPHATES and xanthates are the principal collectors for sulphide minerals, and consequently any knowledge of mineral-collector systems of this type is of value. In the present investigation an attempt was made to obtain information on the interaction of a typical dithiophosphate with galena. In carrying out this study, radioiso-topes, so much discussed in the past few years,', ' were extensively employed. By using radioactive dithiophosphate synthesized from radioactive phosphorus, a rapid and sensitive analytical procedure G. L. SIMARD is in the Research Division, Stamford Research Labs., American Cyanamid Co., Stamford, Conn.; J. CHUPAK, formerly in the Research Division, Stamford Research Labs., is now at Camp Detrick, Frederick, Md.; and D. J. SALLEY is in the Research Division, Stamford Research Labs. AlME New York Meeting, Feb. 1950. TP 2815 B. Discussion (2 copies) may be sent to Transactions AlME before April 30, 1950. Manuscript received Oct. 17, 1949. was at hand. This permitted determination of such important quantities as the rate of uptake of dithiophosphate by the mineral, the amount existing at equilibrium on the mineral surface and in the solution, and the desorption of the agent from the surface. Such measurements were possible even on single crystals of galena. In addition the exchange of dithiophosphate between the solution and the sorbed phase was examined, a matter which could be accomplished only by the use of isotopes. It is desired to point out at this time that throughout this paper the term "sorption" has been employed to designate the uptake of agent by mineral, without implication as to the nature of the process by which the uptake was accomplished. Experimental Materials: Galena: The galena was from the Tri-State district. For studies on ground mineral four preparations were used during the course of the investigation. These were prepared from selected large crystals by wet grinding in order to reduce surface oxidation. Alcohol was chosen as a convenient medium for this purpose. The ground mineral was then fractionated by sedimentation in alcohol, dried by evacuation, and stored in a nitrogen-filled desiccator. Data on the preparations are tabulated in table I. The size analysis indicated that the areas of the preparations were of comparable magnitude, even though the absolute values may be somewhat incorrect. Dithiophosphates: Nonradioactive dithiophbsphate (di-isopropyl or di-secondary butyl) was obtained by purification of a commercial product. An aqueous acid solution of the agent was extracted with petroleum ether, the ether layer dried, and the dithiophosphate precipitated as ammonium salt with anhydrous ammonia. Several repetitions of this process resulted in a nearly colorless, flaky product of good purity. (General formula (RO,)PSSNH,). Radioactive dithiophosphate was synthesized by heating radioactive elementary red phosphorus* • For early experiments (1943 to 1944), the elementary red phosphorus was obtained from the cyclotron group at the Crocker Radiation Laboratory of the University of California. Berkeley, through the courtesy of Dr. Joseph W. Hamilton. For more recent work (1946 to 1949). the elementary radioactive Phosphorus has been supplied by the Oak Ridge National Labarotories on allocation from the U. S. Atomic Energy Commission. with sulphur at 270" to 300°C to produce radioactive P,S,. The latter was then treated with the desired purified alcohol (isopropyl or secondary butyl) at 60" to 80°C to form the dithiophosphoric acid derivative. Purification was effected in the same manner as for the nonradioactive material. The effectiveness of the purification method was established by the isotopic dilution method." The same technique was used to show that only negligible decomposition of neutral or of carbonate solutions of the dithiophosphate took place over a period of a day; this was true whether or not galena was suspended in the solutions. Procedures: Radioactivity: The activity of a solution was obtained by counting with a small glass-jacketed, silvered Geiger counter, using a conventional scaling circuit.' Crystals and other solids were counted under a bell-shaped, mica-window counter tube. Sufficient counts were made so that the probable error of counting was of the order of +I-3 pct. The specific activity in terms of counts per minute

Jan 1, 1951

By E. T. Turkdogan, L. E. Leake

A number of measurements have been made on the vapor pressure of pure iron at 1600°C. Experiments were carried out by the transportation method in which a sample of iron is exposed in a furnace to a stream of pure argon, metered at a predetermined flow rate for a specified period of time. The vapor pressure was obtained from the weight loss of the sample. A detailed diagram of the apparatus used for the experiments is given in Fig. 1. It consisted of a horizontal molybdenum-wire-wound furnace fitted with a recrystallized alumina tube 1 1/8 in. internal diam. The boats, 1 by 3/16 by 1/8 in., were fired in argon at 1600°C to constant weight before use. After this treatment, subsequent heating of the boats to 1600°C gave little or no further change in weight, e.g. ±0.05 mg in 24 hr. The furnace and reaction tube were separately fed with argon from two independent flowmeters. These were connected to a common supply source via an argon purification furnace containing metallic titanium sponge at 700°C, and an anhydrone drying-tower. A rotary displacement-type meter was included in the gas train to provide a direct means of measuring the total volume of gas passed through the reaction tube. The material used was vacuum melted high-purity iron in the form of wire 2mm in diam. The following impurities were present in the iron: 0.008 pct C, 0.002 pct Si, 0.005 pct Mn, 0.008 pct S, 0.001 pct P, 0.01 pct Ni, 0.001 pct Cr, 0.006 pct Cu, and 0.001 pct Al. Samples consisting of three small pieces of this wire were laid end to end in a recrystallized alumina-combustion boat, and were separated by small fragments of alumina. The wire samples were then melted in argon to form spherical beads 2 to 3 mm in diam. After weighing, the boat with its contents was placed on the boat carrier and introduced into the cool end of the reaction tube. The entire furnace system was then flushed with argon for 30 min. At the end of this period, the flow of argon to both furnace and reaction tubes was adjusted to the desired level; then the boat was slid rapidly into the hot-zone of the reaction tube. After a known volume of gas had passed through the reaction tube, the boat was withdrawn quickly to the cool end of the furnace. When quite cool, the boat was removed from the fur-mace and placed in a desiccator for subsequent re-weighing. The semi-micro balance used in these experiments had a sensitivity of 0.005 mg. The above procedure was repeated at several flow rates within the range of 25 to 300 ml per min. The flow of argon in the annular space between the two tubes was at a rate of 300 ml per min in all experiments. During all the experiments the furnace temperature was maintained at 1600° ± 5°C by means of a temperature controller. The temperature of the reaction zone was measured with a Tinsley high precision disappearing filament pyrometer which was initially calibrated against a Pt-13 pct Rh/Pt thermocouple; the errors due to temperature measurements were within * 5°C. RESULTS Assuming that the iron vapor is in the monatomic state, the vapor pressure can be calculated from the weight loss of the sample and the volume of the carrier gas. The results obtained are plotted in Fig. 2 against the rate of flow of argon through the chamber containing liquid iron beads. At low flow rates, the thermal diffusion of iron gives an apparent high vapor pressure, but at high gas flow rates, the carrier gas is not saturated with the vapor, and therefore, low vapor-pressure values are obtained. This is now a well-known phenomenon. There is a distinct inflexion of the curve at about 120 to 160 ml per min rate of argon flow and the vapor pressure of iron within this

Jan 1, 1961

By L. Zwell, H. A. Wriedt

X-ray Lattice parameter and bulk density measurements were made at room temperature on solid solutions of nitrogen in purified a, iron, containing from 0 to 0.053 wt pct N. When nitrogen is dissolved in a, iron, the fractional increase in unit cell volume (X-ray diffraction) and the fractional increase in volume per gram of iron (bulk density measurement) are the same within experimental error. The two sets of results when averaged show that the unit cell edge of a, iron increases linearly by 3.2 X 10-2 A per wt pct N dissolved and that the partial gram-atomic volume of nitrogen at infinite dilution in a, iron is the same as it is in nitrogen-martensite, that is, 5.90 cm3. RECENT reviews17' of literature dealing with the lattice parameter of ferritic iron-nitrogen alloys indicate that the dilating effect of dissolved nitrogen on the bcc unit cell of a iron is not known with confidence. Five investigations3-7 either revealed no effect of nitrogen or were inconclusive. Among other investigations, where quantitative data were obtained, the results of Osawa and Iwaizumi8 indicate too large an effect, and those of Eisenhut and Kaupp9 show the lattice parameter of ferrite varying with the nitrogen content at concentrations far beyond the known solubility limit. It is not clear in Burns'10 data what value should be used for the lattice parameter of nitrogen-free ferrite in calculating the dilation. Burdese11 shares with Burns the shortcoming that the iron-nitrogen alloys were solution-treated and quenched with undissolved nitride present. The consequence is that the un- certainties in the solubility limit1 are added to those in the lattice parameter measurements when the variation of lattice parameter with nitrogen content is computed. For a system of such widespread interest, we felt that a new investigation was merited. Both X-ray diffraction and bulk density measurements were used to determine the dilation of the , a iron lattice by dissolved nitrogen. EXPERIMENTAL PROCEDURE Material. The bulk density and X-ray diffraction experiments were both made with specimens of a purified iron (denoted as "B iron")- from Battelle Memorial Institute. The impurity contents were as follows: As, C, Cu and Pb—50 ppm; Ag, Al, Co, Ga, 0, Ti-11 to 50 ppm; B, Be, Ca, Cd, Cr, Mg, Mn, Mo, N, Ni, S, Sb, Si, Sn, V, W-10 ppm or less. The vacuum-cast ingot was hot-forged and annealed. Pieces of the forged stock were machined and cold-rolled to give strip stock 0.08 and 0.002 in. thick for density and for X-ray measurements, respectively. Preparation of Specimens. Starting with a piece of the cold-rolled iron stock, the general sequence of operations, after an initial recrystallizing anneal, was to measure the density or lattice parameter, nitrogenize, remeasure the property, age or denitrogenize, and again measure the property. Duplicate analyses for nitrogen were made by a modified Kjeldahl method on portions of the actual density specimens and on pieces nitrogenized to equilibrium alongside the X-ray specimens. Annealing of the density specimens was performed by sealing the pieces with the as-rolled surfaces removed by filing into evacuated "Vycor" capsules and treating for 1 hr at 750°C followed by furnace cooling. (TO check the effect, if any, of annealing procedure, a specimen also was

Jan 1, 1962

By R. D. Burlingame, T. L. Joseph, Gust Bitsianes

DESPITE almost fifty years of commercial practice, the sintering of iron ore has received little fundamental study. Much of the theoretical work1-'has dealt with the constitution of sinter produced under widely varying conditions. While these studies have broadened our knowledge of the changes that occur in the sintering zone and in the freshly formed sinter during the early stages of cooling, they provide little insight into the changes that precede the formation of sinter. These preliminary changes merit study as a part of the overall process. Hessle. working with beds of Swedish magnetite concentrates, was one of the first investigators to study the sintering process in its entirety. On the basis of temperatures observed at various levels of the bed during sintering, he postulated a number of distinct reaction zones to account for the chemical changes leading to the formation of sinter. A more direct method of attack is that of arresting the sintering zone after it has progressed part way through the bed. A study of a vertical cross section through such a quenched bed provides direct information on the changes taking place at various levels. This method was used by McBriar et al.' to show that several well-defined zones of chemical change existed within beds that were typical of British sintering practice. The same general method of attack was developed independently in the present investigation to study partially sintered beds typical of American practice. Experimental Sintering Equipment The sintering operation was carried out on an experimental scale with the equipment shown in Fig. 1. The refractory-walled sintering chamber A was 11 in. deep and averaged 9 in. in diameter. Air was introduced through a tapered flow section B, which contained the orifice C for accurate metering of the incoming air. This section was located directly above the square ignition housing D, which in turn rested upon the sintering chamber A. The bed was ignited with burner E. The required suction for the operation was furnished by a fan F, which had an air capacity of 500 cfm (stp). Hot exhaust gases from the sintering chamber were cleaned in the dustcatcher G before entering the exhaust fan. In the study of partially sintered beds, it was essential to find some technique for removing the entire charge from the sintering pot without disarranging the unsintered bottom portion. This problem was finally solved by sintering the charge in a removable basket, which snugly fitted the sintering chamber. This basket was constructed of two thicknesses of window screen and was lined with a 3/16-in. layer of asbestos paper. The bottom of the basket consisted of two thicknesses of wire screen, which were fastened to the basket wall. For high fuel mixtures, additional insulation was provided by a somewhat thicker layer of asbestos cement. Preparation of Partially Sintered Mixtures The moist feed was carefully placed in the sintering basket, to prevent segregation of the particles, which varied widely in size and composition. A thermocouple was placed in the center of the basket with the hot junction halfway down, and the mixture was evenly distributed around it. During ignition and throughout the sintering of the upper half of the bed, the hot junction temperature increased very little. When the sintering zone reached the halfway point, as indicated by the sudden increase in the hot junction temperature, the charge was quenched. During quenching the suction was turned off and the orifice was tightly stoppered to prevent further influx of air. At the same time, nitrogen was admitted to the sintering chamber through the orifice tap. As soon as the nitrogen had displaced the air and products of combustion, the charge was removed from the sintering pot for immediate dissection. It is impossible to preserve the exact zone structure of the bed at the instant that combustion is arrested unless the downward transmission of heat is also immediately stopped. Fortunately, heat transfer is very slow in beds containing a stationary fluid, especially if the particle size is small. It follows that the minimum quantity of nitrogen should be used to displace the air and that static conditions be established as soon as possible. A very steep temperature gradient across the combustion zone for some time after the quench was evidence of in-

Jan 1, 1957

By Paul G. Shewmon

The migration of slightly solzrhle spherical particles through a solid under the infllrence of a temperature gradient is analylzed for the cases of various transport mechanisms. It is shown that the variation of the velocity of the particles with radius, r, depends on the dominant mechanism of matter transport around or through the inclusion. Thus the velocity varies as r-1 jor surface-dijf1~sion controlled migratzon. is independent of r for volume diffusion in either phase, and varies as if the rate is determined by an interfacial reaction (n is the order of the interfacia1 reaction). These same results hold tor the migration of a cvlinder of length much greater than its radius. and .for other types of potential gradients, e.g., an electrical field. These equations are combined with recent electron-microscopic ohservations to show that the rate of migratzolz of small helium-silled bubbles through copper is determined by surface diffusion of the metal atoms. With these equations and the temperature gradients attainahle in an electron-microscope joil, the dominant transpar/ mechanism (or any migrating pnrtzclos can he determined. AS a result of fission, rare-gas atoms are created in the hot fuel element of a nuclear reactor. These insoluble atoms precipitate to form bubbles of the gas in the fuel. The subsequent migration and coalescence of these bubbles is thought to play a dominant role in the swelling of fuel elements which in turn can limit the fuel-element life. As a result of this practical problem and because of the relative simplicity of the system, workers in several laboratories have imbedded rare-gas atoms in metals with the aid of an accelerator and studied the formation and behavior of the bubbles that form on annealing. Recently Barnes and Mazey have studied the migration of such helium-filled bubbles in copper foils using the electron microscope and the temperature gradient that can be induced in the foil by the electron beam. They found that the smaller bubbles moved faster than the larger ones. It is shown below that, if this is true, the rate-controlling step in their migration is surface diffusion of metal atoms instead of volume diffusion, vapor transport, or an interfacial reaction. The analysis given is in no way limited to gaseous inclusions so the variation of velocity with particle size for any relatively insoluble precipitate particles could be used to obtain information about the relative importance of surface diffusion, volume diffusion, and interfacial reaction in such two-phase systems. VOID MIGRATION IN A TEMPERATURE-GRADIENT ANALYSIS Barnes' studies indicate that helium does not dissolve or diffuse in metals to a measurable extent, so that when the voids move they must do so through the movement of metal atoms from the leading to the trailing sides of the void.' Thus voids might move by surface diffusion, diffusion of vacancies in the surrounding lattice, or vapor transport. We consider first the case of flow by surface diffusion alone. We assume that there is a force, in the sense of irreversible thermodynamics, tending to move the atoms around the bubble in a given direction. We designate this direction as the x axis and the force per atom as Fa. The net rate of flow of atoms from one side of the bubble to the other, under the influence of this force, is the surface flux, Js, times the cross-sectional area available for flow, A,. A, is taken as the circumference times the thickness of the high-diffusivity surface layer 6. Thus where 51 is the atomic volume. For bubbles to advance a distance dx, a volume equal to nr : dx must flow around the void so that The minus sign enters because the bubble moves in the direction opposite to that of the force on the atoms. Equations for volume diffusion and diffusion through the vapor can be obtained in the same manner. For vapor transport we have Ag = and the ratio of the densities of metal atoms in the gas and the solid (pg/pl) enters so that

Jan 1, 1964

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'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,' 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 R. J. Lutton

Empirical data from 91 rock excavations have been used to construct a family of slope curves on a chart relating excavation height and inclination. The highest and steepest slopes from each excavation are plotted and connected by a line. The 31 1ines appear to establish one or two geometrical slope fields through which the curves are projected. The curves apparently represent a lumped eflect of many factors too complex to be considered individually. Important factors such as geological structure or ground-water conditions can dominate the picture, but where these factors do not overshadow others, the slope chart should be useful for estimating or checking optimum inclination. The U.S. Army Corps of Engineers (USAE) has been engaged since 1962 with the U.S. Atomic Energy Commission in a joint research program to develop nuclear excavation technology. The Corps is responsible for collecting the requisite data on engineering and construction problems associated with nuclear excavation. The ultimate objective is to develop a capability to use nuclear explosives as a construction tool on public works projects such as harbors and canals. The present study on empirical inclination-height curves for conventionally excavated slopes is an outgrowth of an investigation' sponsored by the USAE Nuclear Cratering Group on applicability of data from existing excavations in establishing guides for engineering judgment in crater excavation. Data were generously contributed by over 50 mining companies among other organizations. Inasmuch as several companies preferred that their contribution be anonymous, all data are treated so here. Some Factors Affecting Stability Many factors affect or are suspected of affecting the stability of excavated slopes, e.g., adverse structural orientation, degree of structural ordering, ground water, climatic conditions, mechanics of excavation, and plan-profile configuration. Such factors are lumped together in developing a slope chart. Obviously geological structure and ground water can overshadow all other factors. Where such is the case, the simplification of slope charts may give an erroneous picture (not conservative enough). A further complication results from the fact that the concept of stability may vary according to the use of the excavations. For example, slope adjustments that would be regarded as failure in a powerhouse excavation, might be tolerable in a mining operation. Mine slopes are continually being modified by further excavation, and instability that would develop in a similar permanent excavation slope over a period of years might not have time to develop in a mine. Inclination vs. Height Charts Charts of inclination vs. height for particular formations or conditions have been used in the past as an aid for designing excavation slopes. Some of these have been based upon empirical analyses of collections of data and experience. MacDonald" and Lane have presented slope tables and charts for excavated and natural slopes in relatively weak sandstone and shale. Coates' has shown an inclination-height chart for slopes in incompetent rock. Most organizations have developed slope design criteria which relate bench widths, heights, and inclinations to use in various rocks. Slope data collected in present studies can be similarly used to develop inclination-height charts; however, a plot of all slopes on such a chart shows very little because of the wide spread of the data. Reasons for the dispersion of points are: (1) many slopes are not carried at optimum inclination, particularly in mines where maintaining roadways and following irregularities of ore bodies are more important than achieving steep inclinations; (2) many engineers and geologists with varied backgrounds and viewpoints have been involved in designing these slopes; and (3) each slope is characterized by a unique combination of factors affecting stability and in turn optimum inclination. Significant curves can sometimes be constructed where the points can be grouped into related clusters from the same excavation. The essence of this approach appears when only two slopes from each excavation are considered—the highest slope and the steepest slope, connected by a line segment (Fig. 1). This reduces considerably the usable data because in many cases only one of these two slopes is available. Nevertheless, the concession seems justified. Construction of Slope Curves Ninety-one pairs of points and connecting line segments were assembled in this study. The line segments were assumed to approximate a geometrical slope field (Fig. 2), and a family of curves has been visually projected through to represent the slope field. It should be

Jan 1, 1971

By D. S. Bloom

RECENTLY a report has been published on an investigation of the MO-RU system by E. Raub.' In this report it is stated that below approximately 1200°C the system consists of two terminal solid-solution phases and the intervening two-phase field; at 1200°C and above, an intermetallic compound labeled Mo,Ru, makes an appearance. Along with some other little known systems in which it was considered possible for a u phase to form, the Mo-Ru system had been under investigation in this laboratory. Since molybdenum and ruthenium have very high melting points and also since ruthenium is expensive, the investigation was confined to X-ray diffraction by sintered powder compacts. The compositions which were studied were (in atomic percentages): 75 Mo-25 Ru, 67 Mo-33 Ru, 50 Mo-50 Ru, and 25 Mo-75 Ru. All compacts were made from the pure powders, and no chemical analyses were attempted. Each compact weighed about 5 g. All annealing was done in evacuated Vycor capsules, and even though the capsules completely collapsed at 1250°C, they still admitted no air. The results of this investigation in general corroborate the work of Raub. Up to 1150°C the two terminal solutions and the intervening two-phase field were found, and at 1200°C and above an intermetallic compound was found. However, the composition limits of the compound were estimated to lie close to 70 atomic pct Mo rather than 62.5 atomic pct Mo as Raub had reported. At least the X-ray diffraction results indicated that the 75 atomic pct Mo specimen consisted of the molybdenum solid solution plus the compound, while the 67 atomic pct Mo specimen consisted of the ruthenium solid solution plus the compound and the equiatomic composition contained only very little of the compound. The most interesting observation, however, was that the diffraction pattern of the compound was similar to that of the well known u phases, except that unusually large lattice constants were indicated. The d-values, or interplanar spacings, of the diffraction lines (as produced by filtered copper KCX radiation) of the compound are given in Table I, as determined from specimens annealed at 1250°C for 9 hr and then quenched in water. Also shown are the lines of the Mn-Mo u phase as given by Decker, Waterstrat, and Kasper,' the lines of the Fe-Mo a as given by Goldschmidt," and the lines of the Mo-Ru phase multiplied by constants in order to make comparison with the Mn-Mo and Fe-Mo patterns easier. These results indicate that the compound in the Mo-Ru system is apparently isomorphous with the other o- compounds. The rather large lattice constants of the Mo-Ru a phase are acceptable in view of the comparatively large size of the constituent atoms. The data in Table I for the Mo-Ru compound check quite well with those given by Raub, not shown here, though there are some discrepancies between the two sets of data in the estimated intensities of a few lines. Although very little is known at present about this u phase, there are some things which may be pointed out, mainly in comparison with other better known u phases. Even though molybdenum and ruthenium are in the same columns in the Table of Elements as chromium and iron, respectively, the Mo-Ru u phase contains much more molybdenum than ruthenium, while the Cr-Fe u phase centers around or very nearly around the equiatomic composition; furthermore, the Mo-Ru u is stable only above approximately 1200°C, but the Cr-Fe u is stable only below about 825 °C. With respect to its being unstable below 1200°C, the Mo-Ru u is similar to the other binary molybdenum u phases in the Co-Mo and Fe-Mo systems. Similar to the latter two systems, the Mo-Ru u apparently exists over a rather narrow composition range, whereas the Cr-Fe u at lower temperatures is stable over a much wider composition range. The Mo-Ru u thus is closer to the other molybdenum u phases than to the Cr-Fe cr phase. The most striking feature of the Mo-Ru u phase, however, is the absence of any of the transition elements of the First Long Period.

Jan 1, 1956

By B. A. Eaton, R. H. Jacoby

This paper presents the depletion-performance correlations developed using data from PVT studies and well-completion tests of 27 rich gas-condensate and volatile-oil reservoir fluids. The PVT behavior for each fluid war determined experimentally in the laboratory, and the depletion performance of each fluid was then calculated. Well-completion test data consisting of reservoir pressure and temperature, initial total gas-oil ratio, and stock-tank oil gravity were used with the depletion-performance data to develop general performance correlations. Three correlations are presented. The first equation shows the empirical relation of gas in place per barrel of hydrocarbon pore space with reservoir pressure and temperature, and initial total gas-oil ratio. The second equation is the correlation of stock-tank oil in place per barrel of hydrocarbon pore space. The third equation relates stock-tank oil production (to 500-psia depletion pressure) with pressure, temperature and oil gravity. All three correlations are also presented in convenient graphical form. Gas production to 500-psia depletion pressure is approximately 92.6 per cent of the gas in place for each fluid, so no correlation was developed for gas production. INTRODUCTION The rate of discovery of shallow, low-pressure and low-temperature oil reservoirs in the United States has been declining in recent years. For this reason, the search for oil has gone to greater depths where high pressures and temperatures are encountered. A high-pressure and high-temperature reservoir is the environment in which many rich gas condensates and highly volatile oils are found. Because of this trend, the performance prediction of such reservoirs has become an important task of the reservoir engineer. The need and usefulness of a performance correlation based on field data that are available from the usual well-completion tests have previously been established. These earlier attempts have shown that the phase behavior of rich gas-condensate systems and volatile-oil systems can be correlated with fluid properties, pressure and temperature. However, very little information on gas-condensate depletion performance5 was available at the time of these earlier attempts. The availability of more recent data has made possible the development of an improved correlation. The data, as listed in Tables I and 2, are for 25 gas-condensate and two volatile-oil systems that were studied. The problem was to correlate the data for in-place fluids and the production data with the initial total gas-oil ratio, initial reservoir pressure and temperature, and stock-tank oil gravity. These correlations were obtained by multiple regression analysis, whereby the data were fitted to an equation by the method of least squared error. BASIS OF THE CORRELATIONS 1. The data used in the development of these correlations were obtained from depletion-performance calculations6 and well-test or production measurements. 2. All of the independent variables used in the correlations are available from the usual well-test completion data. 3. The reservoir volume considered is 1 bbl of hydrocarbon pore space (HCPS). 4. The gas-oil ratio used is the total standard cubic feet of gas (at 14.7 psia, 60F) coming off the entire separator train per barrel of stock-tank oil. This minimizes the effect of separator conditions which might vary from system to system. 5. The correlated pressures are the actual reservoir pressures which might or might not be the saturation pressure of the reservoir fluid.

Jan 1, 1966

By R. A. Burton, J. T. Hansford, D. A. T. Donohue

Substantial evidence indicates that many petroleum producing horizons contain naturally occurring, ordered fracture systems and that within a particular geologic zone, vertical fractures induced in wellbores often will be directed along a particular compass direction. Both conditions will seriously alter the fluid displacement behavior within reservoirs. In this study the effect of induced fracture orientation and length on sweep efficiency is determined for a five-spot pattern. In general, it is assumed that all wells are fractured and directed along the same compass direction. Using the electrical analog to steady state, two-dimensional fluid flow in porous media, boundary conditions are obtained from which flood fronts are tracked numerically. The numerical computations require a particle tracking routine for approximating flood front histories. It is shown that recovery is sensitive to the length and orientation of fractures for the pattern studied. with the proper design of fracture-pattern systems, recovery can be enhanced considerably. INTRODUCTION Hydraulic fracturing introduced in 1949l gave the industry a rather inexpensive means of increasing the fluid injection or production capacity of wells. It has been used with particular success to increase the production rate of wells completed in tight formations, such as in western pennsylvania2 where producers have fractured in depleted or near-depleted fields and observed economic responses. Once the natural energy declines in such a reservoir where all wells have been fractured, waterflooding is generally suggested as means of further increasing recovery. Of the dual objective sought in waterflooding — high injectivity and high breakthrough sweep efficiency — the former condition can be obtained if all wells in the flood pattern are fractured; the latter condition should depend on the nature of the fracture system. Considerable theoretical work has been published on the nature of fractures induced in boreholes.3-5 Although discussion persists concerning the possibility of forming a horizontal fracture at a given point within the wellbore, it is generally conceded that only vertical fractures will develop below a given depth, i.e., where the fracturing Pressure is less than the overburden load. Given the fact that fractures will be vertical in most cases of interest, it is also important to know whether there is order to fracture orientations within a given geological region. Kehle has suggested that in tectonically relaxed areas of uncomplicated geology, the stresses are fairly uniform and all fractures in the region should be parallel.5 Dunlap arrived at a similar conclusion in a theoretical investigation of localized stress conditions surrounding the borehole.6 He concluded that most vertical fractures are propagated in a preferred azimuthal direction. Fraser and Pettitt, in extending these theoretical suggestions to a specific field case, used an impression packer to record both a vertical fracture and the orientation of this fracture in the wellbore of a well in the Howard Glasscock field, Tex.7 Use of this information enhanced the waterflood recovery of the field. Anderson and Stahl also used impression packers on three fractured wells in the Allegheny field. N. Y.. and found that the fractures were oriented more or less along the same compass direction.8 Orientation of the fractures in this manner depends on the stress condition within the formation during fracturing. Elkins and Skov have demonstrated that a natural, oriented, vertical fracture system exists within the Spraberry field? Heck suggests

Jan 1, 1969

By W. Philippoff, Donald E. Cadwell, S. R. B. Cooke

THE importance of contact angles in flotation has long been recognized, but little has been done to get quantitative relationships between the surface coverage of the mineral by the reagent, the length of the hydrocarbon chain, and the contact angle. It is well known that for a complete monolayer on the surface of a mineral the contact angle 8 is determined only by the reagent1 and principally by the chain length of the hydrocarbon radical. Although for flotation the monolayer usually is regarded as being complete, early experiments of Wark and Cox&apos; showed that at very small concentrations of potassium ethyl xanthate the contact angle on galena changed in a continuous way from 0&apos; to the equilibrium value of 60". Further, Gaudin and Vincenta showed a similar continuity using heptylic acid and sphalerite. This shows that with probably incomplete monolayers, 0 varies with the degree of surface coverage. At the time these experiments were made it was impossible to measure the actual amount of surface coverage, especially since the decrease of the collector concentration in the liquor could be influenced by chemical side reactions. Through the use of the radioactive tracer method for the measurement of the amount of collector adsorbed on the surface of the mineral, Gaudin and Bloecher&apos; were able to determine accurately the actual surface coverage of dodecylamine acetate on quartz, but they did not measure any contact angles. It is believed that the relationship between the surface coverage and the contact angle is extremely important in flotation, especially as Gaudin and Bloecher showed that a 95 pct recovery is possible with a coverage of only 5 pct. Theoretical Considerations The work of adhesion W is the energy bound (in ergs per sq cm) when an interface is formed. It is determined by the difference of the free surface energies (surface tensions) of the respective phases 7j and yZ before contact and the interfacial free surface energy y, after contact. The definition of the contact angle permits the elimination of the unknown surface energy of the solid and hence the calculation of W from the surface tension of the liquid y and the contact angle 8: W = y (1 + COS0) [1] Consider a surface consisting of two components, identified as 2 and 3, 1 being the liquid. The amount of 2 in the composite surface is x, where 0 < x < 1. The respective contact angles with 1 and air are 8, and 8.. The total work of adhesion of such a surface is the sum of the values of the components multiplied by their respective areas. A formal relation can be written: Wm = x-W2+ (l-x)-W, [2] in which W, is the work of adhesion of the composite surface. Eq 1 can be introduced into Wt and Wa, but in the case of W, some discussion is needed. If the two components are segregated, each component forming an integral part of the composite surface there is no physical meaning for a contact angle 8m calculated from W,, by using eq 1. If, on the other hand, the area of each patch of the components is small in comparison with, say, the diameter of the bubble used in measuring, it could be expected that 0m would have a physical significance, because of the action of the surface tension of the liquid-gas interface tending to smooth out sharp corners. How small these patches would have to be is difficult to predict, but by using composite surfaces with microscopically

Jan 1, 1953

By S. R. B. Cooke, W. Philippoff, Donald E. Cadwell

THE importance of contact angles in flotation has long been recognized, but little has been done to get quantitative relationships between the surface coverage of the mineral by the reagent, the length of the hydrocarbon chain, and the contact angle. It is well known that for a complete monolayer on the surface of a mineral the contact angle 8 is determined only by the reagent1 and principally by the chain length of the hydrocarbon radical. Although for flotation the monolayer usually is regarded as being complete, early experiments of Wark and Cox&apos; showed that at very small concentrations of potassium ethyl xanthate the contact angle on galena changed in a continuous way from 0&apos; to the equilibrium value of 60". Further, Gaudin and Vincenta showed a similar continuity using heptylic acid and sphalerite. This shows that with probably incomplete monolayers, 0 varies with the degree of surface coverage. At the time these experiments were made it was impossible to measure the actual amount of surface coverage, especially since the decrease of the collector concentration in the liquor could be influenced by chemical side reactions. Through the use of the radioactive tracer method for the measurement of the amount of collector adsorbed on the surface of the mineral, Gaudin and Bloecher&apos; were able to determine accurately the actual surface coverage of dodecylamine acetate on quartz, but they did not measure any contact angles. It is believed that the relationship between the surface coverage and the contact angle is extremely important in flotation, especially as Gaudin and Bloecher showed that a 95 pct recovery is possible with a coverage of only 5 pct. Theoretical Considerations The work of adhesion W is the energy bound (in ergs per sq cm) when an interface is formed. It is determined by the difference of the free surface energies (surface tensions) of the respective phases 7j and yZ before contact and the interfacial free surface energy y, after contact. The definition of the contact angle permits the elimination of the unknown surface energy of the solid and hence the calculation of W from the surface tension of the liquid y and the contact angle 8: W = y (1 + COS0) [1] Consider a surface consisting of two components, identified as 2 and 3, 1 being the liquid. The amount of 2 in the composite surface is x, where 0 < x < 1. The respective contact angles with 1 and air are 8, and 8.. The total work of adhesion of such a surface is the sum of the values of the components multiplied by their respective areas. A formal relation can be written: Wm = x-W2+ (l-x)-W, [2] in which W, is the work of adhesion of the composite surface. Eq 1 can be introduced into Wt and Wa, but in the case of W, some discussion is needed. If the two components are segregated, each component forming an integral part of the composite surface there is no physical meaning for a contact angle 8m calculated from W,, by using eq 1. If, on the other hand, the area of each patch of the components is small in comparison with, say, the diameter of the bubble used in measuring, it could be expected that 0m would have a physical significance, because of the action of the surface tension of the liquid-gas interface tending to smooth out sharp corners. How small these patches would have to be is difficult to predict, but by using composite surfaces with microscopically

Jan 1, 1953

By K. P. Gupta

The Cb-rich boundary of the (Cb,Al) a phase field at 1250OC is near 41 pct Al. The Al atoms tend to occupy the C. N. 12 sites in this structure. A homologous (Ta,Al)a phase was identified. No a phase was found in the Mo-Al system at 1200°C. The first binary o-phase with a non-transition element as a major component was found1,2 in the Cb-Al system. The composition of this phase was reported2 as approximately 34 at. pct Al, based on X-ray diffraction patterns taken of alloys in the as-cast condition. Further study of the composition of this o-phase, therefore, appeared desirable. Since Si was previously found3,4 to occupy preferentially the lowest C.N. sites (I and IV) in the a phase, and preliminary resultsa indicated that Al may show similar ordering, one of the aims of the present work was to obtain more complete information on ordering in (Cb, Al) o. Among the binary systems of Al with Ti-, V-, and Cr-group elements, the Ti-Al, Zr-Al, V-Al, and Cr-Al systems are known to comprise no o-phase. In the present work a Ta-Al and a Mo-Al alloy were studied in an effort to find additional o phases with Al as a major component. EXPERIMENTAL PROCEDURES AND RESULTS An alloy with the intended composition of Ta + 40 at. pct Al was prepared by arc melting in He atmosphere. In both the as-cast condition and after annealing for 10 days at 1250°C and quenching in cold water this alloy consisted of two phases, as seen in the X-ray pattern and the microstructure. One of these phases was identified as the o-phase; the observed and calculated d-spacings are shown in Table I. The lattice parameters of this o-phase are a = 9.972 A, c = 5.214 A and c/a =0.5228, as determined from a Debye-Scherrer pattern using Fe K a radiation. The d-spacings for the unknown second phase are given in Table 11. The alloy contained approximately 25 pct of the unknown phase after annealing, as estimated on the basis of microscopic examination. A Mo-Al alloy was prepared by arc melting, with an intended Al-content of 35 at. pct. The alloy button was annealed for 7 days at 1200°C and water quenched. The X-ray pattern of the alloy in both the as-cast and the annealed state showed the reflections of Mo3Al (Cr30 type structure) and an unknown phase different from a. Six Cb-Al alloys were prepared in the composition range 30 to 50 pct Al. All alloys were arc melted in He atmosphere. After annealing for three days at 1175oC in evacuated silica capsules and quenching in water, the alloys with 30 to 40 pct Al contained three phases, namely the o-phase, Cb3Al (Cr3O-type structure) and an unknown phase. The alloys with more than 40 pct Al contained two phases, namely, what appeared metallographically, the o-phase and the same unknown phase. In the alloys containing less that 38 pct Al, the unknown phase was not present after annealing for 4 days at 1250°c,

Jan 1, 1962

By T. Vasilos, J. T. Smith

THE mechanism of pressure sintering, or hot pressing, for ceramic materials, has been investigated by several researchers.1-8 Plastic flow has been suggested as the rate-determining mech-anism1,2 while grain boundary sliding3,4 and fragmentation processess have been found controlling in other studies. Vasilos and Spriggs5,6 have reported that pressure sintering occurs by a diffusion-controlled mechanism. For the pressure sintering of metals, investigations with lead7 and with tin6 have not identified the operative mechanism during consolidation of these powders. This note reports the results of a pressure sintering study initiated to determine the mechanism controlling the densification of spherical copper powder. Temperatures of 300°, 400°, 500°, and 600°C at 2500, 5000, 7500, and 10,000 psi pressures were investigated. The copper powder for this study was obtained from Metals Disintegrating Co., Elizabeth, N.J. The minimum purity was reported to be 99.9 pct. The powder size was -325 mesh and a lineal analysis showed the average size to be less than 1 p. An alumina die body and punches were employed. Graphite spacers were placed between the copper powder and the punches before pressing. It was expected that the graphite would form carbon monoxide with any entrapped air and form a reducing atmosphere within the die cavity. This condition was generally realized during pressing although a minor amount of oxidation occurred at 500" and 600°C. The oxide particles were located randomly in the pressed samples and were not considered to influence the densification process. Calibration tests showed the temperature of the copper pellet to be about 20°C less than the die wall temperature, probably resulting from heat losses through the punches. This difference was compensated during the experimental pressing operations. The hot pressing equipment employed for this work has been described by Spriggs et a1.9 and was calibrated with a Baldwin-Lima-Hamilton load cell. Travel of the punches was monitored with a dial indicator showing increments of travel to 0.0005 in. Relative density was calculated at selected time intervals for a known copper weight, punch travel, and die diameter. The accuracy of this calculation was *1 pct. Average grain size after hot pressing was obtained by lineal analysis. Typical densification curves are presented in Fig. 1 and Fig. 2 where relative density is plotted vs log time as a function of applied pressure for the 300" and 600°C pressure sintering temperatures, respectively. The curves for 400" and 500°C were similar to those at 300°C and consequently are not shown. The curves at 300°C as well as 400" and 500°C do not show an end-point or limiting density for a particular applied pressure. At 600°C, a density in excess of 95 pct of theoretical has been reached such that further densification is extremely slow for the 5000, 7500, and 10,000 psi pressures. It is suggested that further densification at these pressure levels may be retarded or prevented by discontinuous grain growth, by entrapped gases, and by other microstructural limitations as described by Cob1e.10 The curve for 2500 psi hot pressing pressure is a straight line over the time interval although a slight change in slope may be occurring at the last time intervals. The plastic flow models,1,2 derived for hot pressing, predict the existence of an end-point (or limiting) density dependent on the yield point of the material at the temperature of interest. The yield stress of copper at a 0.005 strain level has been

Jan 1, 1965

By S. C. Sun

With the aid of emulsifiers, intense high-frequency sound waves are capable of emulsifying any collector in water. The data show also that ultrasonically emulsified collectors are more effective in floating minerals than the nonemulsified collectors. THE use of ultrasonics in forming emulsions is not new. As early as 1927 Wood and Loomis reported preparation of emulsions with ultrasonics. In 1935 Rschevkin and OstrawskyV escribed the use of great ultrasonic power in producing fine emulsions of various oils and paraffin in water. Recently Oyama and Tanaka3 employed ultra-emulsification to increase the effectiveness of sodium ethyl xanthate in flotation of chalcopyrite and galena. An emulsion is a two-phase system consisting of two incompletely miscible liquids, the one being dispersed as finite droplets In the other. The dispersed liquld is known as the internal or discontinuous phase, and the surrounding liquid is termed the external or continuous phase. There are two types of emulsions; one is oil-in-water (O/W) and the other water-in-oil (W/O). The word oil refers to the liquid other than water. Circumstances exist in which the emulsion type is not clearly defined, and the internal and external phases both contain portions of the opposite phase. This is said to be a dual emulsion. Among the many hypotheses, 5a, B proposed for the formation of emulsions, the Bancroft&apos;s adsorbed film or double interfacial tension theory is widely accepted. Bancroft 7, 8 deduced that in the process of emulsification the interfacial tension between oil and water is lowered by the formation of an emulsifying film, which contains the adsorbed molecules and/or ions from the emulsifying agent and the two liquids. This film has two interfacial tensions, one with the water and the other with the oil, which are not necessarily equal. The difference in interfacial tension between the two surfaces of the film is chiefly responsible for forming different types of emulsions. For example, if the interfacial tension between water and film is less than that between oil and film, the film will become convex on the water side, thereby tending to form an oil-in-water emulsion. On the other hand, if the interfacial tension between water and film is greater than that between oil and film, the film will become concave on the water side, thereby tending to make a water-in-oil emulsion. In line with this theory, emulsifying agents soluble in water have the tendency to form oil-in-water emulsions, while those soluble in oil form emulsions of the reverse type. Apparatus and Experimental Procedure: The ultrasonic apparatus shown in Fig. 1 consisted of a hypersonic generator (A), Brush Development Co. model Bu-204; a hypersonic transducer bowl (B) whose resonant frequency is 400 kc per sec; and a round-bottomed glass tube (C) of 2.2 cm ID and 21 cm in length. The acoustical output power of the hypersonic transducer bowl was standardized with a Hewlett Packard vacuum tube voltmeter, model 41 0B, across the hypersonic generator output. The glass tube, containing the materials to be emulsified, was placed 1 cm above the central surface of the transducer bowl, which was filled with water as shown in Fig. 2. Ultrasonic emulsification was performed in three steps, although a one-step method has been used: 1) emulsifying the predetermined amounts of col-

Jan 1, 1956

By R. F. Sheldon

The discovery of the Carlin deposit was the result of discriminating geologic research and prospecting devoted to the objective of finding a gold deposit that could be mined by open pit methods. By the late 1950s, Newmont Mining Corp. was becoming increasingly concerned about the trend of rapidly rising underground mining costs unless bulk mining methods could be applied. The desirability of finding an open-pittable gold deposit was apparent. The attention of Newmont geologists was directed to Nevada by the publication of two papers: "Paleozoic rocks in North-central Nevada" (1958) and "Alinements of Mining Districts in North-central Nevada" (1960), both authored or co-authored by Ralph J. Roberts of the United States Geological Survey. John Livermore, geologist of Newmont Exploration Ltd., attended a talk given by Roberts in Ely, Nevada in the summer of 1961. These papers and the address by Roberts gave details concerning the Roberts Mountain overthrust, a 483 km (300-mile) long, shallowdipping fault which pushed clastic and volcanic rocks of early and middle Paleozoic age eastward over younger marine formations. Subsequent uplift and doming with consequent erosion had locally removed the upper plate strata exposing windows of lower plate carbonate rocks. Roberts noted that the principal mineral deposits of the region, including gold, were associated with these windows which exhibited a preferred alinement. In the summer and fall of 1961 Newmont&apos;s exploration geologists John Livermore and J. Alan Coope began a systematic examination of gold occurrences associated with these windows, aided by further discussion with geologists of the US Geological Survey. Attention was directed to the Lynn and Carlin windows, particularly to those formations lying immediately above and below the Roberts Mountain fault. It was appreciated at the time that many of the gold occurrences in the region were unusual in that no colours were obtained even when panning high grade samples. A large number of rock samples were collected and analysed using fire assaying procedures, and background values for gold were established. This systematic rock sampling resulted in the identification of a distinct area of anomalous gold values, and a block of claims was staked in late October, 1961. These claims, plus an adjoining optioned 32.4 ha (80 acres) of ground, cover the main area of the present Carlin gold mine. Prior to snowfall that winter, one of the bulldozed assessment pits required to establish a claim&apos;s discovery exposed 24 m (80 ft) of mineralization assaying 0.007 kg/t (0.22 oz per st) gold. In the spring of 1962 a program of trenching, sampling, and geological mapping followed by rotary drilling was underway. Other properties in the area were acquired. The generally undistinguished nature of the dolomitic siltstones and silty dolomitic limestones hosting the micron-sized gold particles, coupled with the lack of visually associated guide minerals, made identification of the gold bearing areas very difficult. The entire drill column had to be assayed to ensure that values were not overlooked, as very often sections that might be assumed to be waste turned out to be high grade. On September 10, 1962 a high grade intersection of 24 m (80 ft) assaying over 0.03 kg/t (1 oz per st) gold was encountered in the third hole drilled. An expanded program of both rotary and diamond drilling led to the further delineation of the ore body. By December 1963, the exploration program had established an initial reserve of 10 Mt (11 million st) grading 0.01 kg/t (0.32 oz per st) gold. A 1.8 kt/d (2,000 stpd) processing plant was constructed and the first gold bullion was poured in May, 1965, just two years and eight months after the discovery hole was drilled. REFERENCES Roberts, R.J., Holz, P.E., Gilluly, J., and Ferguson, H.G., 1958, "Paleozoic Rocks in North-central Nevada," Bulletin American Association of Petroleum Geologists, Vol. 42, No. 12. Roberts, R.J., 1960, "Alinements of Mining Districts in North-central Nevada," Professional Paper 400-B, US Geological Survey, Article 9.

Jan 1, 1985

By W. A. Hockings, M. E. Volin, A. L. Mular

Batch grinding tests at short times were made in a laboratory rod mill with 10 x 14 mesh quartzite in corn syrup-water mixtures of varying viscosity. The weight fraction broken and size modulus were found to be independent of viscosity up to 20 cp, but at higher viscosities breakage of the feed decreased while the size modulus increased. The mechanisms of the effect of viscosity are discussed on the basis of particle dynamics. The effect of viscosity of the suspending medium on grinding has not been accorded much attention, although both wet and dry grinding are used in bene-ficiation processes and the viscosities of water and air differ greatly. schweyerl investigated the rates of grinding of quartzite in a pebble mill with air, water and glycerol as the suspending media and found the rate in terms of new surface developed per thousand revolutions of the mill to be constant and dependent on viscosity up to 20,000 rev, but to decrease and become independent of viscosity for longer grinding times. Based on considerations of the drag forces exerted on suspended particles and on the grinding media under turbulent and laminar flow conditions, viscosity can be expected to inhibit the rate of grinding in a given system as it changes the flow conditions from turbulent to laminar. The objective of this study was to determine the effect of viscosity of the suspending fluid in the batch grinding of a homogeneous feed of uniform size for short residence times, a region of more practical interest than the long times investigated by Schweyer. In actual grinding operations, the viscosity of the fluid does not change, but the consistency (apparent viscosity) of the pulp increases with additions of fines. In this study the consistency of the pulp was not measured because it was thought that the grinding times were too short to alter the apparent viscosity appreciably.* *Minus 200 mesh quartz at 65% solids has an apparent viscosity of about 25 cp as measured by a simple consistometer. Personal communication from D. F. Kelsall to A. L. Mular. For the purposes of this study, the effect of viscosity on grinding can be shown sufficiently well on the basis of the cumulative weight fraction finer than the feed size at any time, and the size modulus, ku, of the finer than feed sizes. The parameter, ku, is obtained from a form of the Gaudin-Schuhmann equation. METHOD AND MATERIAL The grinding tests were accomplished in a laboratory rod mill 10-1/2 in. long and 8 in. bore with a 20-lb rod charge consisting of two 1-in., eight 3/4-in., eight 1/2-in., and eight 1/4-in. diam rods. The mill speed was 43.2 rpm. Charges of 400 g 10 x 14 mesh Wisconsin quartzite** were ground for times of 60, **Courtesy of Minnesota Mining and Mfg. Co. 120, 180 and 240 sec in 500 cc of fluid made up of corn syrup and water in measured proportions. The temperature of the pulp was measured immediately upon completion of grinding, and the size distribution of the quartzite was determined by a wash-wet-dry screening technique. Corn syrup was chosen because of its high viscosity and ideal viscous behavior, and also because its density is not greatly different from that of water. The viscosity of each fluid mixture was measured with an Ostwald viscometer at 25 C. and a correction was made for the temperature of the pulp according to tabulated values for sucrose solutions. The density differences were so small that they probably did not significantly affect breakage. RESULTS AND DISCUSSION The conditions of the grinding tests, computed viscosities, weight fractions finer than the feed size and values of a and ku are listed in Table I. The values of a and ku were taken from the linear portions of the log-log plots of cumulative weight fraction finer vs size for the various grinding times. The plots for tests in fluids of average viscosity 8.6 cp are shown in Fig. 1. In general all of the sets of curves were linear throughout most of the size

Jan 1, 1965