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By Harold L. Hinds

The Homestake Ledge or Lead was discovered by Fred and Moses Manuel on April 9, 1876. They recovered a small amount of gold from the quartz outcrop, but, unfortunately, they were prospectors not hardrock miners. Their claim was sold to a group of experienced California mining men in 1877. These mining men incorporated their holdings as the Homestake Mining Company. This was the beginning of one of the greater gold mining enterprises of the Western World. Metallurgical operations progressed over the years from an eighty- stamp grinding circuit using amalgamation for recovery to the more complex circuit of today. The Homestake Mine, today, is an underground mine with the deepest winze reaching the 8,000-foot level. The ore is hoisted to the surface by two primary shafts, the Ross Shaft and the Yates Shaft. See Figures 1 and 2. It is crushed in three-stage crushing plants located in the headframes. From here, it is trammed to the mill fine- ore bins by electric locomotives. The Lead grinding plant milling circuit, known as the South Mill, receives ore from the crushing plant at minus 112 inch (Figure 3). This material is dumped into overhead fine-ore bins from five- ton rail cars. The fine-ore bins have a live capacity of about 3,700 tons. The South Mill bins can also be fed by a conveyor system which reclaims ore from an 80,000-ton capacity stockpile. This stockpile is built up from peak mining production periods and available surface low grade material. It is then reclaimed during low mine production periods. The grinding circuit at the South Mill consists of four rod mills in open circuit followed by four ball mills in closed circuit. Three of the rod mills are 6-foot by 12-foot Marcy's. The other is

Jan 1, 1983

By J. J. Bowman, E. H. Dix

A lack of experimental data illustrating the effect of composition, particularly in respect to impurities, on the mechanical properties and corrosion resistance of aluminum-alloy die castings induced the authors and their associates to undertake a limited study of these relations. A number of commercial alloys and several experimental variations of a commercial alloy were used for the investigation. Mechanical property, growth, steam, paraffin, salt spray and atmospheric exposure tests were employed. This paper deals with the more accelerated tests and the results they have produced. It is concluded that a high-silicon alloy with all impurities except iron strictly limited to small amounts will develop an excellent resistance to corrosion and retain satisfactory mechanical properties and casting characteristics. As a direct result of this investigation an alloy of this character with superior corrosion resistance is now available commercially. In general, copper increases the strength and decreases the elongation and corrosion resistance. Tin reduces the mechanical properties and the resistance to corrosion. Iron reduces the elongation and, if excessively high, may adversely affect the tensile strength. Even excessively high iron contents do not affect the corrosion resistance, which is fortunate for the die caster as it is this element that is the most difficult to control. Nickel and zinc in limited amounts do not seem to affect the properties or corrosion resistance of at least the high-silicon alloy. Growth tests have confirmed the previous common belief that dimensional changes under either dry or wet conditions at 100" C. are too small to be of practical importance. Introduction The technical literature contains numerous papers describing die castings, their production, compositions and uses, but nearly all of these

Jan 1, 1935

By J. J. Bowman, E. H. Dix

A lack of experimental data illustrating the effect of composition, particularly in respect to impurities, on the mechanical properties and corrosion resistance of aluminum-alloy die castings induced the authors and their associates to undertake a limited study of these relations. A number of commercial alloys and several experimental variations of a commercial alloy were used for the investigation. Mechanical property, growth, steam, paraffin, salt spray and atmospheric exposure tests were employed. This paper deals with the more accelerated tests and the results they have produced. It is concluded that a high-silicon alloy with all impurities except iron strictly limited to small amounts will develop an excellent resistance to corrosion and retain satisfactory mechanical properties and casting characteristics. As a direct result of this investigation an alloy of this character with superior corrosion resistance is now available commercially. In general, copper increases the strength and decreases the elongation and corrosion resistance. Tin reduces the mechanical properties and the resistance to corrosion. Iron reduces the elongation and, if excessively high, may adversely affect the tensile strength. Even excessively high iron contents do not affect the corrosion resistance, which is fortunate for the die caster as it is this element that is the most difficult to control. Nickel and zinc in limited amounts do not seem to affect the properties or corrosion resistance of at least the high-silicon alloy. Growth tests have confirmed the previous common belief that dimensional changes under either dry or wet conditions at 100" C. are too small to be of practical importance. Introduction The technical literature contains numerous papers describing die castings, their production, compositions and uses, but nearly all of these

Jan 1, 1935

By N. K. Chen, R. Maddin

THE textures of straight-rolled and of cross-rolled molybdenum were first determined with the aid of pole figures by Custers and Riemersma.' These authors have shown that for straight-rolling, the main texture was (100) [0111 with a considerable spread about the rolling direction. After cross-rolling a second texture was obtained in which there was a [111] axis perpendicular to the rolling plane, possessing a rotary symmetry. Recently Semchy-shen and Timmons2 in their study of preferred orientation of arc-cast molybdenum sheet obtained similar pole figures. In these two investigations, polycrystalline materials were used. In the main, the textures of molybdenum in these cases are qualitatively consistent with rolling textures of other body-centered cubic metals, such as iron and Fe-Si alloys." In the present investigation, single crystals of molybdenum were deformed by rolling with respect to specific crystallographic planes and directions. Since the deformation textures of polycrystalline aggregates have been related intimately to the behavior of individual grains,4 a study of possible correlations of final textures with respect to the initial orientations of the single crystals might conceivably lead to a better understanding of the textures. Annealing treatments were carried out after deformation in order to study the recrystallization characteristics as well as the recrystallization texture. Rolling of Single Crystals Single crystals of molybdenum (about 1/8 in. in diarn x 1-in. long), grown by the method previously described,5 were cold-rolled without intermediate anneals. Except for specimens MR-1 and MR-2, which were rolled at random in the preliminary test in order to find a proper rate of reduction, all other specimens were carefully documented as to their respective orientation before deformation by means of X-ray Laue back-reflection methods. A stereo-graphic projection was constructed from which it was possible to determine a particular plane and direction to be considered for rolling. Parallel flat surfaces were then polished metallographically with respect to a reference scratch on the specimen which was mounted in sealing wax. These flat surfaces contained the plane chosen for rolling. After etching, a Laue back-reflection photogram was again made of one of the flat surfaces to determine the exact plane of rolling. The initial orientations of all the specimens (specified by two elements for each crystal, direction of rolling and the pole of the rolling plane) are summarized in Fig. 1. The specimens were mounted in plasticene between two hardened Si-Fe plates. The sandwich was then rolled down, keeping the direction constant in the case of straight-rolling. In cross-rolling (MR-10, MR-11, and MR-12) the sandwich was rotated 90" after each pass so that every first and third pass contained the same rolling direction. Specimens MR-14, MR-15, and MR-16 were compression-rolled following the manner of Barrett." In these cases the direction of the sandwich through the rolls was changed by 3" to 5" for each pass until the specimens were rolled to the desired reduction in thickness. It was found that if extreme care was exercised in rolling, i. e., the amount of deformation per pass was extremely small, the specimens could be rolled to a large reduction in thickness. The rate of reduction used, with a single exception of MR-1. was generally 0.001 in. per 10 passes. Thus, it took about 800 passes to reduce a specimen to a final reduction in thickness of 87 to 98 pct. The results of rolling are shown in Table I. Cold-Rolling Textures The final orientations were determined by the conventional Laue transmission method," using molybdenum radiation, with or without a zirconium filter. Pole figures were plotted from (1101 and (200) reflections in which three degrees of intensity— heavy, medium, and light—were determined visually. Three main types of textures have been observed from the deformed single crystals. These are: 1—a

Jan 1, 1954

By O. Mellgren, A. M. Gaudin, P. L. De Bruyn

The adsorption density of ethyl xanthate on pyrite was determined as a function of xanthate concentration. Surface preparation of the mineral appears to have asafunctionsome effect on the subsequent adsorption process, A monolayer of xanthate on the surface is exceeded only in presence of oxygen. The effect of OH- , HS- (and x and CN- S=)and on the amount of xanthate adsorbed was investigated. Competition between OH- and X- (xanthate) ions for specific adsorption sites is indicated over a wide pH range. IN the flotation of sulfide ores, xanthates are most commonly used to prepare the surface of the mineral to be floated so that attachment to air takes place. The quantity of agent required to make the mineral hydrophobic is usually very small, of the order of 0.1 to 0.25 lb per ton of mineral. Details of the mechanism of pyrite collection are for the most part unsettled. Adsorption of collector has long been believed to involve an ion exchange mechanism as demonstrated for galena' and for chalcocite.2 In the work on chal-cocite it was also demonstrated that a film of xanthate radicals unleachable in solvents that dissolve alkali xanthates, copper xanthate, or dixanthogen was formed at the surface of the mineral. The unleachable product increased with increasing addition of xanthate up to a maximum corresponding to an oriented monolayer of xanthate radicals. Pyrite is extremely floatable with xanthate if its surface is fresh.9 ut the floatability decreases rapidly as oxide coatings increase in abundance. Pyrite shows zero contact angle when in contact with ethyl xanthate solution at pH higher than about 10.5;4 at neutrality, a contact angle of 60" is obtained at a reagent concentration of 25 mg per liter. Alkali sulfides and cyanides are pyrite depressants. In this study of pyrite collection the writers have sought to relate measured xanthate adsorption to the method used in preparing pyrite, to the presence or absence of oxygen, to concentration of hydroxyl, hydrosulfide, sulfide, and cyanide ions. The principal experimental tool has been radioanalysis," " using xanthatcx marked with sulfur 35. Experimental Materials Pyrite: Unlike most sulfides, pyrite is a poly-sulfide. The structure given by Bragg7 resembles that of sodium chloride, the iron atoms corresponding to the position of sodium and pairs of sulfur atoms corresponding to the position of chlorine. The edge of the unit cell in pyrite is 5.40 A and in halite 5.63 A. The S-S distance in pyrite is 2.10 A; the Fe-S distance, 3.50 A: and the Fe-Fe distance, 3.82 A. Natural pyrite from Park City, Utah, was used in this investigation. Pyrite 1 was obtained by hand picking pure crystals. Pyrite 2 and Pyrite 3 were obtained from finer textured crystalline material containing inclusions of silicates. The same cleaning technique was utilized for the preparation of Pyrite 2 and Pyrite 3, whereas a different cleaning technique was used for Pyrite 1. Pyrite 1 was prepared as follows: The crystals were ground in a porcelain ball mill and the 200/400 mesh fraction was separated by wet screening with distilled water, followed by washing for 1 hr with deoxygenated distilled water acidified with sulfuric acid to pH 1.5. The acid was removed by rinsing with deoxygenated distilled water on a filter until a pH of 6.0 was reached in the effluent. This filtration was carried out under nitrogen. The sample was then dried in a desiccator under nitrogen. The period of time for which this pyrite sample was in contact with water containing oxygen was about 4 hr. The specific surface as determined by the BET gas adsorption method was 582 cm2 per g. Final material assayed 53.12 pct sulfur and 46.5 pct iron (theoretical, for FeS,: S, 53.45 pct; Fe, 46.55 pct). After crushing, Pyrite 2 and Pyrite 3 were washed with 1 M HCl. rinsed, and fed to a laboratory shakinq table to remove the small amount of silicates. The concentrate obtained was ground in a laboratory steel ball mill. The 200/400 mesh fraction was separated by classification in a Richards hindered settling tube. This fraction was then given a final wash with 0.1 M HCl and deoxygenated water was filtered through the sample. The final effluent showed a conductivity equivalent to that of a solution having a salt concentration of 0.3 ppm. Aqueous hydrogen sulfide solution was then added to the sampln (about 100 ml saturated H,S solution to about 1000 g pyrite under a few hundred milliliters of water) which was stored wet under nitrogen. The sample stored in this manner showed no indication of formation of iron oxides, whereas iron oxides appeared

Jan 1, 1957

By William Sharp

Discovery of new ore in the Eureka district, Nevada, as a result of bold and persistent exploration based on a geologic interpretation of structure has recently aroused wide comment in mining circles. It may therefore be of interest to the profession to have a summary of the historical background and an account of the recent program of development. The mines of Eureka, discovered in the late 1860's, were the first important silver-lead mines in the United States. They have a production record of more than fifty-one million dollars.' After the ore bodies were apparently bottomed in the 1880's, repeated attempts to find new ore were unsuccessful until 1940, when a diamond-drill hole cut a 40-ft width of sulphide ore 1409 ft below the 841-ft level of the Locan shaft. The next hole cut 30 ft, of ore and three additional holes drilled in 1943 and 1944 showed the ore body to be continuous, Shaft sinking to reach and open up the ore body has been in progress since 1945. Geology Stratigraphy The ore in the Eureka district occurs in a series of Cambrian sediments which is exposed through a thickness of over 6000 ft. The stratigraphic column is as follows:2 Thickness. Ft Ordovician : Pogonip limestone (upper part). Thin bedded limestone with some chert. Upper Cambrian: Pogonip limestone (lower part). Thin-bedded limestone (with shaly limestone and chert).... 425 + Dunderberg shale. Shale (clay and calcareous shale) and thin-bedded limestone............. 34°+ Hamburg dolomite. Dolomite and limestone.................... 900+ Middle Cambrian: Secret Canyon shale. Shale and thin-bedded limestone........ 1,035 Geddes limestone. Carbonaceous, flaggy limestone with some shale partings................ 335 Middle (?) and LoweR Cambrian: Eldorado dolomite. Dolomite and limestone.................... 2,000 Lower Cambrian: Prospect Mountain quartzite. Quartzite with occasional intercalated conglomerate and shale 1,660+ The Prospect Mountain quartzite has been subdivided into two formations: Upper part, Pioche shale. Shale, quartzite with some intercalated limestone (Lower Cambrian fossils)-200 ft. Lower part, Prospect Mountain quartzite proper- 1,460Sft. Total thickness................ 6,695 + Much the most productive of these formations has been the Eldorado dolomite, which yielded more than $42,000,000 at Ruby Hill and an additional amount

Jan 1, 1949

By William Sharp

Discovery of new ore in the Eureka district, Nevada, as a result of bold and persistent exploration based on a geologic interpretation of structure has recently aroused wide comment in mining circles. It may therefore be of interest to the profession to have a summary of the historical background and an account of the recent program of development. The mines of Eureka, discovered in the late 1860's, were the first important silver-lead mines in the United States. They have a production record of more than fifty-one million dollars.' After the ore bodies were apparently bottomed in the 1880's, repeated attempts to find new ore were unsuccessful until 1940, when a diamond-drill hole cut a 40-ft width of sulphide ore 1409 ft below the 841-ft level of the Locan shaft. The next hole cut 30 ft, of ore and three additional holes drilled in 1943 and 1944 showed the ore body to be continuous, Shaft sinking to reach and open up the ore body has been in progress since 1945. Geology Stratigraphy The ore in the Eureka district occurs in a series of Cambrian sediments which is exposed through a thickness of over 6000 ft. The stratigraphic column is as follows:2 Thickness. Ft Ordovician : Pogonip limestone (upper part). Thin bedded limestone with some chert. Upper Cambrian: Pogonip limestone (lower part). Thin-bedded limestone (with shaly limestone and chert).... 425 + Dunderberg shale. Shale (clay and calcareous shale) and thin-bedded limestone............. 34°+ Hamburg dolomite. Dolomite and limestone.................... 900+ Middle Cambrian: Secret Canyon shale. Shale and thin-bedded limestone........ 1,035 Geddes limestone. Carbonaceous, flaggy limestone with some shale partings................ 335 Middle (?) and LoweR Cambrian: Eldorado dolomite. Dolomite and limestone.................... 2,000 Lower Cambrian: Prospect Mountain quartzite. Quartzite with occasional intercalated conglomerate and shale 1,660+ The Prospect Mountain quartzite has been subdivided into two formations: Upper part, Pioche shale. Shale, quartzite with some intercalated limestone (Lower Cambrian fossils)-200 ft. Lower part, Prospect Mountain quartzite proper- 1,460Sft. Total thickness................ 6,695 + Much the most productive of these formations has been the Eldorado dolomite, which yielded more than $42,000,000 at Ruby Hill and an additional amount

Jan 1, 1949

By H. H. Dievendorff, F. W. Hertel

The method of drilling deep wells into the earth for the recovery of oil and gas is beset with many hazards. This is especially true in the Ventura Avenue field, which has the distinction of being the hardest field in California in which to complete a deep well. The hard, shifting and squeezing formations must be penetrated to great depths in the face of tremendous gas pressures. This field presents problems that keep the operators abreast with all of the latest developments in oil-field tools and machinery and in oil-well drilling practices. Equipment must be strong, and adapted to deep-well drilling and the handling of long heavy strings of casing. High-pressure sands require the utrnost care and attention of the operators and no chances can be taken, since a serious blowout may cause the loss of a well that has cost months of labor and expense. Equipment must meet these requirements or be discarded. Although the deepest wells in the world are not in this field, nor hav:. the longest strings of casing been set, nevertheless, the consistency with which deep wells are drilled and long strings of casing are set places the Ventura Avenue field foremost, in this respect, among the oil fields of the world. The V'entura Avenue field dors claim the deepest commercial oil-producing well in the world, in the Shell Co. of California's "Edison" No. 18. This well was drilled 7015 ft. and came in flowing 3280 bhl. of oil per day. This field also claims the deepest average depth of producing wells in that its Ill producing wells average 5676 ft. in depth. Of these 111 producing wells, 50 arc 6000 ft. or deeper, and 16 are 6500 ft. or deeper. Also, of the 111 producing wells 100 arc flowing, and 11 arc pumping wells. This paper is intended to set forth the methods used in the drilling of deep wells with rotary tools and the handling of long heavy strings of casing in the Ventura Avenue field.

Jan 1, 1928

By Harlan A. Walker

Rock-drill steel has an important bearing on costs in many mining operations, both directly and indirectly. Direct factors include such items as shop expense, steel consumed per ton of ore produced, cost of distribution and the dust hazard. The latter, although no specific amount may be assigned to it, is an ever-present problem, and is receiving increased attention as the science of mining progresses. Indirectly drill-steel performance affects consumption of compressed air, maintenance of drills and drilling speed. The latter, in turn, increases or retards the tempo of mining and development. These factors, while not all inclusive, are preponderant in their importance. Thus it is evident that in an extensive operation drill-steel expense may run to many thousands of dollars and that thoughtful research leading toward more efficient practice is warranted. Experimental Work During the late spring of 1939, experiments were undertaken at Homestake in reducing changes in drill-steel gauge from ? in. to 1/16 in. In drifts and crosscut headings mounted machines were set up and holes were drilled with ?-in. bit-gauge changes and other holes a few inches

Jan 1, 1940

By Harlan A. Walker

Rock-drill steel has an important bearing on costs in many mining operations, both directly and indirectly. Direct factors include such items as shop expense, steel consumed per ton of ore produced, cost of distribution and the dust hazard. The latter, although no specific amount may be assigned to it, is an ever-present problem, and is receiving increased attention as the science of mining progresses. Indirectly drill-steel performance affects consumption of compressed air, maintenance of drills and drilling speed. The latter, in turn, increases or retards the tempo of mining and development. These factors, while not all inclusive, are preponderant in their importance. Thus it is evident that in an extensive operation drill-steel expense may run to many thousands of dollars and that thoughtful research leading toward more efficient practice is warranted. Experimental Work During the late spring of 1939, experiments were undertaken at Homestake in reducing changes in drill-steel gauge from ? in. to 1/16 in. In drifts and crosscut headings mounted machines were set up and holes were drilled with ?-in. bit-gauge changes and other holes a few inches

Jan 1, 1940

By Thomas A. Simpson, Russell A. Walker

Hydrogeological techniques were used to solve problems of slope stability in open-pit mines of the Eufaula bauxite district, Ala. Geologic and hydrologic data were evaluated and used to design a system of dewatering wells to enable the operators to mine bauxite more efficiently and economically. Walls of open-pit mines in the district were subsequently stabilized by the operation of the dewatering system. Three open- pit mines, each at varying stages of the mining process, of the A.P. Green Refractories Co., were used to develop a sequential series of guidelines that indicate how to effectively remove ground water from the formations surrounding the ore bodies in the district. The use of sound engineering principles in well design, in combination with the correct interpretation of the pit hydrology provided the basis for solutions of the slope-stabilization problem and aided in the economical removal of bauxite from mines of the district.

Jan 1, 1976

By Robert D. Pehlke, Kazuhisa Okajima

The activity of zinc in dilute liquid lead alloys containing small additions of silver and gold has been measured using a multielectrode galvanic cell with a fused chloride salt electrolyte. The range of temperatures studied in the Pb-Zn-Ag system was 550" to 670°C and in the Pb-Zn-Au system was 680" to 800°C. The interaction parameters between zinc and the precious metals in the respective temperature ranges are ThE lead-rich corners of the Pb-Zn-Ag and Pb-Zn-Au ternary systems are of considerable industrial importance. The use of zinc additions for the desilvering The results of this investigation have Provided a senzi-quantitative determination of the liquidus phase boundaries in the lead-rich corner of these ternary diagrams. of liquid lead either by the Parkes process or by the more recent Williams continuous process is an important refining phase of lead production.1 Several in-ve~ti~ations~-~ have been carried out on the Pb-Zn-Ag system with the hope of improving the efficiency of refining lead in this manner. The addition of zinc also provides a means for separating gold from lead. Since gold is eliminated more easily than silver, a two-stage removal of gold and silver is possible.8'7 The thermodynamic interactions between zinc and these precious metals in dilute solution in liquid lead

Jan 1, 1968

By John Wulff, J. H. Hollomon

THE opinion has been widely held that the corrosion of alpha brass occurs by the selective solution of zinc. As late as 1939, Fink1 and Evans2 suggested that in the initial stage of the corrosion the selective solution of zinc produces copper-rich areas, which subsequently act as cathodes that facilitate the deposition of copper. Previously Abrams3 had shown that most of the copper found on corroded brass was redeposited and not residual, although he did not consider the nature of the initiation of the corrosion process. Enough data exist to indicate that any metal surface is sufficiently heterogeneous to provide the anodes and cathodes necessary for the initiation of corrosion.4,5 Thus, for alpha brass we need postulate not an initial selective solution of zinc, but only the existence of local differences in electrochemical potential. The heterogeneity responsible for potential differences may arise from oxide and other films as well as from alloy concentration gradients. Even though selective corrosion may be possible in some alloy systems, previous data on alpha brass as well as the experimental work reported in this paper do not require this supposition. Bengough and May,6 in a discussion of Abrams' paper, first suggested the addition of small amounts of arsenic (0.03 per cent) to alpha brass to prevent the redeposition of copper (dezincification). This suggestion was later substantiated by Nixon.7 In their studies of the inhibiting influence of arsenic, Evans and Fink were led to the selective-solution hypothesis in order to explain the initial corrosion of such alloys. They believed that an arsenic film covered anode areas and prevented the formation of copper-rich spots capable of acting as cathodes for the deposition of copper. They did not consider, however, the mechanism by which the arsenical film was formed. Bengough and May,8 in another publication, suggested that the commonly found gray or black arsenical film may act to: (I) carry oxygen to the brass surface, (2) increase the discharge potential of copper on brass, (3) precipitate cuprous chloride from colloidal suspension in chloride solutions. Masing9 assumed that the film found upon arsenical brass was metallic arsenic. His measurements of hydrogen overvoltage of bulk arsenic led him to believe that the inhibition of dezincification occurs because the overvoltage of a brass surface is lowered by the arsenic film. He reasoned that this film would permit the more rapid reduction of hydrogen at the cathode, which would prevent the redeposition of copper. In a recent paper,10 we have pointed out that the film formed during the corrosion of arsenical brass and copper in stagnant solutions is essentially arsenious oxide (As203),

Jan 1, 1942

By William E. Ford, Edward Salisbury Dana

Examination in the Wet Way Examination by Means of the Blowpipe 479. The complete investigation of the chemical composition of a .mineral includes, first, the identification of the elements present by qualitative analysis, and, second, the determination of the relative amounts of each by quantitative analysis, from which last the formula can be calculated. Both processes carried out in full call for the equipment of a chemical laboratory. An approximate qualitative analysis, however, can, in many cases, be made quickly and simply with .few conveniences. The methods employed involve either (a) the use of acids or other reagents " in the wet way," or (b) the use

Jan 1, 1922

By G. T. Davis, C. C. Mattax, M. O. Denekas

The effects of crude oil cornponents on the wellabil-ities of sandstone and limestone were investigated. Fractions containing cornponents differing in molecular weight and molecular structure were obtained from crude oils by distillation, extration and chromatography. Individual fractions were then tested for their effects on rock wettability. Tests indicate that sundstone wetta-bility may he changed by a complex variety of surfactants varying both in molecular structure and molecular weight. Limestone appears to be particularly sensitive to basic, nitrogenous surfactants. INTRODUCTION Investigations in recent years have shown that petroleum reservoir rock wettability can exert a significant influence on the efficiency with which oil can be produced by water flooding. While most reservoirs are presumably water-wet, they niay range in their degree of water-wettability from near-neutral to strongly water-wet.'" Reservoir wettabilities other than strongly water-wet are likely to be induced by adsorption of surface-active components froni the crude oil on the pore walls of reservoir rock.:' Little is known, however, about the nature of the surface-active materials which are likely to be adsorbed by the reservoir rock. Due to the complexity of crude oils. attempts made in the past90 isolate these surface-active components have met with only limited success. It is probable that many different types of surface-active materials arc indigenous to crude oils and that many of these may be adsorbed to varying degrees by reservoir rock. This was cxolored in the studies discussed in this paper. The over-all objective in these studies is to ascertain whether the wettability of a given reservoir can be determined by examining the surfactant content of the reservoir crude. To this end, crude oils were examined to determine the variability of indigeneous surfactants with regard to chemical type and molecular weight. Crude oils were separated by distillation into fractions differing principally in molecular weight, by chroma-tography into fractions containing compounds differing in polarity, and by solvent extraction into nitrogenous and non-nitrogenous fractions. Individual fractions were then tested for their effects on the wettabilities of sandstone or limestone rock samples. EXPERIMENTAL PROCEDURES Fractionation of the Crude Oils Samples of Miocene, Eocene and Jurassic crudes were distilled at temperatures not exceeding 200°C. The final stages of distillation were completed in a molecular still at pressures down to three microns of mercury. Fifteen to 30 fractions were obtained from each crude oil. These cuts were sufficiently broad that separation can be considered to have been effected principally on the basis of the molecular weights of the constituents of the crude oil. A considerable portion (20 to 40 per cent) of the crudes would not distill under these conditions. The residues were recovered and tested with the other fractions. Fractions differing in polarity were separated from a crude of Pennsylvanian age and an extracted sample of Miocene oil by chromatography, using a solid adsorbent. Since surfactants are, for the most part, polar compounds, chromatography should separate many of the surfactants from the crude oil. Such a separation should provide fractions containing compounds differing in molecular structure. Nitrogeneous compounds were extracted from Miocene crude oil with a solution of sulfuric acid in meth-anol. The residual oil was further processed by chonia-tography. Each of the fractions obtained by thesc procedures was dissolved in a non-polar solvent (xylene) and diluted to its original concentration in the crude oil. No attempt was made to maintain an anaerobic atmosphere above the samples while they were being dissolved. These solutions of the fractions were then tested for their effects on the wettability of sandstone and limcstone as discussed in the next section. Measurement of the Effects of Crude Oil Fractions on Rock Wettability No entirely satisfactory method for measuring rock wettability has yet been developed. All methods used are empirical. The imbibition test was used in these studies. This test is based on the tendency of a rock to imbibe the wetting phase spontaneously. For example, if a strongly water-wet rock is first saturated with oil and then placed in water, the water will quickly invade the rock by capillarity and much of the oil will be displaced. If the rock is slightly water-wet, water irnbibition will proceed more slowly and, in many instances, considerably less oil will be displaced. A water-saturated, oil-wet rock will imbibe oil. The initial rate with which water (or oil) imbibition takes place indicates, qualitatively, the degree of water (or oil) wettability of the rock.

By Gordon H. Geiger, John M. Svoboda

One mechanism of metal penetration into mold aggregates by cast steels is vapor state mass transport. In order to further understand and quantify this mechanism, the steady-state diffusion of metallic vapors was studied at 1250" to 1600°C in controlled oxygen pressure atmospheres by measuring the weight loss from a metal bath whose vapors were allowed to diffuse through a porous aggregate compact held at constant temperature. Mass transport rates substantially greater than those predicted from the assumption that the vaporizing species was the elemental metal vapor were observed. Vaporization rates were found to increase with an increase in the oxygen partial pressure in the gas atmosphere with maximum vaporization occurring at oxygen partial pressures just below those in equilibrium with a liquid oxide layer at the given temperature. When the liquid oxide layer was present, no vaporization was observed. Metal carbonyls were ruled out as the vapor species involved because of their thermodynamic properties. The species with the enhanced volatility were deduced to be gaseous metal-oxygen molecules, probably the polynuclear oxides (FeO)2 and (Mn0)2. Diffusion followed the ordinary diffusion mode, and Knudsen diffusion is not important in normal foundry molds. The interdiffusivities of the metallic vapors and the mold atmosphere, through the porous aggregates, were measured. The effective interdif-fusivity of the vapor species and mold atmosphere through the aggregate may be expressed as follows: Deff,12 - — where E is the void fraction of the aggregate and 7 is the "tortuosity factor". Aggregate material had no effect on diffusion rates, and the only relevant parameter was the void fraction. Values for 7 ranged from 3 to 6 for normal foundry aggregates with 4 being considered a good representative value. An area of interest in high-temperature metallurgical processes which has received little attention in the past is the diffusion of metal vapor species in porous aggregates. Research into the metal penetration phenomenon' in foundry molds has shown that a major penetration mechanism is the vapor transport of metallic species into the porous foundry sand molds, followed by condensation of metallic films on the sand grains. Considerable study of the vaporization of metallic species has been reported in the literature, and the vapor transport properties of many metallic species have been determined.2'3 Many instances have been observed where the vaporization behavior could only be explained by the existence of a metallic species with a vapor pressure greater than the elemental metallic species. These species were identified or, in some cases, presumed to be carbonyls,4,5 hydroxides,6-9 or vaporous oxides.10-16 The diffusion of gases through porous aggregates has received considerable attention in the literature pertaining to catalysis, although primarily at low temperature, and more recently in the literature concerned with ore reduction.17-22 The following experiments were devised and carried out in order to determine the nature of the metallic species involved in the metal penetration phenomenon, and the effective diffusivities involved. EXPERIMENTAL APPROACH Steady-state diffusion was selected for experimental convenience. The experimental systems used, shown in Figs. 1 and 2, consisted of a porous aggregate specimen contained in an impermeable alumina tube held above, and just separate from a metal bath. The entire system was held at constant temperature and pressure in a furnace with a controlled oxygen partial pressure atmosphere. After a brief period of nonsteady state behavior, a steady flux of metal vapor through the porous aggregate will develop due to the concentration gradient of metallic vapor in the gas phase. The flux of metallic vapor from pressure may be neglected because there is no pressure gradient. There is no flux from convection because there is no net flow of gas within the metal-aggregate system, and thermal diffusion is negligible compared to the flux from ordinary diffusion. If the material being studied is allowed to vaporize until steady-state behavior is attained, the experimental results may be analyzed using Fick's First Law.

Jan 1, 1970

By Milton E. Wadsworth, Daniel B. Brimhall

Column leach studies of a low-grade porphyry copper ore were made. The technique used involved alternating oxygen absorption and copper leach cycles. The leach solution was displayed from the column with oxygen. The volume of oxygen reacting with the ore was measured with a gas burette. The copper released as a result of exposure to oxygen was correlated with the oxygen uptake. The oxidation rate was found to be dependent on the pH of the solution wetting the particles and was markedly increased by increasing the temperature of the system. Decreasing the particle size of the sample increased the oxidation rate. A material balance on the system indicated 1 mole of oxygen yielded in excess of 1 mole of copper in solution. A discussion of the important parameters is presented and the results are related to dump leaching in general.

Jan 1, 1974

By O. D. Gonzalez

ThIS communication presents the results of a determination of the permeabilities of hydrogen and deuterium in a iron from 360° to 560°C. Recently Heu-mann and primas' have given values of the diffusivity and solubility in a iron of the two isotopes from which the permeability can be calculated. The work reported in the present communication, however, is a direct measurement of the rate of permeation of the isotopes through an identical iron specimen under the same conditions, so that systematic errors can be minimized in the calculation of the ratio of the permeabilities—the value which is usually of main importance in establishing limits for isotopic differences in diffusive processes. Experimentally the procedure used was the usual one: a steady-state flow of gas produced by a pressure difference across an iron membrane was observed as the pressure rise with time in a previously evacuated, calibrated volume connected to the outlet side of the membrane, while a constant pressure of gas was maintained on the opposite inlet side. The membrane was a cylindrical tube 9.38 cm long, 0.730 cm inside diam, 0.187 cm wall thickness, fabricated of 99.95 pct vacuum-melted National Research Corp. iron (less than 0.003 pct C). One end was sealed by a heliarc-welded iron (99.95 pctj lid of 0.147 cm thickness; the other end of the tube was welded to a 304 stainless-steel tube (0.318 cm ID and 0.318 cm wall) which connects to a vacuum system and to the calibrated volume including a dibutylphthalate manometer. The temperature of the iron membrane was maintained constant to ±0.l°C and was measured with an iron-constantan thermocouple which was calibrated against a standard Pt/Pt-Rh thermocouple: the temperature variation along the length of the membrane did not exceed ±0.5°C. Hydrogen was allowed to pass through the membrane assembly for 72 hr at 615°C before permeability measurements were begun. The system was tested at temperature before and after the experiments by a substitution of helium for hydrogen in the inlet side; under these conditions the pressure rise observed in the outlet side was negligible at all times. The gases used for the permeability measurements were 99.95 pct Matheson prepurified H2 and 99.7 pct D2 (0.3 pct HD) from the Isomet Corp. The gases were dried with liquid N2 before use. In Fig. 1 the logarithms of observed flows, jt, for a pressure difference of 73.4 cm Hg are plotted against T-1 Each point in Fig. 1 represents the slope determined by a least-square evaluation of a plot of the pressure in the outlet side of the membrane against time, including at least two separate sets of observations. Each point in the figure has an uncertainty of ±0.6 pct arising from the experimental uncertainty in the pressure and time measurements. The standard deviation of the observed pressures from the straight lines in all cases is less than the experimental precision of the measurements. The observed flow, jt, includes a small but not negligible flow through the stainless-steel connection.

Jan 1, 1968

By D. H. Davis, I. Fatt

Oil bearing rocks, usually found at depths of 2,000 to 10,000 it, are elastically deformed by overburden pressure. Although the change in porosity with pressure in a number of example rock.: has been shown to be small, it was thought that overburden pressure might have a significant effect on permeability. This note presents results of an investigation to determine the magnitude of the change in permeabilty with pressure. In routine core analysis permeabilities are measured on rock samples which are not under overburden pressure. If permeablity measured in this way differs from permeabilities measured under overburden pressure, a systematic error is introduced into well productivity calculations. The experiments described in this report were made to determine the magnitude of the change and thus to give an estimate of the error introduced into the calculations. The error introduced by the neglect of the change in permeability when overburden pressure is removed may account for part of the difference between well productivity calculated from core analysis and the actual well productivity. The results obtained in this investigation have only quali-tative significance because of the difficulty in reproducing in the laboratory the stress conditions on the rock buried in the earth. The assumption which is usually made is that the rocks in the earth are under a uniform pressure equal to the weight per unit area of the vertical overburden column from the rock in question to the surface of the earth less the pressure of the liquid in the pores of the rock. For an overburden consisting of sandstones and shales (of assumed average specific gravity of 2.3) and for a liquid pressure equal to the pressure in a salt water column (of specific gravity 1.0) reaching from the rock to the surface, the resulting net pressure on the rock is approximately 0.56 psi per ft of depth. EXPERIMENTAL METHOD Clean, dry sandstone core plugs one in. in diameter and about three in. long were mounted in a copper foil jacket as shown in Fig. 3 or molded in a Lucite jacket as shown in Fig. 4. All cores except those labeled "2" in Fig. 1 and "8" in Fig. 2 were measured in the copper foil jacket. Cores "2" and "8" were measured in the Lucite jacket. The jacketed core was placed in a high pressure hydraulic bomb in which the liquid pressure outside the jacket could be raised to 15,000 psi. Flow lines from the core were brought out of the bomb through special fittings in the bomh head and connected to a laboratory type gas permeameter. Measurements were made with nitrogen gas; the maximum mean gas pressure in the core was 16.1 psia. RESULTS The specific permeability of sandstone decreases with in. crease in overburden pressure. Most of the decrease takes place over the range of zero to 3,000 psi overburden pressure. If the net pressure on the rock is assumed to be 0.56 psi per ft of depth as discussed above, 3,000 psi of overburden pressure is equivalent to about 5,000 ft of overburden. At 3,000 psi overburden pressure, the permeability of the eight sandstone core samples tested ranged from 59 to 89 per cent of the permeability without overburden pressure. Figs. 1 and 2 show the permeability reduction as a function of overburden pressure. The permeability of the eight cores without overburden pressure ranged from 4.35 md to 632 md; these permeabilities are listed in Figs. 1 and 2. REFERENCES 1. Carpenter and Spencer: "Measurements of Compressibility of Consolidated Oil Bearing Sands," U. S. Bureau of Mines, R.I. 3450, (1940). * * *

Jan 1, 1952

CHARGING of an open-hearth heat is begun as soon as possible after the previous heat has been tapped. Ordinarily, about 40 min is required to drain and dress the furnace hearth, make up the taphole, and perform routine repairs of the banks. Repairs to the upper back wall and to the front wall and jambs can ordinarily be done while the first scrap charge is being heated and are therefore allowed to wait in order to save furnace time. Any major repairs required on the hearth or other parts of the furnace necessitate longer delays because such repairs must be made while the furnace is empty. Although charging practice varies considerably in detail with the type and proportions of scrap and iron used, many factors are common to all varieties of charge. Such general considerations are dealt with first. CHARGING EQUIPMENT AND STOCK HANDLING The physical equipment available for loading and weighing the stock, transporting it to the furnace, and charging it, may have a major effect on charging practice. Limestone, scrap, and all other solid melting stock are charged mechanically by means of equipment illustrated in Fig 2-1. The charging of hot metal is shown in the background of this figure. Mechanical equipment and plant layout for stock handling are described in Chapter 1. It is generally desirable to charge the scrap about as fast as the physical volume can be put into the furnace. Charging scrap that is too heavy or adding the charge too rapidly (less than 45 min) may be detrimental to melting rate because of excessive chilling of the entire furnace system and also because of poor conduction of heat to the lower layers in the furnace; but the more common problem is the reverse one of charging light 'scrap fast enough to maintain a normal heat time. A limiting factor may be the height to which the scrap may he piled in the fur-

Jan 1, 1951