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By R. C. Thompson

THE lead-zinc mill of Phelps Dodge Corporation, Copper Queen Branch, Mines Division, Bisbee, Arizona, is about 3 miles from the main hoisting shafts of the Junction and Campbell mines at Lowell. All the ore treated in the mill is obtained from these two mines. The mill was designed for an all-flotation treatment of 450 tons of lead-zinc ore per day, and has been operated at that capacity since the start of milling operations on Nov. 17, 1945. An expansion program is underway whereby the mill capacity will be doubled, but this article describes only the original program and presents results of the 45o-ton operation. GENERAL DESCRIPTION The milling plant consists of an ore-receiving bin and three steel-constructed buildings housing, respectively, the primary crushing equipment, the secondary crushing equipment, and the ore-storage bins, grinding, flotation, and filtering equipment. The mill site is the one that was used for a previous copper-concentrating plant, which was operated over a period of years and then dismantled. There remained from this operation some milling equipment, a reservoir for mill-water supply, railroad tracks, tailings-disposal ponds, and a steel-constructed building, all of which were incorporated in the design of the present lead-zinc mill. The location plan of the plant layout is shown in Fig I. The flowsheet of the mill is based on the conventional scheme for lead-zinc treatment, however, several innovations were made necessary in order to utilize the existing building. Placing of equipment also was governed by the design of the building; thus making the mill unique in many respects. The following brief description of the mill building as adapted to the flowsheet points out the compactness of the installation and some of its unusual features. The first floor (Fig 2) houses the grinding equipment, with connecting conveyors for ore feeding, also an air compressor, two vacuum pumps, bins for lead and zinc concentrate storage with individual conveying systems for loading the two kinds of concentrates. Filtering of concentrates is done on the second floor, the concentrates discharging directly into the concentrate-storage bins. On this floor are the lead and zinc filters, two diaphragm pumps, sample-filtering equipment, sample-preparation room and a change room for the mill employees. The flotation machines are on the third floor, at elevations allowing a gravity flow of the lead and zinc concentrates to the thickeners. The annex to the building contains a freight elevator and provides space for all reagent mixing and feeding, also storage of reagents and grinding balls. All the water used for milling purposes is pumped from the Junction mine and

Jan 1, 1947

By L. D. Woodworth, E. E. McGinley

During the past several years has occurred what, in the light of future events, may aptly be called the rebirth of the acid Bessemer process. The increased attention given to the technical and metallurgical details involved in the production of Bessemer steels has been exceedingly fruitful, and indicates the value of further research and p1ant development. In times like these, when the steelmaking capacity of the country is operating at a maximum rate to supply materials for the national defense program, it behooves the Bessemer operator not only to strive to increase production but also to maintain a high standard of quality. The opportunity is ripe, it seems, to recapture fields of application once considered the birthright of Bessemer steels, but supplanted in recent years by open-hearth grades. This involves cooperation all along the line, from the blast-furnace operator to the metallurgical contact man and salesman. The metallurgist's part in this program involves the study of the many steelmaking variables and the measures necessary to ensure constancy in the finished product. It is equally important that the knowledge gained be disseminated widely to ensure the wise application of Bessemer steels in new fields. The merits of Bessemer steels for certain work are well understood. The combined properties of good weldability, machinabil-ity and stiffness are unique and fully explain the strong entrenchment of Bessemer steels in certain fields; e.g., skelp for small butt-weld conduit, screw steels machined in automatics, and certain tin-plate applications. It is the purpose of this paper to review briefly the physical properties of Bessemer steels as contrasted with those of open-hearth steels, to discuss control measures now employed in the making of Bessemer steel, and to consider the advantages derived from the use of these control measures. Physical Properties oF Bessemer vs. Open-hearth Steels A number of Bessemer blows and open-hearth heats were tested for tensile strength, ductility and impact strength. The steels selected were confined to sections from 3/4 to 1 1/4-in. diameter, inclusive, and the carbon content covered was sufficient to yield parallel ranges in ultimate strength for the comparison. Other factors, such as the extent of deoxidation of the steel and variations in chemistry, were kept as comparable as possible. Machined test pieces of 0.505-in. diameter with an 8-in. gauge length were pulled. The data obtained are shown in Fig. I, ultimate strength being plotted against carbon content. This graph shows that for equivalent carbon content Bessemer steel has on the average 15,000 lb. per sq. in. greater tensile strength and, conversely, for the same tensile strength Bessemer steel requires on the average 0.14 per cent less carbon. The average phosphorus content for the Bessemer steel was 0.090 per cent,

Jan 1, 1941

By E. E. McGinley, L. D. Woodworth

During the past several years has occurred what, in the light of future events, may aptly be called the rebirth of the acid Bessemer process. The increased attention given to the technical and metallurgical details involved in the production of Bessemer steels has been exceedingly fruitful, and indicates the value of further research and p1ant development. In times like these, when the steelmaking capacity of the country is operating at a maximum rate to supply materials for the national defense program, it behooves the Bessemer operator not only to strive to increase production but also to maintain a high standard of quality. The opportunity is ripe, it seems, to recapture fields of application once considered the birthright of Bessemer steels, but supplanted in recent years by open-hearth grades. This involves cooperation all along the line, from the blast-furnace operator to the metallurgical contact man and salesman. The metallurgist's part in this program involves the study of the many steelmaking variables and the measures necessary to ensure constancy in the finished product. It is equally important that the knowledge gained be disseminated widely to ensure the wise application of Bessemer steels in new fields. The merits of Bessemer steels for certain work are well understood. The combined properties of good weldability, machinabil-ity and stiffness are unique and fully explain the strong entrenchment of Bessemer steels in certain fields; e.g., skelp for small butt-weld conduit, screw steels machined in automatics, and certain tin-plate applications. It is the purpose of this paper to review briefly the physical properties of Bessemer steels as contrasted with those of open-hearth steels, to discuss control measures now employed in the making of Bessemer steel, and to consider the advantages derived from the use of these control measures. Physical Properties oF Bessemer vs. Open-hearth Steels A number of Bessemer blows and open-hearth heats were tested for tensile strength, ductility and impact strength. The steels selected were confined to sections from 3/4 to 1 1/4-in. diameter, inclusive, and the carbon content covered was sufficient to yield parallel ranges in ultimate strength for the comparison. Other factors, such as the extent of deoxidation of the steel and variations in chemistry, were kept as comparable as possible. Machined test pieces of 0.505-in. diameter with an 8-in. gauge length were pulled. The data obtained are shown in Fig. I, ultimate strength being plotted against carbon content. This graph shows that for equivalent carbon content Bessemer steel has on the average 15,000 lb. per sq. in. greater tensile strength and, conversely, for the same tensile strength Bessemer steel requires on the average 0.14 per cent less carbon. The average phosphorus content for the Bessemer steel was 0.090 per cent,

Jan 1, 1941

By Frank Foote, E. R. Jette

Precision lattice-constant measurements have been widely used in the study of cubic solid solutions but as yet have been rarely applied to noncubic solid solutions. (See, however, references I and 2.) With the high precision at present attainable in the measurement of lattice constants, the X-ray method should be readily applicable to noncubic solid solutions. In the work reported here, hexagonal close-packed magnesium was used as the solvent and either lead, bismuth or gold as the solute. In the magnesium-lead and magnesium-bismuth systems the a and c lattice constants were determined as a function of composition, densities were calculated from these lattice-constant data, these theoretical densities were compared with those directly measured and the solid solubility limit was determined on quenched specimens over a considerable range of temperature. In the magnesium-gold system, the solid solubility is very small but we have obtained an indirect check on the solubility limit previously reported. Materials and Preparation oF the Alloys The magnesium used was obtained from the Aluminum Company of America and was 99.987 per cent pure. Impurities as reported On the label were: Fe, Al, 0'004 per cent; Si, 0.009 per cent; Zn, trace; Cu, Pb, nil. The bismuth was Merck's analytical grade, minimum purity 99.95 per cent. Maximum impurities as listed on the label were: Fe, 0.008 per cent; Pb, 0.010 per cent; Ag, 0.010 per cent; Cu, 0.005 per cent; Sn, 0.003 per cent; Sb, 0.00; As, 0.000; S, 0.01 per cent. The gold was purified by double precipitation with sulphur dioxide. The lattice constants of these three metals have been previously reported.3 The lead used was test lead, silver free and with a maximum of 0.10 per cent heavy metal impurities. The lattice constant 01 this lead has been measured and found to be 4.94057 ± 0.00016 at 25°C. The alloys were prepared by melting together weighed amounts of the constituent metals in magnesia-lined alundum crucibles under an atmosphere of hydrogen purified by passing over magnesium heated to 500°C. The magnesia lining prevented contamination 01 the alloys with aluminum. Vacuum melting could not be used because of the volatility of magnesium. A high-frequency induction furnace was used for the melting operation and the stirring action of the current resulted in thorough mixing of the constituents. The melts were allowed to freeze in the crucible, the ingots obtained weighed about 10 grams. An extremely thin white film formed on the surface of the melts, sometimes covering only a part of the exposed surface. The ingots were filed clean, placed in small iror crucibles with close-fitting lids and indi. vidually sealed into Pyrex glass tubes Before sealing off, the tubes were alter

Jan 1, 1941

By Frank Foote, E. R. Jette

Precision lattice-constant measurements have been widely used in the study of cubic solid solutions but as yet have been rarely applied to noncubic solid solutions. (See, however, references I and 2.) With the high precision at present attainable in the measurement of lattice constants, the X-ray method should be readily applicable to noncubic solid solutions. In the work reported here, hexagonal close-packed magnesium was used as the solvent and either lead, bismuth or gold as the solute. In the magnesium-lead and magnesium-bismuth systems the a and c lattice constants were determined as a function of composition, densities were calculated from these lattice-constant data, these theoretical densities were compared with those directly measured and the solid solubility limit was determined on quenched specimens over a considerable range of temperature. In the magnesium-gold system, the solid solubility is very small but we have obtained an indirect check on the solubility limit previously reported. Materials and Preparation oF the Alloys The magnesium used was obtained from the Aluminum Company of America and was 99.987 per cent pure. Impurities as reported On the label were: Fe, Al, 0'004 per cent; Si, 0.009 per cent; Zn, trace; Cu, Pb, nil. The bismuth was Merck's analytical grade, minimum purity 99.95 per cent. Maximum impurities as listed on the label were: Fe, 0.008 per cent; Pb, 0.010 per cent; Ag, 0.010 per cent; Cu, 0.005 per cent; Sn, 0.003 per cent; Sb, 0.00; As, 0.000; S, 0.01 per cent. The gold was purified by double precipitation with sulphur dioxide. The lattice constants of these three metals have been previously reported.3 The lead used was test lead, silver free and with a maximum of 0.10 per cent heavy metal impurities. The lattice constant 01 this lead has been measured and found to be 4.94057 ± 0.00016 at 25°C. The alloys were prepared by melting together weighed amounts of the constituent metals in magnesia-lined alundum crucibles under an atmosphere of hydrogen purified by passing over magnesium heated to 500°C. The magnesia lining prevented contamination 01 the alloys with aluminum. Vacuum melting could not be used because of the volatility of magnesium. A high-frequency induction furnace was used for the melting operation and the stirring action of the current resulted in thorough mixing of the constituents. The melts were allowed to freeze in the crucible, the ingots obtained weighed about 10 grams. An extremely thin white film formed on the surface of the melts, sometimes covering only a part of the exposed surface. The ingots were filed clean, placed in small iror crucibles with close-fitting lids and indi. vidually sealed into Pyrex glass tubes Before sealing off, the tubes were alter

Jan 1, 1941

By B. F. Decker, J. H. Keeler, W. R. Hibbard

Textures of hot-rolled, of cold-rolled, and of cold-rolled and annealed zirconium sheets were determined by use of an X-ray spectrogoniometer. All textures showed a tilt of the basal planes 240" from the rolling plane about the rolling direction. Deformation textures showed the [1010] direction to be approximately in the rolling direction. After recrystalliza-tion, the 111201 direction was approximately in the rolling direction. This texture was sharpened by annealing above the allotropic transformation. Textures of sheet produced by alternately cold rolling and then annealing were less strongly oriented than sheets that underwent severe deformation without intermediate anneals. THIS study of the deformation and annealing textures of high purity zirconium was carried out to supplement an investigation of zirconium and zirconium-base alloys. The spectrogoniometer method of pole figure determination was used and yielded more detailed and precise information than the photographic techniques used by previous investigators. Earlier investigations of the rolling textures of hexagonal metals titanium,1,2 beryllium," and zirconiumL having a c/a ratio slightly less than 1.6 disclosed a rotation of the basal planes from the rolling plane about the rolling direction so that the basal poles were inclined toward the transverse direction, and with one exception,& the [1010] direction was found parallel to the rolling direction. Similarly, hot rolling produced a spread of the basal poles in the transverse direction,2,3,5 With the [1010] direction parallel to the rolling direction. The textures of these metals after recrystallization differ somewhat from each other although still exhibiting the transverse rotation of the basal poles about the rolling direction. Zirconium" was found to have the [1120] direction in the rolling direction, beryllium" continued to have the [1010] direction in the rolling direction, and titanium' was shown to have the [1010] direction in the rolling direction (the cold-rolling texture) when annealed at 1000°F, changing to the [1120] direction in the rolling direction when annealed at 1500°F. It was suggested2 that the titanium retains the deformation texture after re-crystallization, and preferred grain growth at higher temperatures produces the second texture. Annealing above the allotropic transformation temperature did not appreciably change the high temperature recrystallization texture for titanium.' Coarsegrained zirconium showed more spread" in the transformation texture than in the recrystallization texture. The material used in this investigation was crystal-bar zirconium prepared by the iodide process. The major impurity was hafnium which was less than 0.3 pct. The composition obtained by spectro-graphic analysis is given in Table I. The hot-rolled specimen was prepared from a 50-g button of zirconium arc-melted in a water-cooled crucible under an argon atmosphere. This button was enclosed in a welded sheath of soft iron and the ensemble was rolled at 825°C. After each pass the sheath was put back into the furnace to allow it to return to the desired temperature. The zirconium ingot was reduced in this manner to a thickness of about 0.035 in., a reduction of approximately 90 pct. The sheet after removal from the sheath was alternately polished and etched to a thickness of 0.001 in. Cold-rolled specimens were prepared from crystal bar by a series of reductions of approximately 0.010 in. until the sheet reached a thickness of 0.010 in. after which it was cold-rolled to 0.001 in. thickness between sheets of alloy steel. The total cold reduction amounted to about 99.8 pct. Specimens were annealed in an evacuated Vycor or quartz tube. The transmission pole figures were obtained by the quantitative method of Decker, Asp, and Harker6 modified by Geisler7 using an X-ray spectrogoniometer with Cu Ka radiation. Unless otherwise specified all four quadrants were examined with 5" increments along the radius of the pole figure. Absorption corrections were made for changes in length of the X-ray path through the sample as inclination of the

Jan 1, 1954

By J. H. Reynolds

The possibility of using a semiconductor, metal, semiconductor structure as a light detector is discussed. A brief theoretical argument is presented which predicts that this structure should have pho-toresponse characteristics similur to those of a metal-semiconductor diode, but with the magnitude of the current increased by a transistor gain factor. Measurements made at low frequencies on a particulur S-M-S device agree u~th this prediction aizd shoul that significant gain factors are attainable. The current gain is substantially higher than that predicted for the metal base transistor. It is proposed that the operation of these units is more closely approxinzated by the metal-gate model which predicts higher current gains. A qualitative discussion of its high-frequency performance indicates that detection of light modulated at microwave frequencies by a S-M-S deuice is possible. ADVANCES in the technology of chemical vapor deposition'-4 have made it possible to form a S-M-S structure consisting of a thin metallic layer sandwiched between layers of single-crystal semiconductor. It has been proposed5-7 that, if the metal layer is made sufficiently thin, this structure could be used in an amplifier having several advantages over presently available transistors including higher-frequency performance. Calculations8 predict that the maximum gain-bandwidth product is nearly an order of magnitude higher than that of a bipolar transistor having the same geometry. Maximum oscillating frequencies in the microwave range are predicted. Electrical measurements made on S-M-S devices have shown that, although the theoretical frequency characteristics are not presently attainable, current and power gain is obtained. Another possible application of the S-M-S structure is its use in a light detector. This structure is a three-layer relative of the metal-semiconductor diode. Light detection using M-S diodes is the subject of considerable present interest. They are known to have a short response time and the ability to detect light having a photon energy below the semiconductor bandgap. In this paper, the mechanism by which S-M-S photocurrent is generated is discussed. An expression is derived which shows that the response characteristics are similar to those of a M-S diode, but that the magnitude of the current is increased due to the transistorlike behavior of the device. The results of low-frequency response measurements on a particular S-M-S structure are presented. These agree with the theoretical predictions and show that significant gain factors are attainable. A qualitative discussion of the high-frequency characteristics is presented which predicts that detection of light at microwave frequencies by a S-M-S device is possible. THEORY In this discussion, the photocurrent, iT, measured across terminals attached to the semiconductor emitter and collector layers is related to the current pho-toemitted from the metal base layer. The latter will be referred to as the primary photocurrent. The behavior of the primary photocurrent is determined by the characteristics of the two metal-semiconductor diodes. The diode photoemission is illustrated in Fig. 1, which shows the emitter and collector potential barriers. The metal thickness has been greatly exaggerated. As will be discussed later, the actual barrier shape can be much more complex, but this diagram illustrates the essential features of the photoemission process. An absorbed photon having an energy greater than the barrier height can emit an electron into the emitter or collector. Since this process is discussed

Jan 1, 1968

By E. S. Bumps, H. D. Kessler, M. Hansen

The titanium-rich end of the Ti-AI phase diagram has been determined to the compound TiAI3 (62.7 pct Al), thus joining the aluminum-rich portion previously investigated by others and completing the diagram. Micrographic analysis and X-ray diffraction were the chief methods used to determine the phase relationships. THE Ti-Al phase diagram has been investigated as part of a program on titanium phase diagrams for the Wright Air Development Center. Included in the available information concerning the phase relationships in titanium-rich Ti-A1 alloys is a brief statement by Brown' that: "aluminum raises the transformation temperature to 1000°C (183Z°F)." This observation is interesting in that it is the first example of a metallic alloying component raising the transformation temperature of titanium, and consequently widening the field of the a solid solution. Busch and Freyer' presented resistivity data which indicated the formation of titanium-rich solid solutions of 1 and 3 pct A1 alloys prepared by powder metallurgy methods. Duweza found that there is only one other intermediate phase other than the known compound TiA1, (62.7 pct Al). This phase, designated as y, is of variable composition; its crystal structure is of the AuCu type and is therefore based on the composition TiAl (36.02 pct Al). Earlier work on the constitution of the aluminum-rich alloys has been reviewed by Hansen, and need not be discussed here. The tetragonal crystal lattice of TiAl,, as found by Fink, Van Horn, and Budge," was confirmed by Brauer." Recently, Schubert7 has reported that TiA1, is homogeneous within a limited composition range; however, the solubility limits were not given. The Ti-A1 phase diagram as presented in. this paper was determined by micrographic analysis of alloys containing from 1 to 62 pct Al, annealed at and quenched from temperatures between 700" and 1400°C. The phases and phase ranges investigated extend to the compound TiA1, (62.7 pct Al) to join the aluminum-rich end of the system determined by other investigators, thus completing the diagram. Methods of Investigation Preparation of Alloys: Iodide titanium, 99.9+ pct pure, obtained from the New Jersey Zinc Co., and high-purity (99.99+ pct) aluminum sheet from the Aluminum Co. of America were used to make up alloy ingots weighing 10 to 20 g. Detailed descriptions of melting techniques have been presented previously for work on the Ti-Mo and Ti-Cb> nd Ti-Si" phase diagrams. Briefly, the melting practice consisted of arc melting an accurately weighed charge in a copper block crucible insert in a non-consumable tungsten electrode furnace, under helium at atmospheric pressure. All ingots were carefully weighed after melting to detect possible losses. Comparison of weight before and after melting showed no appreciable weight changes. Also, chemical analyses were in close agreement with nominal compositions, Table I. The diagram as presented is, therefore, based on nominal compositions. Alloys were prepared having the following nominal aluminum contents: 1 ... 36 (1 pct increments), 38, 40, 41, 42.5, 44, 45, 46, 47.5, 49 . . . 64 (1 pct increments), 67, 70, 80, and 90. Ingots with up to 14 pct A1 were cold-pressed various amounts in order to increase the rate of attaining equilibrium structures on heat treatment. The amount of cold deformation that could be applied decreased with increasing aluminum content, until alloys containing 12 pct A1 or more cracked after only a few percent deformation. Annealing Treatments: Samples annealed at temperatures of 700" to 1000°C were sealed in

Jan 1, 1953

By H. J. Levinstein, H. J. Guggenheim

RbFeF3 is a transparent ferromagnet with a large faraday rotation which permits the direct observation of magnetic domain structures in bulk crystals. If the position of dislocations within the crystal were known a study of domain wall dislocation interactions would be possible. In this paper an etch pitting solution is described which gives a one-one correspondent between the etch pits and the dislocations intersecting the (100) surfaces of RbFeF3 crystals. In addition, RbFeF3 is shown to have sufficient plasticity so that known arrays of dislocaticms can be put into the crystal. It is concluded that RbFeF, is an ideal material for the investigation of domain wall dislocation interactions. THE influence of lattice defects on the motion of domain walls in ferromagnetic materials has been studied extensively both theoretically and experimentally.4 The experimental data obtained has been qualitative in nature due to the lack either of a quantitative knowledge of the magnetic domain array in the material or of the nature of the dislocation configuration in the material. At room temperature RbFeFJ has the cubic perovskite structure. It is ferromagnetic below 86°K.5,6 It is also transparent and has a large faraday rotation in the magnetic state.7 The domain structure of this material is observable in three dimensions in crystals which are millimeters in thickness.' Since RbFeF3 satisfies the requirements of having an easily visible three-dimensional magnetic domain structure, it was of interest to determine if the dislocation structure of the material could be determined and if the material was sufficiently plastic so that dislocations could be introduced into the as grown crystals. This is a report of the results of that investigation. EXPERIMENTAL PROCEDURE The crystals of RbFeFs used in this experiment were grown by a technique described elsewhere.5 In order to obtain flat strain-free surfaces, the samples were first cut to the crystal orientation desired and the surfaces were polished by employing standard metallographic techniques. The samples were then immersed in a solution of 1 to 3 g of KOH in 100 ml of water. This solution removes the damaged surface layers uniformly leaving a film on the surface of the sample. Etch pits are obtained by immersing the sample in an approximately 50-50 solution of 30 pct peroxide and concentrated acetic acid. The film formed during the KOH treatment turns deep red in color in the etching solution and flakes off the sample. The etching time required depends upon the pit size desired and

Jan 1, 1970

By J. C. Deppe

A method is presented for calculating approximate injection rates in secondary recovery operations. The method can be applied to cases of unequal fluid mobilities, irregular well patterns and boundary patterns. The steady-state pressure distributions for the four flood patterns reported by Muskat and for five additional patterns reveal that most of the difference in pressure between the injection and producing wells occurs in regions around the wells which can adequately be described as regions of radial flow. This leads to a method of calculating injectivity by approximating the flood pattern with radial flow elements (or a combination of radial- and linear-flow elements for some patterns such as the direct line drive). Irregular and boundary patterns can also be approximated by radial and linear elements. Each of these elements can be described by radial-and linear-flow equations and the results combined as series flow resistances to give an approximate equation for the initial injection rate. The mobility ratio does not affect the initial rate; therefore, if the well pattern is one of those regular patterns for which theoretical rate equations have been derived for unity mobility ratio, the approximate initial rate equation can be improved by adjusting it to match the theoretical equation. The available theoretical rate equations are listed, including five new cases. As the flood progresses, the injectivity changes because in general the flood front will divide the pattern into areas of different fluid mobilities. Simple shapes can be assumed for the flood front so that both areas can be divided into radial- and linear-flow elements. Radial- and linear-flow equations are applied to these elements to account for the change in flow resistance behind the front. To calculate injection rates after breakthrough, it is necessary to know the sweep efficiency at breakthrough. Areal sweep data are available in the literature for a number of patterns, and sufficiently accurate breakthrough sweep efficiency can be estimated from these data if it is not otherwise available. Again, simple shapes for the flood front can be assumed after breakthrough, and injection rates can be calculated for the remainder of the flood. When areal sweep data are available, these data can be used to cbeck. the calculated injection rates after breakthrough. Injection rates calculated by this approximate method compare favorably with available model data. INTRODUCTION When the fluid mobilities in the swept and un swept regions are equal, the injectivity will not change as the flood front advances; and for regular patterns it can be calculated by mathematical formu1as.l When the fluid mobilities in the swept and unswept regions are not equal, the injectivity will increase or decrease as the flood front advances. In this case, the injectivity has not been calculated by analytical means for any practical well pattern; and, furthermore, scale model and analog4,6 results have been published only for the five-spot pattern. The main object of this paper is to present an approximace method for calculating injectivity for the case of unequal mobilities. The method can be applied to regular, irregular and boundary patterns. Before the approximate method is discussed, the analytical formulas for equal mobilities will be summarized, and the analytical solution for radial flow with unequal mobilities will be used to show how the injectivity changes as the flood progresses. EQUAL MOBILITIES, REGULAR PATTERNS In a flooding operation the injectivity, the rate at which fluid can be injected per unit difference in pressure between injection and producing wells, depends on basic physical properties and, in addition, on three variables to be treated here—the area of the swept region, the fluid mobilities in the swept and unswept regions, and the well geometry (pattern,

By H. R. Hose

The total crude fluorspar reserves in Western Europe, including the USSR and the Soviet sphere, Thetotalare estimated to exceed 17 million metric tons. The total fluorspar production in 1951 in Western Europe, excluding the USSR and Soviet sphere, amounted to 371,109 metric tons. The chief fluorspar-producing countries in Europe, excluding Russia and the Soviet sphere, are France, Western Germany, Italy, Spain, and the United Kingdom. TOTAL crude fluorspar reserves in western Europe, containing more than 35 pct CaF2, are estimated at 12 million metric tons, while reserves in the USSR and Soviet sphere may exceed 5 million metric tons. The bulk of these reserves are concentrated in the USSR, Spain, United Kingdom, Western Germany, and Italy. Since published estimates of the tonnages of individual mines and explored deposits are not available for most countries in Europe, the estimates given in Table I for individual countries are necessarily approximate, as they have been compiled from various sources and modified and combined according to the author's judgment. The majority of fluorspar deposits in Europe belong to the late Paleozoic metallogenetic epochs and have been found within or along the borders of the Hercynian massifs. Deposits in the Central and Esterel massifs of France, those of Western and Eastern Germany, Sardinia, the Catalonian coastal range and the Sierra de los Santos in Spain, and those of Devonshire and Cornwall belong to the Hercynian metallogenetic epochs. The deposits in southern Norway and Sweden belong to the middle Paleozoic or later, those of northern England to the late Paleozoic or later, those of northern Spain and Greece to the late Mesozoic, and those of northern and probably central Italy and Switzerland to the early Tertiary. Fluorspar occurs typically in veins, lenses, and stringers, but also in bedded replacement deposits and pockets, and may be colorless to white, yellow, green, pink, brown, blue, or purple to almost black. Except for the colorless variety, the only kind which can be used for the optical industry, the color of the fluorspar does not affect its ultimate use. Crystalline cubic or octahedral fluorite of CaF2 composition, with 48.9 pct fluorine and 51.1 pct calcium, has a specific gravity of 3.18. The ore in place, however, usually averages 3.0 metric tons per cubic meter owing to the quantity of other minerals asso- ciated with the fluorspar in the veins and the physical state of the fluorspar, which may vary from sugary to massive crystalline or microscopic inter-growths with barite or quartz. Barite of 4.5 sp gr, quartz of 2.66 sp gr, and chert and calcite are commonly associated with fluorspar. Other minerals usually present in lesser amounts are celestite, wad, silver, lead, zinc, copper, iron, and uranium minerals. In some cavity fillings the rhythmic deposition of the fluorspar, barite, and quartz into successive crusts may make it possible to handpick the crude ore on belts or to separate the fluorspar from other minerals while the actual mining is carried on. Where metallurgical grade lump spar is required for foundries, separation of quartz and barite may be made also by jigs and heavy media, and in some mines the lead and zinc sulphides may be separated and recovered by vibrating tables. However, except in the case of unusually high grade deposits, acid grade fluorspar is obtained by flotation. By this process fluorspar deposits grading down to 35 pct CaF2 in the crude ore can be worked at a profit when fluorspar, lead, zinc, and silver prices are high, as the sulphides of these ores can be separated from the fluorspar by flotation and concentrated.

Jan 1, 1956

By Sherwin F. Kelly

THIS is intended as a simple review of the principles and practice of geophysics, so will not be of interest to the geophysicist, who is hereby warned of its elementary character. The engineers for whom it is written are those who, having glimpsed the formidable formulas and discussions of the geophysicists, give all publications on the subject a wide berth. For a few years now the geo-physicists have had a tendency to be ingrowing at their meetings, going deeper and deeper into theory and instrument construction, and forgetting to present the topics that would interest the practicing engineer who desires merely to know how geophysics can help him, not why.

Jan 1, 1934

J. M. TIPPETT? Colorado Springs, Co1o.-There are several points which offer ground for discussion, although the authors' indicated results leave small chance for argument. Under classification of the ores as they come to the mill, it will be noted that these are classified according to their lime contents. In previous years the classification was based upon sulfur contents, CaO not being considered; class A would be called the oxidized ore and class B the sulfides. Classification according to CaO is the first public indication that a decided change in the ore has necessitated improved methods of treatment. The very serious effect that CaO, even in small quantities, has upon extraction has been noted for some years.

Jan 11, 1918

By M. S. Seltzer

High temperature steady-state creep rates have been determined jor lead sulfide single crystals whose defect concentrations were fixed by equilibration under controlled sulfur pressure. The activation energy of creep, Qc , for undoped lead sulfide, is a function 01 composilion, decreasing from 2.9 to 2.2 ev as the carrier concentration increases from 9 x 1016 to 8 1018 electrons cm-3 for lead excess crystals, and increasing from 1.7 to 2.3 ev as the concentration of holes increases from 4 x 1017 to 1 x 1018 cm-3 in sulfur excess material. For five different composilions, Qc for undoped and bismuth-doped crystals has been found to be equal to Qpb + Qs, the self-diffusion activation energies for lead and sulfur in PbS. It is well-established1 that high-temperature steady-state creep of pure metals is a diffusion-controlled process, where the activation energy of creep is equal, within experimental error, to the activation energy of self-diffusion. The relationship between the activation energy for steady-state creep and those for self-diffusion in binary compounds is more complicated, however, because two different diffusing species must be considered, and becayse the activation energies may be influenced by compositional variations and by foreign atom additions.2-4 In some cases experimentally determined creep activation energies are correlated with those for self-diffusion of the slower-moving species, but such agreement is by no means universal. Interpretation of experimental results is difficult because few investigations include measurements of creep rates and self-diffusion coefficients of both diffusing species on single crystals of similar composition and foreign atom concentration. The objective of this investigation, therefore, is to determine the influence of stoichiometric defects and foreign atoms on steady-state creep and self-diffusion for a well-characterized binary compound. Lead sulfide, a compound semiconductor which crystallizes in the NaC1-type structure, and whose homogeneity range includes compositions on either side of the 1:l atom ratio, was chosen for study in this investigation. The pressure-temperature-composition relations for PbS are available,5,3 and deviations from stoichiometry may be monitored by electrical measurements.7 Single-crystal specimens are available to allow observation of effects due to bulk phenomena without interference from grain-boundary effects. These crystals have been employed to determine steady-state creep rates under compressive stress for "pure" and bismuth-doped PbS as a function of sulfur pressure and temperature as well as crystal orientation and applied stress in order to establish the relationships between defect concentrations and creep rates. EXPERIMENTAL PROCEDURES Crystal Growth. Lead sulfide crystals, prepared by the Bridgman method, are grown in evacuated quartz crucibles, filled with almost equal atomic proportions of high-purity (99.999 pct) lead and sulfur, and heated to a temperature above the melting point of PbS (about 1127°C) so that the lead and sulfur react to form molten PbS. The crucible and melt are dropped through the hot zone of the crystal-growing furnace at the rate of 1 cm per hr. The maximum melting point of PbS is slightly on the lead-rich side of the 50:50 composition; hence crystals grown from a near stoichiometric melt are usually n-type semiconductors containing excess lead atoms. Typically the lead excess concentration in solid solution with the PbS is 3 x 1018 atoms cm-3. Crystals containing either 1/20 or 1/2 mole pct Bi2S3 were prepared by addition of the foreign atoms prior to crystal synthesis. Preparation of Specimens of Controlled Stoichiom-etry. Since it is difficult to grow crystals of desired composition, the process of crystal growth and control of stoichiometry are separated into two distinct operations. Equilibration of as-grown PbS to a desired composition is most easily accomplished by first annealing the n-type crystals under high sulfur pressure (about 1 atm) at temperatures above 700°C. This process serves to put excess lead precipitates into solution, yielding 0 -type crystals upon quenching to room temperature. Inter diffusion occurs readily in crystals so treated, and the methods described by Bloem may then be employed to obtain crystals of controlled stoi-chiometry. For the creep measurements made in this study, this involves heating crystals in mixtures of H2 and H2S The equilibrium constant for H2S is given by: Thus the sulfur partial pressure is obtained from knowledge of the H2/H2S ratio and Kh2S for the temperature in question. Fig. 1 shows the p-T-x diagram for PbS. It can be seen that, within the stability limits for single-phase lead sulfide, desired compositions may be obtained by equilibrating under a specified sulfur pressure and temperature. Characterization of Crystals. The principal methods for evaluating PbS crystals include measurement of electrical properties and mass-spectrographic analysis. The measured electrical parameters include Hall coefficient, conductivity type, and electrical resistivity Bloem7 has shown that there is a 1:l relation between the defect concentration and carrier concentration obtained. Hence, if the contribution to the carrier con-

Jan 1, 1968

By R. W. Gurry

Thermodynamic calculations indicate that boron is a better deoxidizer than silicon but probably is not quite as effective as aluminum. Boron should, therefore, be readily oxidized out of the open-hearth bath, which implies that it is not recovered in significant concentration from any scrap charged; also that, if added in the ladle, it tends to oxidize out during teeming unless protected by the presence of a better deoxidizing agent. These conclusions do not apply to liquid cast iron, in which the oxygen content is much lower than in liquid steel. The possibility of conserving certain strategic alloying elements widely used in steelmaking, notably manganese, chromium and molybdenum, by the use of boron, which in small concentration appears to be extraordinarily effective in promoting hardenability, raises a question as to what extent any boron present in the scrap charged into the open hearth is oxidized out during melting and subsequent refining. This question is significant because the optimum concentration of boron in the finished steel, which is fairly critical, would be very difficult to attain if the boron in the charge were largely retained in the metal. Moreover, unless boron is substantially eliminated in the open-hearth process its use on a large scale would eventually make it impossible to produce boron-free steel except by restricting the charge to virgin material. There is at present, unfortunately, virtually no satisfactory direct evidence to provide an answer to this question; but there are indications from practice that boron is oxidized out in the open hearth in the production of medium or low-carbon steel, although it may be retained if the carbon content remains fairly high; that is, if the oxygen is kept fairly low. In the absence of direct data, it is necessary to rely upon the indications of indirect evidence, the best approach now available being a thermodynamic calculation of the deoxidizing power of boron in liquid steel by the general method used so successfully by Chipman1 in his study of the reactions in the open-hearth process. The thermal data for boron, upon which such a calculation must be based, are reasonably satisfactory; the only quantities not directly determined are the entropy of melting of boron, the activity coefficient of boron in liquid steel, and the activity coefficient of B2O3in an open-hearth slag; but these values may be estimated with ample accuracy. The results of this calculation, which is presented later, are given in Table I, together with corresponding data for other deoxidizing elements. This table shows the calculated residual content of oxygen in equilibrium with different residual concentrations of the deoxidizer in the metal;

Jan 1, 1944

By R. W. Gurry

Thermodynamic calculations indicate that boron is a better deoxidizer than silicon but probably is not quite as effective as aluminum. Boron should, therefore, be readily oxidized out of the open-hearth bath, which implies that it is not recovered in significant concentration from any scrap charged; also that, if added in the ladle, it tends to oxidize out during teeming unless protected by the presence of a better deoxidizing agent. These conclusions do not apply to liquid cast iron, in which the oxygen content is much lower than in liquid steel. The possibility of conserving certain strategic alloying elements widely used in steelmaking, notably manganese, chromium and molybdenum, by the use of boron, which in small concentration appears to be extraordinarily effective in promoting hardenability, raises a question as to what extent any boron present in the scrap charged into the open hearth is oxidized out during melting and subsequent refining. This question is significant because the optimum concentration of boron in the finished steel, which is fairly critical, would be very difficult to attain if the boron in the charge were largely retained in the metal. Moreover, unless boron is substantially eliminated in the open-hearth process its use on a large scale would eventually make it impossible to produce boron-free steel except by restricting the charge to virgin material. There is at present, unfortunately, virtually no satisfactory direct evidence to provide an answer to this question; but there are indications from practice that boron is oxidized out in the open hearth in the production of medium or low-carbon steel, although it may be retained if the carbon content remains fairly high; that is, if the oxygen is kept fairly low. In the absence of direct data, it is necessary to rely upon the indications of indirect evidence, the best approach now available being a thermodynamic calculation of the deoxidizing power of boron in liquid steel by the general method used so successfully by Chipman1 in his study of the reactions in the open-hearth process. The thermal data for boron, upon which such a calculation must be based, are reasonably satisfactory; the only quantities not directly determined are the entropy of melting of boron, the activity coefficient of boron in liquid steel, and the activity coefficient of B2O3in an open-hearth slag; but these values may be estimated with ample accuracy. The results of this calculation, which is presented later, are given in Table I, together with corresponding data for other deoxidizing elements. This table shows the calculated residual content of oxygen in equilibrium with different residual concentrations of the deoxidizer in the metal;

Jan 1, 1944

By H. C. Fiedler

The development of cube-on-edge secondary re crystallization texture in Si-Fe strip depends upon the ability of inclusions, such as manganese sulfide, to restrain nomal grain gvowth. The ability of inclusions to perform this function is shown to depend upon their size and distribution. The desired uniform dispersion of many small inclusions is obtained by controlling the cooling rate from above the solution tempmature of the inclusions or, alternatively, by drastic 'quenching from above the solution temperature followed by heat treating at a lower temperature. The development of the cube-on-edge secondary recrystallization texture in Si-Fe strip depends upon both establishing the proper primary recrystallization texture and having inclusions to restrain normal grain growth. It has been suggested that the first requirement is met with a texture which, though weak, is near (110)[001]. A mechanism for secondary recrystallization originally proposed by ielsen' is consistent with the presence of this primary texture. It is visualized that a secondary grain appears where two adjacent grains happen to be sufficiently similar in orientation to be capable of behaving as a single large grain. This pair of grains will grow at the expense of its smaller neighbors as a consequence of its having lower grain boundary free energy. Other explanations of the origin of the secondary recrystallization texture have been offered,' and it can be concluded that the mechanism is not fully understood. Nevertheless, it is apparent that operationally the necessary primary recrystallization texture is obtained simply by interposing an anneal during the cold reduction to final gage. The role of inclusions in the development of the secondary recrystallization texture has been demonstrated by May and Turnbull4 in a comparison of a high-purity heat and a heat containing manganese sulfide. They showed that the driving force for secondary recrystallization is inversely proportional to the diameter of the matrix grains and that the function of the inclusions is to maintain a small matrix grain size. Other inclusions, such as various sul- fides,')' silicon nitride,8 and vanadium nitride,' titanium carbide,'' and vanadium carbide," have been shown to be effective in promoting secondary recrystallization to the cube-on-edge texture. There is also evidence that silica inclusions in Si-Fe strip made by powder-metallurgy techniques perform this function.' This report is concerned with the second of the two requirements for secondary recrystallization, namely the importance of the metallurgical control of the size and therefore number of inclusions. While the concepts involved are simple, they are fundamental to the making of this material. EXPERIMENTAL PROCEDURE A heat containing 3.27 pct Si, 0.026 pct S, 0.06 pct Mn, and 0.004 pct C was made in an air induction furnace from electrolytic iron, 98 pct ferro-silicon, electrolytic manganese, and iron sulfide. The heat was divided between graphite and baked-sand molds with a cavity 2-5/8 by 5 in. and with walls 2-3/4 in. thick. Slabs, 1 in. thick and 2-5/8 by 5 in., were cut from the ingots and hot-rolled either in the as-cast condition or after one of the heat treatments described later. After pickling, the 80- to 100-mil-thick hot-rolled band was, unless otherwise noted, heat-treated for 5 min at 900°C before being cold-rolled to 25 mils. After a heat treatment of 1 to 3 min at 860°C, the strip was cold-rolled to 12 mils, the final thickness. The percent cube-on-edge texture was determined by dividing the maximum torque as averaged from four samples by the maximum torque of a 3-1/4 pct Si-Fe single crystal having the (110) plane in the plane of the sample. The torque measurements were made in a field of 1000 oe on 1-in.-diam disks. RESULTS AND DISCUSSION The importance of the thermal history of the ingot is evident in Fig. 1 from the appearance of strips heat-treated in a temperature gradient. The sample

Jan 1, 1964

By J. C. Swartz

New measurements of graphite and cementite solubilities in ferrite have been obtained to resolve disagreements among previous data. To measure graphite solubility, specimens of iron were equilibrated with rarious carburizing atmospheres at temperatures be-twee~z 480" and 1435°C. The carbon activity of each atmosphere relative to graphite was taken from published data. After quenching from each equilibration treatment the concentration of carbon (typically 10 pprn by wt) was determined from the height of the Snoek peak in the internal friction spectrum. A few inclividual analyses by combustion support the reszdts of Smith on the solubility of graphite near the eutectoid temperature. Combination of these combustion and internal friction analyses determines In a, (at 0.01 wt pct) = 24,000/RT - 12.72, where a, is the activtity relative to graphite in ferrite at fixed cornposition. The same specimens were used to determine the solubility of self-stressed cementite precipitates. The results indicate solubilities of 6.3, 23.2, and 68 pprn carbon by wt at respectively 400°, 500". and 600°C. The once large discrepancy between the cementite solubility determined by internal frictiori and that calculated from flee energy data has been almost completely resolved. A recent study1 (hereafter designated I) on the solubility of cementite in a iron did not fully resolve the disagreement among previous data. The remaining disagreement is illustrated by the phase diagram in Fig. L The data of I are represented by the line labeled "stress-free" cementite. They determine a heat of solution of cementite of (14.8 * 0.2) kcal per mole which contrasts with the (20 * 1) kcal per mole derived from Smith's graphite solubility2 and the formation energy of cementite.3 Toward resolving this disagreement we have obtained new data on the solubilities of graphite and cementite. METHODS As in I the Snoek peak in the internal friction spectrum was used to measure the concentration of carbon dissolved in ferrite. This method relies on the relation C=kQ-1 [1] in which C is the concentration of dissolved carbon, Q-I is the Snoek peak height, and k is a proportionality factor which is a function of the peak temperature, polycrystalline texture, and other parameters characteristic of the ferrite lattice. To determine true heats of solution via Eq. [1], it is necessary to establish that k is independent of the temperature from which the specimen is quenched. Some evidence on this point is contained in a separate report.* Additional evidence is shown by the data points in Fig. 1. These represent the Snoek peaks of two specimens carburized to about 10 ppm C, copper plated, and quenched first from 888º then from 588°C. The copper plate was removed before each Snoek peak measurement. These data show that there is no detectable dependence of k on quenching temperature. The solubility of graphite was determined by repeatedly carburizing various specimens of iron wire with gas mixtures of known carbon activity relative to graphite. To cover a wide temperature range within the a phase boundaries it is desirable to use as low a carbon concentration as is compatible with reasonable precision. With the present internal friction apparatus the best compromise of these desires is a concentration near 10 wt ppm. The dashed line in Fig. 1 was used to approximate the activity of carbon* for

Jan 1, 1970

By Ian William Wark, Keith Leonard Sutherland

MERCAPTOBENZTHIAZOLE and its sodium salt are marketed under the trade names Flotagen and Flotagen S respectively, for use as collectors for cerussite and other minerals. The structural formulas for sodium mercaptobenzthiazole and for sodium ethyl xanthate are: [ ] Chemically there is a resemblance between the two compounds, though the free acid (mercaptobenzthiazole itself) is much more stable than xanthic acid. Both are readily oxidized, e.g., by iodine to disulphides, and can be estimated by iodometric titration. Qualitatively they are similar as collectors in flotation, although there are quantitative differences between them that may be important in practice. It is deduced that the influence of the nitrogen atom is subordinated to that of the sulphur atoms, and that the dominant group of these compounds is the mercapto group -SH or -SNa. The general method of investigation has been based on contact tests. Two temperatures, 10º and 35º C., have been chosen, and with a standard concentration of 20 mg. per liter of mercaptobenzthiazole (i.e., of the free acid) the influence of alkali, cyanide and copper sulphate on contact at sulphide mineral surfaces has been studied. This standard concentration corresponds to about 19 mg. per liter potassium ethyl xanthate; it brings out the differences between the minerals better than a higher concentra-

Jan 1, 1939

By R. S. Rickard, H. D. Peterson, J. D. Miller, M. C. Fuerstenan

Pure chrysocolla is floated with chelating agents that form insoluble complexes with copper at ambient temperature. Complete flotation is obtained with potassium octyl hydroxamate as collector at pH 6. Flotation response is enhanced with increased temperature when low additions of hydroxamate are involved. A natural ore was floated with 0.4 1b per ton octyl hydroxamate at pH 6.5 and 58°C, and a flotation recovery of 76% was obtained with a concentrate grade of 31.6% copper. The flotation characteristics of the oxide copper minerals, malachite, azurite, and cuprite, have not presented the difficulty for concentration as have those of the copper silicate, chrysocolla. The copper carbonates and oxides respond reasonably well to flotation with conventional collectors, whereas chrysocolla will not respond to flotation with fatty acids or xanthates under normal flotation conditions. In this view then, other reagents will have to be devised to function as collectors for chrysocolla. The most obvious general class of reagents for this purpose would seem to be the organic copper chelating compounds. The utility of chelating agents as collectors in flotation systems has already been demonstrated. For example Vivian1 has floated cassiterite using ammonium nitrosophenylhydroxylamine. Holman2 studied the flotation of nickel oxide ores with dimethylglyoxime and also suggested the use of taurine on oxidized lead ores. A rather detailed study on the application of certain chelating agents to some flotation systems was presented by Gutzeit.3 This work indicated that the formation of surface insoluble chelates is probably responsible for flotation in many cases. The role that soluble chelating agents assume was also presented, that is with effective removal of polyvalent cations by complex formation, effective depression of quartz can be obtained. DeWitt and Batchelder4,5 have shown that oximes function well as collectors for chalcocite, malachite, azurite, and cuprite. Ludt and DeWitt6 have presented the possibility of using dyes, such as octyl malachite green, as a collector for chrysocolla. These works presented by DeWitt et al suggest that organic copper chelating compounds offer considerable promise for concentrating chrysocolla, but that the most suitable chelating reagent from the standpoint of cost and flotation response has yet to be determined. The present investigation was undertaken to study the flotation response of chrysocolla to selected copper chelating compounds, that is ethylenediamine, hexamethylenetetramine, potassium octyl hydroxamate, dimethylglyoxime, and benzoin a-oxime. EXPERIMENTAL MATERIALS Chrysocolla: The chrysocolla used in the microflo-tation studies was from New Mexico and analyzed 20.8% copper. X-ray diffraction showed this material to be amorphous in character, but some faint lines of quartz were noted. A natural oxide copper ore from Utah was also used in the investigation. This ore contains malachite principally but also contains chrysocolla and tenorite together with some sulfide copper. The sulfide copper comprises from 15 to 20% of the total copper content of the ore. Water: Conductivity water was used in the microflo-tation experiments, while Golden tap water was used in the experiments with the natural ore. Reagents: Reagent grade n-amyl alcohol was used as frother in the experiments with pure mineral, while MIBC was used in the work with the ore. Ethylenediamine, hexamethylenetetramine, dimethylglyoxime and benzoin a-oxime were reagent grade in quality. Pure potassium octyl hydroxamate was prepared as follows: 1) 1.0 mole of KOH in 140 cc of methanol was combined with 0.6 mole of hydroxyl-amine hydrochloride in 240 cc of methanol at 40°C (KC1 precipitates under these conditions and to effect complete removal of KCl, the system was cooled to 10°C and filtered), 2) a light methanol wash was then given the KC1 cake, 3) the filtrate was agitated at room temperature and 0.33 mole of the methyl ester of the organic acid (i.e. methyl octanoate) was

Jan 1, 1965