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By H. B. Huntington

Some of the basic problems in understanding elec-tromigration in metals are discussed, along with the attempts that are being made to handle them. One such problem is the effect of the electrostatic forces. It is now acknowledged that the momentum exchange with charge carriers plays generally a dominant role in the driving force but the question remains to what extent the electrostatic force may still be effective. The electromigration of interstitial impurities is also an area which presents some intriguing questions. For the substitutional impurity, moving by the vacancy mechanism under the influence of an electric field, the correlation considerations are somewhat more complex than have been previously recognized. Another problem of basic importance in the calculution from first principles is the strength of the "electron friction" force, say for a simple one-band metal. A related problem growing out of the preceding is the prediction of the direction of the "electron wind" force for metals with band structure involving both holes and electrons. THE term electromigration has come to be used to describe the flow of matter in condensed phases carrying high electronic currents such as metals and alloys, whereas one usually reserves the term electrolysis for situations where the current is largely ionic, particularly in the liquid state such as molten salts. It follows that the mass transport number in electromigration is always very small, of the order of 10-7. Studies of electromigration date back some 30 years but the modern period would appear to date from the work of Seith and Wever1 who in the mid 1950's first incorporated markers to display mass motion relative to the lattice and first suggested that the direction of the mass flow was primarily determined by the sign of the charge carriers. Since that time interest in the field has grown steadily and more rapidly recently as certain technological applications became apparent. Chief of these is certainly the deleterious effects that electromigration can cause, even at relatively low temperature, to current-carrying elements in integrated circuitry.2 These phenomena have been the subject of intense study and considerable ingenuity. On the constructive side electromigration has proved a useful tool in the purification of certain metals.3 The interest of this paper is, however, centered more on the basic aspects of the subject than on its technological applications. That high electric currents should give rise to mass flow in metals and that the driving force should be more directly associated with momentum exchange with the charge carriers than with the electrostatic field are ideas that no longer cause surprise or particular interest. The field has matured to the point where the general concepts are widely accepted and continued progress in basic understanding rests on more detailed and quantitative exploration. It is the purpose of this paper to point out what are some of the current problems. As a result, we expect to raise more questions than we answer. The first of these will be the role of electrostatic forces, if any, in electromigration. A second section will deal with the electromigration of interstitials. A third and final section treats with electromigration of substitutional impurities or of the matrix atoms themselves. ELECTROSTATIC DRIVING FORCE In the conceptual treatments of electromigration it has been customary to write the driving force in terms of an effective charge number Z* and to divide it into two terms F = e£Z* = e£[Zel- z(pd/Nd)(N/p)(m*\m*\)] [1] The first of these represents the electrostatic force under immediate consideration in this section and the second and usually dominating term for metals arises from momentum exchange with charge carriers, commonly called the "electron drag" term. As can be seen it is set proportional to the electrons per atom, z, and the ratio of the specific resistivity of the moving entity to the corresponding resistivity per matrix atom. The (m*/Im*I) factor takes into account the fact that the sign of the charge carrier determines the sign of the driving force. The specific resistivity of the moving entity is averaged over its path. In the case of motion of the matrix atoms by vacancies this gives rise to approximately one-half the resistivity at the saddle point since the scattering power of the atom at its equilibrium position bordering the vacancy differs only slightly from that of a normal matrix atom. Although the formulation of the "electron drag" term in Eq. [I] is based on a highly simplified model for electron defect scattering, the essential features implicit in the expression are common to all the theoretical approaches that have so far appeared in the literature.4-6 As for Zel, most treatments of electromigration have included the quantity as the parameter which measures the direct interaction of the electrostatic field with the ion and equated it to the nominal valence of the latter. However, there has been considerable discussion whether this interaction may not be 0 in many cases.6 If the moving ion is always enveloped by the same distribution of shielding charge, then clearly its motion will not involve any work done by the electric field and one can expect there will be no electrostatic force exerted on such a neutral composite. From this point of view the shielding charge around the ion would be said to be complete and hence the entity within the Debye shielding sphere would be unaffected by the electrostatic field per se. There is, however, the prospect that, as the moving ion progresses, new charge comes in to participate in the shielding action

Jan 1, 1970

By T. P. Meloy

The behavior of slime-sized particles in a flotation cell is neither well documented nor well understood. In general, slimes (or 'fines' as they will be alternatively called in this chapter) have been either ignored, eliminated, or treated empirically. Recently, however, some good experimental and theoretical work has been done that leads qualitatively to a clearer understanding of the problems involved. Fines are small particles that, owing to their smallness, behave differently from larger particles of the same material. The smaller the particle, the larger is its surface-to-mass ratio. The difference in the surface-to-mass ratio for a micron-sized particle and a centimeter-sized particle is 10,000 to 1. For our purposes we shall arbitrarily define any particle less than 10 µ 10-3 cm) as being a fine. This is generally considered the upper limit of colloidal-sized particles. Recently, the field of colloidal chemistry has successfully used the concept of the double layer to explain dispersion and flocculation of fine particles in a static system. Flotation, however, is a dynamic system due both to the turbulence of the liquid and to the coursing of the bubbles through the cell. Further more, a flotation system is a heterogeneous system in which there are a number of different types of particles which interact with one another. A further difficulty is that no two flotation systems are the same for minute quantities of a variety of common chemicals will alter the behavior of the system. These reasons make reproducible experimental results that can ex- plain fine-particle behavior difficult to obtain. In spite of these experimental difficulties, millions of tons of ore containing a large amount of fines are successfully floated every year. For example, at the Morning mill of American Smelting and Refining Co., a galena concentrate that was 42% -6 µ and a sphalerite concentrate that was 33% -9 µ were floated leaving a tailing that was 27% - 9 µ.l Ores that contain fines can generally be divided into two classes. In the first are those in which the valuable mineral tends to slime, such as galena and hematite. In the other class, one or more of the gangue minerals forms the slime; a typical example is barite. Though the problems due to the presence of fines are often the same in handling the two classes of ore, the method of handling them is different because of economic considerations. Nonmetallic mineral flotation is particularly affected by slimes, by either slime-coating effects or excessive reagent consumption. Though a given gangue mineral may not float under the conditions prevailing in the flotation cell, it may still be able to adsorb the collector. I£ it also slimes, a significant

Jan 1, 1962

By Enid C. Plante, K. L. Sutherland

PRACTICAL metallurgists are unanimous in stating that oxidation of mined sulphide ore adversely affects separation of the constituent minerals under standard conditions in a mill. Frequently, the need for different operating conditions in different plants is attributed either to the extent of oxidation of the mineral surfaces or to soluble oxidation products. The investigations reported in this paper study the effect of oxidation on the primary condition necessary for flotation, namely that of adhesion of an air bubble to the mineral. OXIDATION PRODUCTS FROM SULPHIDE MINERALS Weinig and Carpenter1 state that the relative rates of oxidation of some sulphides are: FeAsS > FeS2 > CuFeS2 > ZnS >PbS > Cu2S tetrahedrite. They also show that oxidation is rapid at first, that sulphides of older geological formations are more stable than those of recent date and that mixtures oxidize more rapidly than any one mineral alone. The more rapid oxidation of mixtures is borne out by results of Gottschalk and Buehler2 who found that PbS, ZnS and CuS oxidized 8 to 20 times faster when pyrite was present. Only the end products of oxidation, sulphate and the metal ion, were identified in these tests. Gaudin3 states that pyrite is difficult to oxidize in the laboratory. Winchell,4 using pyrite containing 99.98 pct FeS2, allowed water to percolate through a bed of this ground material. At the end of three months only a trace of Fe +++and S04- were found. Even after 10 months the quantity of Fe+++ was only 7.8 mg and S04- 25.5 mg per liter of percolating solution. Carmichael5 confirmed Winchell's results on the slow oxidation of pyrite. Usually the oxidation of sulphide surfaces has been conducted in neutral or acid solutions, the acidity being caused by the oxidation products. Eliseev and Nagirnyak6 found that treatment of pure pyrite with lime gave only thiosulphate, but considered it possible that thiosulphate was obtained not by oxidation of the pyrite itself, but by oxidation of calcium disulphide. Mitrofanov7 suggested that thiosulphate was formed by the following process: oxidation of sulphide to give free sulphur (this frequently happens with marcasite), followed by oxidation of the sulphur to sulphur dioxide and reaction of the sulphur dioxide with sulphur to give thiosulphate. Ferric and ferrous hydroxides, or similar compounds, were shown to be present. The Research Staff of the United Verde Copper Co.8 treated ore from the United Verde mine with lime. Thiosulphate, sulphide and polysulphides were stated to be

Jan 1, 1947

By Thomas F. Bates

ANALYSIS of the chemical and structural differences in minerals often results in a better understanding of the differences in the geological conditions under which they were formed. The minerals in the kaolinite group differ in the amount of interlayer water and in the nature and amount of ordered and/or random shifting of each 1:1 layer with respect to those above and below it. This paper is a progress report resulting from research on the morphology, structure, and origin of fine-grained minerals, supported by Contract N6onr26914 with the Geophysics Branch of the Office of Naval Research. The purpose of the paper is to present data obtained in the laboratories at The Pennsylvania State College and elsewhere, which reveal some of the details of structure of the minerals in the kaolinite group, and to suggest a number of interpretations that bear upon the conditions of origin of these minerals. Be¬cause most of the work in this investigation thus far has been concerned with the relationships of kaolinite, halloysite (4H2O; endellite), and halloysite (2H2O), must of the discussion deals with these members of the group. The first step in the analysis of the differences in two sets of geological conditions is an evaluation of the differences in the minerals that result. Thus the chemical differences between the montmorillonite and the kaolinite clays corroborate other evidence in support of the view that the montmorillonites are commonly formed when solutions are alkaline and leaching poor, while kaolinite usually is associated with acid solutions and good drainage condi¬tions. It is obvious that the greater the differences in the minerals, the more divergent may be the conditions that give rise to them and the more readily one condition can be distinguished from the other. In the kaolinite group, differences between individual members are small, therefore the differences in condition of origin are presumably subtle and difficult to define. At the same time, the very fact that the minerals differ only slightly makes them more sensitive indicators of the exact conditions under which they and the minerals associated with them were formed. Since clay minerals are being used more and more to evaluate the nature, value, and mode of formation of economic mineral deposits, an attempt to define these subtle differences would appear worth while. For purposes of the present discussion, the minerals nacrite, dickite, kaolinite, the so-called "fireclay mineral," halloysite (4H2O), halloysite

Jan 1, 1952

By C. R. Holmgren

A large consolidated sand core was used in this investigation. Four groups of experiments including gas drives, water drives, and water drives combined with gas injection, were made. The results of the gas-drive experiments indicate that greater ultimate recovery may be obtained by higher pressure gradients. However, other considerations challenge the absolute veracity of this conclusion. Results indicate that with connate water present and a low pressure gradient during a gas drive, less gas is required to produce a given amount of oil. The saturation gradient determined during a gas drive is presented. Results of the water-drive experiments indicate that the recovery of oil is not a function of either gradient Or input rate. The presence of initial gas saturation resulted in a slightly lower final oil saturation. Injection of sufficient gas to maintain the initial gas saturation during a water drive resulted in lower final oil saturation. Introduction With the demand for petroleum products reaching an all-time record high and the location and exploitation of new reserves becoming more difficult and expensive, the oil industry must look to more thorough and efficient methods of producing the petroleum already located. Much of the previous work along these lines is exploratory and suggests a more complete investigation. For example, a great amount of laboratory work has been done on flooding sands initially saturated roo pct with oil. Since sands saturated roo pct with oil rarely, if ever, exist in nature, and because the water content is a vital factor in the ultimate recovery from the sand, laboratory investigations on cores without water must be supplemented by comparable work on cores with water present.1'2 Other investigators have done a considerable amount of laboratory work using gas and water drives.3 Krutter and Day4 have reported results of investigations using cores saturated IOO pct with oil and have concluded that " the ultimate recovery obtained, using air drive, from a completely oil-saturated core depends on the pressure gradients used. The higher the pressure gradient, the greater will be the recovery until a certain Pressure range is reached above which the reward of increased recovery is much smaller for similar increments in pressure." Yuster and Day6 conclude that less gas and less time are required to produce a given quantity of oil at high pressure gradients than at low pressure gradients; they also conclude that an increase in the viscosity of the oil requires a proportionate increase in the gas needed for recovery. Their results indicate that the gas required to produce a given quantity of oil is greatly reduced by the presence of connate water. R. C. Earlougher2 concluded, based on results of water-flooding a large number of

Jan 1, 1949

By Coleman D. Hunter, George M. Straughan

Oil and gas development as well as extensive leasing in Kentucky during 1940 has shown a marked improvement over the past three years.$ The most noticeable improvement is the gas development in eastern Kentucky and the deep tests being drilled by major oil interests. In western Kentucky, 406 wells were drilled, of which 173 were oil producers, 12 were gas wells and 221 were dry or abandoned. The number of dry tests was large, because no important, new oil or gas pool was discovered and many of the dry holes could be considered wildcat tests. However, with either oil or gas possibilities from Pennsylvanian formations on through Mississippian, Silurian, Devonian, and Ordovician, this percentage of dry holes seems rather high. Many of the dry tests possibly should have been tested in deeper horizons before being abandoned: namely, Silurian and Ordovician ages. In eastern Kentucky, 213 wells were drilled, of which 113 were gas producers, 61 were oil wells, and 39 were dry holes. Of these wells, 117 were drilled in the most important Big Sandy gas field, in Floyd, Pike, Knott and Martin Counties, and of this number 103 were gas producers, 5 were oil wells, and 9 were dry holes. In the Big Sinking oil field of Estill, Lee and Powell Counties, 70 of the remaining 96 wells were drilled, j6 being oil producers. During 1940, four deep tests were drilled in eastern Kentucky. One test penetrated the Knox dolomite in Knox County and was dry; no St. Peter sand was encountered. Another test in Lee County had some gas in what might be called St. Peter sand, according to the State Department, and also some gas deeper in the Knox dolomite. In Wolfe County, a small oil well was completed in the Ordovician, which was undoubtedly of Trenton age. ilt the present time, four deep tests are being drilled, all of which will go to the Knox dolomite. In Elliott County, on the Burke dome, the Inland Gas Co, is drilling at 3650 ft. In Magoffin County, on the Paint Creek uplift, the Cumberland Petroleum Co. is drilling at 3800 ft. In Clark County, in the Ruckerville fault area, W. 0. Allen is drilling at 1800 ft. In Laurel County, on the Sinking Creek dome, the Globe Oil and Gas Co. is drilling at I750 ft. If production is encountered in the Trenton, St. Peter, or Knox dolomite in any of these tests, eastern Kentucky will experience a marked increase in deep development.

Jan 1, 1941

By George M. Straughan, Coleman D. Hunter

Oil and gas development as well as extensive leasing in Kentucky during 1940 has shown a marked improvement over the past three years.$ The most noticeable improvement is the gas development in eastern Kentucky and the deep tests being drilled by major oil interests. In western Kentucky, 406 wells were drilled, of which 173 were oil producers, 12 were gas wells and 221 were dry or abandoned. The number of dry tests was large, because no important, new oil or gas pool was discovered and many of the dry holes could be considered wildcat tests. However, with either oil or gas possibilities from Pennsylvanian formations on through Mississippian, Silurian, Devonian, and Ordovician, this percentage of dry holes seems rather high. Many of the dry tests possibly should have been tested in deeper horizons before being abandoned: namely, Silurian and Ordovician ages. In eastern Kentucky, 213 wells were drilled, of which 113 were gas producers, 61 were oil wells, and 39 were dry holes. Of these wells, 117 were drilled in the most important Big Sandy gas field, in Floyd, Pike, Knott and Martin Counties, and of this number 103 were gas producers, 5 were oil wells, and 9 were dry holes. In the Big Sinking oil field of Estill, Lee and Powell Counties, 70 of the remaining 96 wells were drilled, j6 being oil producers. During 1940, four deep tests were drilled in eastern Kentucky. One test penetrated the Knox dolomite in Knox County and was dry; no St. Peter sand was encountered. Another test in Lee County had some gas in what might be called St. Peter sand, according to the State Department, and also some gas deeper in the Knox dolomite. In Wolfe County, a small oil well was completed in the Ordovician, which was undoubtedly of Trenton age. ilt the present time, four deep tests are being drilled, all of which will go to the Knox dolomite. In Elliott County, on the Burke dome, the Inland Gas Co, is drilling at 3650 ft. In Magoffin County, on the Paint Creek uplift, the Cumberland Petroleum Co. is drilling at 3800 ft. In Clark County, in the Ruckerville fault area, W. 0. Allen is drilling at 1800 ft. In Laurel County, on the Sinking Creek dome, the Globe Oil and Gas Co. is drilling at I750 ft. If production is encountered in the Trenton, St. Peter, or Knox dolomite in any of these tests, eastern Kentucky will experience a marked increase in deep development.

Jan 1, 1941

By Walter H. Bruckner, George B. Clark

Since the end of World War 11 interest has been increasing in the use of shaped charges in the mining industry and in other industries using explosives for blasting purposes. Shaped charges employ the principle known as the "Munroe effect," which was discovered by Charles E. Munroe more than 50 years ago (in 1888). Details of their design have been explained elsewhere.1,2,3 Fig I shows the essential features of design of two types of shaped charges (with conical and hemispherical cavities) and a schematic sketch of their action upon detonation. The following discussion deals with the behavior of the metal in the cavity liners when they are subjected to intense Pressures exerted when the explosive charge is detonated. Among the conclusions reached in research on shaped explosive charges, the following have been established conceming cavity liners:1'2 I. The optimum wall thickness of a conical cavity liner is dependent upon the apex angle of the cone as well as On the base diameter of the charge. Acute apex angles require thinner walls for optimum perfonnance and more obtuse angles require thicker walls for the same base diameter. '. Cones were more effective in forming a penetrating jet when the walls were tapered; that is, the thickness of the wall of the cone increased from the apex down. 3. The physical and mechanical properties of metals have a marked effect upon their performance as cavity-liner material. Boiling point, ductility, malleability, ten-sile strength, and hardness are among the properties that influence the effectiveness of a metal used as a cavity liner. Lead, for example, makes a wide, flat crater in steel plates. Aluminum makes a deeper crater than lead, and an aluminum alloy having a high tensile strength makes a deeper hole, but slightly smaller in diameter. Cast iron makes a deep, narrow hole. These findings, together with the following analysis under Metallographic Survey of slug, offer solutions to many of the problems involved in solving the mechanism of the formation of Munroe jets. It has been fairly well established that cavity liners collapse in a manner similar to that indicated in Fig 2, Conical liners are known to collapse upon themselves while hemispherical liners are believed to turn inside out in the process of jet formation. The first has been definitely proved by recovery of collapsed portions of cones, while liners from partly detonated charges show that hemispheres may turn inside out. Fig 3 shows a sketch of a recovered slug from a 6-in. shaped charge using a 45" cone made of cast iron. (This size of charge drilled holes up to 3 ft in depth in solid granodiorite.)

Jan 1, 1949

By F. C. von der Weid

The mining district of Sao Fidelis, in the northern part of the State of Rio de Janeiro, is situated on the Paraiba River, where it crosses the Serra do Mar (Mountain of the Sea), in the center of a mountainous country having numerous graphitic outcrops. For a long time, these outcrops were irregularly explored by local people, who had little means and no technical advice. A few years ago, the Cia. Brasileira de Mineracao de Grafite took over the control of some of the more important outcrops and entrusted to me the task of studying the ores and establishing a flowsheet for a pilot plant to be situated in Sao Fidelis—the ore to be concentrated being mostly of a very high grade. Mineralization and Ores The rocks of the district are mostly gneiss and crystalline schists, with occasional interstratification of dolomitic limestone belonging to the Archean Brazilian Fundamental Complex. The general direction of the beds is roughly between 60' and 80°E., with variable dip, generally nearly vertical. Mostly, direction and dip of the graphitic outcrops is concordant with the embanking gneisses or schists. These outcrops seem to be aligned in two or three parallel zones (Padua, Sao Fidelis, Mac- abu), the Sao Fidelis zone being the best known and the most important to date. Two outcrops of the Silo Fidelis zone, Saudade and Sao Benedito, are now being exploited. Mining has beer] carried out, so far, on a small scale. The mineralization consists of a vein of nearly massive graphite in a very compact, partially granitized gneiss, with vertical dip. The vein is most irregular, nith nests and lenses irregularly distributed along the fracture plane. The ore consists chiefly (particularly in Sao Benedito) of massive graphite appearing and disappearing along the main direction of the vein, forming a succession of irregular lenses in a sort of rosary design. The average width is more or less one foot, with variations from zero to 6 feet. The lode minerals are quartz, a little feldspar and garnet (the latter having its origin perhaps in the embedding gneisses), with rare ferruginous clays on the outcrops. In Saudade a little pyrite, pyrrhotite and chalcopyrite is found occasionally, as well as a carbonaceous mineral, very light, black and shiny, with conchoidal fracture, looking like a sort of jet. The composition of this mineral has not yet been established, but it seems to be very complex. The mineralization seems to be hydro-thermal at a rather low temperature, perhaps mesothermal. The paragenesis, according to samples from Saudade, seems to be as follows, the earlier minerals being listed first: pyrrhotite, pyrite, chalcopyrite, with quartz concomitant to the three and graphite formed later. Age of the mineralization is still uncertain, owing to the very in-

Jan 1, 1947

By F. C. von der Weid

The mining district of Sao Fidelis, in the northern part of the State of Rio de Janeiro, is situated on the Paraiba River, where it crosses the Serra do Mar (Mountain of the Sea), in the center of a mountainous country having numerous graphitic outcrops. For a long time, these outcrops were irregularly explored by local people, who had little means and no technical advice. A few years ago, the Cia. Brasileira de Mineracao de Grafite took over the control of some of the more important outcrops and entrusted to me the task of studying the ores and establishing a flowsheet for a pilot plant to be situated in Sao Fidelis—the ore to be concentrated being mostly of a very high grade. Mineralization and Ores The rocks of the district are mostly gneiss and crystalline schists, with occasional interstratification of dolomitic limestone belonging to the Archean Brazilian Fundamental Complex. The general direction of the beds is roughly between 60' and 80°E., with variable dip, generally nearly vertical. Mostly, direction and dip of the graphitic outcrops is concordant with the embanking gneisses or schists. These outcrops seem to be aligned in two or three parallel zones (Padua, Sao Fidelis, Mac- abu), the Sao Fidelis zone being the best known and the most important to date. Two outcrops of the Silo Fidelis zone, Saudade and Sao Benedito, are now being exploited. Mining has beer] carried out, so far, on a small scale. The mineralization consists of a vein of nearly massive graphite in a very compact, partially granitized gneiss, with vertical dip. The vein is most irregular, nith nests and lenses irregularly distributed along the fracture plane. The ore consists chiefly (particularly in Sao Benedito) of massive graphite appearing and disappearing along the main direction of the vein, forming a succession of irregular lenses in a sort of rosary design. The average width is more or less one foot, with variations from zero to 6 feet. The lode minerals are quartz, a little feldspar and garnet (the latter having its origin perhaps in the embedding gneisses), with rare ferruginous clays on the outcrops. In Saudade a little pyrite, pyrrhotite and chalcopyrite is found occasionally, as well as a carbonaceous mineral, very light, black and shiny, with conchoidal fracture, looking like a sort of jet. The composition of this mineral has not yet been established, but it seems to be very complex. The mineralization seems to be hydro-thermal at a rather low temperature, perhaps mesothermal. The paragenesis, according to samples from Saudade, seems to be as follows, the earlier minerals being listed first: pyrrhotite, pyrite, chalcopyrite, with quartz concomitant to the three and graphite formed later. Age of the mineralization is still uncertain, owing to the very in-

Jan 1, 1947

By F. C. von der Weid

The mining district of Sao Fidelis, in the northern part of the State of Rio de Janeiro, is situated on the Paraiba River, where it crosses the Serra do Mar (Mountain of the Sea), in the center of a mountainous country having numerous graphitic outcrops. For a long time, these outcrops were irregularly explored by local people, who had little means and no technical advice. A few years ago, the Cia. Brasileira de Minerasgo de Grafite took over the control of some of the more important outcrops and entrusted to me the task of studying the ores and establishing a flowsheet for a pilot plant to be situated in São Fidelis—the ore to be concentrated being mostly of a very high grade. Mineralization and Ores The rocks of the district are mostly gneiss and crystalline schists, with occasional interstratification of dolomitic limestone belonging to the Archean Brazilian Fundamental Complex. The general direction of the beds is roughly between 60" and 80°E., with variable dip, generally nearly vertical. Mostly, direction and dip of the graphitic outcrops is concordant with the embanking gneisses or schists. These outcrops seem to be aligned in two or three parallel zones (Pádua, São Fidelis, Mac- abu), the Sao Fidelis zone being the best known and the most important to date. Two outcrops of the São Fidelis zone, Saudade and Sao Benedito, are now being exploited. Mining has been carried out, so far, on a small scale. The mineralization consists of a vein of nearly massive graphite in a very compact, partially granitized gneiss, with vertical dip. The vein is most irregular, with nests and lenses irregularly distributed along the fracture plane. The ore consists chiefly (particularly in Sao Benedito) of massive graphite appearing and disappearing along the main direction of the vein, forming a succession of irregular lenses in a sort of rosary design. The average width is more or less one foot, with variations from zero to 6 feet. The lode minerals are quartz, a little feldspar and garnet (the latter having its origin perhaps in the embedding gneisses), with rare ferruginous clays on the outcrops. In Saudade a little pyrite, pyrrhotite and chalcopyrite is found occasionally, as well as a carbonaceous mineral, very light, black and shiny, with conchoidal fracture, looking like a sort of jet. The composition of this mineral has not yet been established, but it seems to be very complex. The mineralization seems to be hydro-thermal at a rather low temperature, perhaps mesothermal. The paragenesis, according to samples from Saudade, seems to be as follows, the earlier minerals being listed first: pyrrhotite, pyrite, chalcopyrite, with quartz concomitant to the three and graphite formed later. Age of the mineralization is still uncertain, owing to the very in-

Jan 1, 1948

By F. C. von der Weid

The mining district of Sao Fidelis, in the northern part of the State of Rio de Janeiro, is situated on the Paraiba River, where it crosses the Serra do Mar (Mountain of the Sea), in the center of a mountainous country having numerous graphitic outcrops. For a long time, these outcrops were irregularly explored by local people, who had little means and no technical advice. A few years ago, the Cia. Brasileira de Minerasgo de Grafite took over the control of some of the more important outcrops and entrusted to me the task of studying the ores and establishing a flowsheet for a pilot plant to be situated in São Fidelis—the ore to be concentrated being mostly of a very high grade. Mineralization and Ores The rocks of the district are mostly gneiss and crystalline schists, with occasional interstratification of dolomitic limestone belonging to the Archean Brazilian Fundamental Complex. The general direction of the beds is roughly between 60" and 80°E., with variable dip, generally nearly vertical. Mostly, direction and dip of the graphitic outcrops is concordant with the embanking gneisses or schists. These outcrops seem to be aligned in two or three parallel zones (Pádua, São Fidelis, Mac- abu), the Sao Fidelis zone being the best known and the most important to date. Two outcrops of the São Fidelis zone, Saudade and Sao Benedito, are now being exploited. Mining has been carried out, so far, on a small scale. The mineralization consists of a vein of nearly massive graphite in a very compact, partially granitized gneiss, with vertical dip. The vein is most irregular, with nests and lenses irregularly distributed along the fracture plane. The ore consists chiefly (particularly in Sao Benedito) of massive graphite appearing and disappearing along the main direction of the vein, forming a succession of irregular lenses in a sort of rosary design. The average width is more or less one foot, with variations from zero to 6 feet. The lode minerals are quartz, a little feldspar and garnet (the latter having its origin perhaps in the embedding gneisses), with rare ferruginous clays on the outcrops. In Saudade a little pyrite, pyrrhotite and chalcopyrite is found occasionally, as well as a carbonaceous mineral, very light, black and shiny, with conchoidal fracture, looking like a sort of jet. The composition of this mineral has not yet been established, but it seems to be very complex. The mineralization seems to be hydro-thermal at a rather low temperature, perhaps mesothermal. The paragenesis, according to samples from Saudade, seems to be as follows, the earlier minerals being listed first: pyrrhotite, pyrite, chalcopyrite, with quartz concomitant to the three and graphite formed later. Age of the mineralization is still uncertain, owing to the very in-

Jan 1, 1948

By R. C. Earlougher, F. G. Miller, T. D. Mueller, H. J. Ramey

There are many studies of flow in radial systems that can be used to interpret unsteady rerervoir flow problems. Although solutions for systems of infinite extent can be used to generate solutions fur finite ow systems by superposition, application is tedious. In this paper a step is made toward simplifying calcu1ations of such solutions for finite flow systems. Superposition is used to produce a tabulu-lion of the dimension1e.s.s pressure drop function at several locations within a bounded square that has a well at its center. The square system provides a useful building block that may be used to generate flow behavior for any rectangular shape whose sides are in integral ratios. Values of the tabulated dimensionless pressure drop function are simply added to obtain the dimensionless pressure drop function for the desired rectangulm system. The rectangular system may contain any number of wells producing at any rates. Furthermore, the outer boundaries of the rectangular system may be closed (no-flow) or they may he at constant pressure. Mixed conditions also may be conyidered. Tables of the dimensionless pressure drop function for the square system are presented and various applications of the technique are illustrated. Introduction In 1945, van Everdingen and Hurst' published solutions for the problem of water influx into a cylindrical reservoir. Since this problem is mathematically identical with the depletion of a cylindrical reservoir with a well at the origin, the van Everdingen-Hurst solution may be used to study the depletion problem. In their analysis, they assumed that the fluid had a small, constant compressibility such that flow was governed by the diffusivity equation For a constant production rate q starting at time zero, van Everdingen and Hurst showed that the unsteady pressurc distribution for both finite and infinite systems could be expressed in terms of a dimensionless pressure 'Sabulations of the dimensionless pressure drop for a unit value of r, were provided by van Everdingen and Hurst,' and later by Chatas.' Others also presented values in graphical or tabular form." If the radius of the well becomes vanishingly small, r,+ O, the line source solution may be used for Eq. 2 when infinite systems are considered. Eqs. 5 and 6 are excellent approximations for Eq. 2 under certain conditions: In 1954, Matthews, Brons and HazebroekV emonstrated that solutions such as Eq. 5 can be superposed to generate the behavior of bounded geometric shapes; i.e., the behavior of a bounded single-well system can be calculated by adding together the pressure disturbances caused by the appropriate array of an infinite number of wells producing from an infinite system. These wells are referred to as image wells. Matthews, Brons and Hazebroek considered systems containing a single well producing at a constant rate. This superposition can be represented analytically as

Jan 1, 1969

By Nicholas Kowall, K. L. Clark

Maximum furnace efficiency and close control of final steel composition demand that the steel melter be able to follow closely the variations in the carbon content of the bath. For many years, the fracture test has been used by melters for estimating carbon, because it requires only a very short time to pour a sample into a chill mold, cool it in water, break it with a sledge hammer, and observe the fracture. After long experience gained from the observation of such fractures, most melters are able to estimate the carbon content of steel with amazing accuracy, particularly in the lower carbon ranges. Notwithstanding the utility of the fracture test, there has been widespread interest in other methods for rapid carbon determination to supplement it and to ensure against possible errors in human judgment. Several methods, based upon measurement of magnetic properties as functions of carbon content, have been described in the literature1-6 and have been found to give reasonably reliable results in plant practice when scrap composition is known and controlled. A difficulty encountered in the use of analyzers of the magnetic type is that alloying elements do change the relationship between carbon content and magnetic properties and it becomes necessary to establish calibration curves for all the expected combinations of alloy residuals that are not oxidized in the bath. The work reported here is of an investigation of a method that is independent of alloying elements normally present in constructional steels, being based upon the relatively well-known fact that in plain carbon and low-alloy steels martensitic hardness is a function of carbon content alone. Work oF Other Investigators In I938, Burns, Moore and Archer published & curve? that showed that the hardness of martensite is a function of carbon from 0.10 to 0.50 per cent and is independent of grain size or alloy content, at least within the rallge found in construc-tional S.A.E. compositions. Some of the deeper hardening types investigated, however, contained carbon to a maximum of only o.2o per cent. Using this principle, Kern8 developed a method of rapid carbon determination for S.A.E 43xx steels, His procedure consisted of chill-casting a test bar that was large enough to give a a that could be prepared for Brinell indentations. The test piece was quenched immediately after solidi fication was complete and hardness readings were taken, so that the carbon content could he read from an experimentally determined curve giving the relationship between as-quenched hardness and carbon. Experimental Work Although Kern's work had been done with a relatively deep-hardening steel, it

Jan 1, 1944

By K. L. Clark, Nicholas Kowall

Maximum furnace efficiency and close control of final steel composition demand that the steel melter be able to follow closely the variations in the carbon content of the bath. For many years, the fracture test has been used by melters for estimating carbon, because it requires only a very short time to pour a sample into a chill mold, cool it in water, break it with a sledge hammer, and observe the fracture. After long experience gained from the observation of such fractures, most melters are able to estimate the carbon content of steel with amazing accuracy, particularly in the lower carbon ranges. Notwithstanding the utility of the fracture test, there has been widespread interest in other methods for rapid carbon determination to supplement it and to ensure against possible errors in human judgment. Several methods, based upon measurement of magnetic properties as functions of carbon content, have been described in the literature1-6 and have been found to give reasonably reliable results in plant practice when scrap composition is known and controlled. A difficulty encountered in the use of analyzers of the magnetic type is that alloying elements do change the relationship between carbon content and magnetic properties and it becomes necessary to establish calibration curves for all the expected combinations of alloy residuals that are not oxidized in the bath. The work reported here is of an investigation of a method that is independent of alloying elements normally present in constructional steels, being based upon the relatively well-known fact that in plain carbon and low-alloy steels martensitic hardness is a function of carbon content alone. Work oF Other Investigators In I938, Burns, Moore and Archer published & curve? that showed that the hardness of martensite is a function of carbon from 0.10 to 0.50 per cent and is independent of grain size or alloy content, at least within the rallge found in construc-tional S.A.E. compositions. Some of the deeper hardening types investigated, however, contained carbon to a maximum of only o.2o per cent. Using this principle, Kern8 developed a method of rapid carbon determination for S.A.E 43xx steels, His procedure consisted of chill-casting a test bar that was large enough to give a a that could be prepared for Brinell indentations. The test piece was quenched immediately after solidi fication was complete and hardness readings were taken, so that the carbon content could he read from an experimentally determined curve giving the relationship between as-quenched hardness and carbon. Experimental Work Although Kern's work had been done with a relatively deep-hardening steel, it

Jan 1, 1944

By George Sachs

I deeply appreciate the honor of being selected to deliver the twentieth Annual Lecture of the Institute of Metals Division. The subject of my paper is extremely involved and voluminous, therefore I shall discuss only some more recent experimental material and speculate somewhat on the physical and mechanical fundamentals of these changes. The flow and the rupture of a solid material are rather different phenomena. It is therefore surprising that up to a rather advanced stage in metallurgical science these two fundamental phenomena have been simultaneously treated and forced into the general conception of the "failure" of solid material. Only in this century, and particularly during the last 20 years, have the very different physical meanings of flow and rupture been clearly recognized. Several hundred of the more recent publications deal with these subjects.1 LAW OF SIMILARITY The basic values commonly considered responsible for the mechanical behavior of any material are the stresses. From this standpoint both a large and a small article made from the same homogeneous metal and of geometrically similar shapes should behave identically, i.e., they should deform geometrically in a similar manner, if subjected to the same stress values at corresponding points. This "law of similarity" was introduced about 60 years ago simultaneously by Barba2 and Kick3 and was derived from the classical theory of elasticity. As far as the plastic behavior of a metal is concerned, this rule appears to be valid. The conventional properties of large and small tension or compression test bars, machined from larger sections, are identical; while the force required to deform a section is proportional to its cross-sectional area and the work consumed in deforming geometrically similar articles in a geometrically similar manner is proportional to its volume. The general trend of the stress-strain diagram of a metal is independent of the section size (Fig. I). No exceptions from this rule are known. However, if the deformation of a metal is continued until rupture occurs, and the breaking stress or the work consumed is measured, a test bar of large cross section appears to fail before or at lower stresses than does one having a small cross section. Thus, the specific impact energy has been often found to decrease with increasing size of the test specimen, particularly for materials with a limited ductility.4 Another exception from the rule of similarity is offered by fatigue-strength values, which usually decrease with increasing section size. 5,6 The conclusion must be drawn from these experimental facts that the ductility of a homogeneous metal decreases with increas¬ing section size (Fig. x). This effect has been actually confirmed by Docherty,7 who observed that in static notch bending tests large specimens failed earlier and in a more brittle fashion than small specimens ma-

Jan 1, 1941

By R. J. Teitel

FOUR or five years ago an investigation was initiated to study and develop basic information on llquid metal fuels for future power nuclear reactors. The objective was to find fluid forms of uranium (solutions or dispersions) in low melting alloys. A summary of the different fuels was presented in a recent article by Teitel, Gurinsky, and Bryner.' The combination of uranium and bismuth, with its low thermal neutron cross section and low melting point, is of basic interest to the development of these fuels. Most of the previous effort on the U-Bi phase diagram was done under security regulation. Ahmann and Baldwin' reported their findings on the U-Bi system in 1945. Their results indicated that the phase diagram had at least two compounds and possibly one more. UBi, and UBi were established by chemical analyses of residues after high temperature centrifugation of alloys. UBi, decomposed peritectically at1980°C and there were signs of another reaction above that. UBi melted at a very high temperature, and there were also signs of a monotectic at high temperatures in high uranium alloys. The solubility of uranium in liquid bismuth has received attention by three groups of authors: Bareis,X ayes and Gordon,' and Ahmann and Baldwin.' The latest and most widely accepted data is that of Bareis, and it is included in Fig. 1 along with new data at higher temperatures. Brewer et al." and Ferro"'' have used X-ray diffraction to determine the number and crystal structure of the compounds. Brewer identified the structure of UBi to be a simple NaCl cubic structure having a cell edge of 6.364A. The density of the compound was calculated to be 11.52 g per cu cm. Two other unindexed patterns were presented as possibly belonging to two other compounds. Ferro agreed with Brewer on the crystal structure of UBi and identified the structure of UBi, and U,Bi,. The intermetallic compound UBi, has a tetragonal cell with a = 4.445A and c = 8.908A. The density of the compound was determined and the number of atoms per cell (six atoms) was calculated. The X-ray density reported was 12.35 g per cu cm. The compound UsBir was treated in a similar way and it was reported to have a cubic structure 9.35A on an edge and to contain 28 atoms per cell. The density was given as 12.59 g per cu cm. Teitel reported that there was a compound UaBi, and no UBi, compound. (The difference in the compositions is 3.3 pct U.) This conclusion was based upon the extrapolation of some 20 tie lines in the

Jan 1, 1958

By R. A. Bell, R. Schultz, P. G. Hallof

The Ballyvergin area is located in County Clare on the southwest coast of Ireland. It is one of six areas in County Clare in which mining operations were carried out during the last century. The ores mined were high grade Cu-Pb-Ag deposits in the form of small fracture fillings and gash veins in the lower Carboniferous limestones. The zone of primary economic interest is situated on the north limb of a geosyncline which plunges moderately to the southwest. The zones of mineralization previously mined were associated with local structures and folds, and the initial geophysical investigations took the form of reconnaissance induced polarization measurements around, and between, the old mines. This work located an anomaly which, on drilling, resulted in a small extension of the Pb-Cu ore at the Ballyvergin mine. However, a potentially more important zone of mineralization resulted from the drilling of another IP anomaly near Ballyvergin. This wide anomaly was found to be a domal shaped deposit of disseminated chalcopyrite located at a depth of more than 100 ft. The deposit is controlled by local folding in the sediments and is of a type previously unknown in the area. More IP investigations are under way to locate other deposits of the same type. The Ballyvergin area is located in County Clare, about 35 miles northeast of Shannon Airport, near the Atlantic west coast of Southern Ireland (Fig. 1). Interest in the area stems from a number of occurrences of small, but high grade, Pb-Ag deposits. From the summer of 1960 to the spring of 1961, Irish Base Metals carried out a comprehensive exploration program on a 38-sq mile concession in east-central County Clare in an attempt to locate additional deposits of this type. Field operations consisted of geologic mapping, geochemical soil and stream sampling, geophysical surveying and diamond drilling. The geophysical program consisted primarily of detailed induced polarization (IP) surveys in the general vicinity of old mine workings, supplemented by electromagnetic and self-potential investigations. Subsequent diamond drilling of a well defined IP anomaly close to the old Ballyvergin mine disclosed a sizeable deposit of low grade disseminated copper, a type of deposit previously unknown in this area. REGIONAL GEOLOGY Topography: The topography is of the Karst type with low regional relief. The northern parts of the area are covered almost completely with glacial deposits including a large number of drumlins. Elsewhere the overburden is patchy and only moderately deep. A close network of roads makes every part of the area readily accessible, and rail and harbor facilities are available nearby — Fig. 2. Stratigraphy: The area was mapped on a reconnaissance basis by the Geological Survey of Ireland during the latter part of the 19th century at scales of 1 and 6 in. to the mile. Mapping is complicated in

Jan 1, 1962

By R. I. Jaffee, H. R. Ogden, D. J. Maykuth

Phase diagrams for the Ti-W and Ti-Ta systems were determined. The Ti-W system is characterized by a wide, two-phase region of ß plus tungsten which is derived from a peritectic reaction between the liquid and tungsten solid solutions. The ß field terminates in a eutectoid reaction between a titanium and tungsten terminal solid solution. Tantalum and ß titanium form a complete series of solid solutions. Other features of this system are the extensive a-ß field at low temperatures and an appreciable solubility of tantalum in a titanium. BOTH tungsten and tantalum were first thought to form ß-isomorphous systems with titanium as a result of early work' using powder-metallurgical techniques. Later work2 on arc-melted Ti-Ta alloys, made using a commercial titanium base, showed that, in the range of 0 to 10 pct, tantalum was soluble in ß titanium and that the a solubility extended to between 2 and 5 pct Ta at 790 °C. The present investigation covered the entire alloy range in both systems and was chiefly concerned with high-purity alloys at the titanium-rich end. The constitution of titanium-rich alloys made with a commercial titanium base was reported by Holla-day, Kura, and Jackson.3, 4 As will be shown in detail later, the early prediction of a isomorphism was true for the case of the Ti-Ta system, but not for the Ti-W system. The results of this investigation will be presented first. The experimental methods used are described in the Appendix. Ti-W System The entire Ti-W phase diagram is shown in Fig. 1. Details of the titanium-rich side are shown in Fig. 2. The chief features of the system are a ß eutectoid and a high-temperature peritectic between liquid and tungsten solid solution. Melting Range: Examination of cast structures of low and medium-tungsten-content ingots showed cored ß phase as the primary constituent. Fig. 3a illustrates a typical cast structure for alloys in the range of 20 to 30 pct W. From 30 to 72 pct W, coring was very severe. Alloys containing 72 through 88 pct W, however, showed definite evidence of a peritectic reaction between the liquid and a terminal solid solution of titanium in tungsten. Fig. 3b shows the cast structure for an 80 pct W alloy. A 95 pct W alloy, shown in Fig. 4, consisted primarily of primary tungsten solid solution plus a small quantity of ß probably rejected during cooling. Incipient-melting experiments located the peritectic temperature between 1850" and 1900°C and indicated that the reacting phases are liquid containing about 25 pct W and tungsten terminal solid solution containing about 8 pct Ti. Figs. 5 and 6

Jan 1, 1954

By P. Campbell, E. M. Gardy, L. Hachkowski

Introduction The efficient process control of a uranium mill and its associated mining operation requires a nearly continuous knowledge of the uranium concentration in the ore. Generally, the approach is to use laboratory assays of grab samples from the mill feed belt. In some cases, elaborate and expensive systems have been used to ensure random sampling, but even with these systems, mass-balance discrepancies still exist. There is a requirement for an on-line instrument that can give a prompt, accurate analysis of a large portion of the feed stock. The authors have recently evaluated a laboratory system that achieves these goals using neutron activation and delayed neutron counting. The development of the on-line uranium ore analyzer is a consequence of previous work done at the Whiteshell Nuclear Research Establishment (WNRE) (Campbell et al., 1978 and 1981), and is based on the emission of delayed neutrons after the neutron irradiation of fissionable materials. The mechanism of delayed neutron emission has been described (Keepin, 1965), but briefly is as follows. The fission fragments resulting from irradiation are in an excited state. Certain of these delayed fission products, precursors, decay to a more stable state by the emission of a delayed neutron. The delayed neutrons can be divided into six groups with effective half-lives ranging from 0.2-55 sec. It is important to note that more than 50% of the delayed neutrons are emitted within the first 6 sec after irradiation; this has an influence on the design of the analysis instrument. Measurement Cycle The measurement cycle involves a neutron irradiation, a delay time, and a counting period. The laboratory demonstration model of the ore analyzer comprises a californium-252 neutron source, a source chamber, a pneumatic transfer facility, and a neutron irradiation and counting module [(Fig. 1)]. The ore sample is placed in the irradiation chamber. The neutron source is transferred to the center of the chamber for a 5-sec irradiation while the helium-3 thermal neutron detectors are switched off. As the source returns to the storage chamber, the detectors are switched on and the delayed neutrons counted. The total assay cycle is 16 sec. The current instrument design calls for the ore to be cut from the main belt every 16 sec by a mechanical arm and dropped into the analyzer directly, or via another belt. The cycle starts when there is a sufficient mass of ore in the irradiation chamber to depress a switch and stops when the delayed neutron count is finished. The ore is then dropped through the bottom of the analyzer chamber and returned to the main belt. The counts from each cycle are accumulated and the data reduced to give the desired information.

Jan 1, 1985