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By Irving B. Cadoff, Alvin A. Machonis

The resistivity, Hall coefficient, Seebeck coefficient, and thermal conductivity were measured as a function of temperature for cation-rich alloy single crystals covering the composition range across the PbTe-SnTe system. Alloying of PbTe with up to 20 pct SnTe was found to have little effect on the energy gap. Above 20 pct SnTe the alloys were "p" type but below this range the sign could be varied by heat treatment. The lattice thermal resistivity of the compounds SnTe and PbTe is raised by alloying one with the other. Z values in the order the interesting values obtained. THE PbTe-SnTe system has several interesting features. For one, PbTe is a useful thermoelectric material and the possibility of improving its figure of merit by alloying with SnTe, an isomorphous compound, has been suggested since these pseudo-binary solid solutions generally have a more favorable ratio of electrical conductivity to thermal conductivity than either of the components.' Other interesting features relate to the conductivity mechanism, band structure, and stoichiometry of the compounds and their alloys. PbTe is a semiconductor with an energy gap of about 0.29 ev2 at room temperature whose conductivity sign and magnitude can be varied from "n" to "p" by controlling the proportion of lead and tellurium with respect to the stoichiometric ratio.3 Excess lead results in "n"-type conduction. SnTe is found to exist only as a "p"-type material of relatively high conductivity. This behavior is attributed to stoichiometric deviation by Brebrick4 but Sagar and Miller proposed that the behavior of SnTe must be due in part to the presence of an overlapped band. An investigation of alloys of this system, therefore, might give additional information which would permit one to evaluate which of the two proposals is the more appropriate one. Abrikosov et al.' studied the room-temperature electrical properties of these alloys and reported data for Seebeck coefficient and resistivity on poly-crystalline alloys. The present work is a more exhaustive survey of the PbTe-SnTe system. Re- sistivity, Hall coefficient, Seebeck coefficient, and thermal conductivity were measured over a wide temperature range for single crystals at 10-pct intervals of lead/tin ratio across the pseudobinary system. The relative concentration of tellurium was controlled so as to obtain metal-ion excesses in all cases. SAMPLE PREPARATION The crystals were prepared by melting elemental lead, tin, and tellurium in weighed proportions in evacuated Vycor capsules. The lead and tellurium were high-purity grades obtained from American Smelting & Refining Co. The tin was supplied by Comico. The proper calculated proportions of lead, tin, and tellurium were weighed and charged into prepared Vycor capsules prior to evacuation. The capsules were prepared from 15-mm Vycor tubing. A sharp point was worked on one end of the tube. A pyrolytic graphite coating was deposited on the Vycor walls by heating the tip to 800°C in an atmosphere of acetone-saturated argon. An additional coating of graphite was deposited on the pyrolytic coating from an Aquadag suspension. Above the coated tip the tube was reduced in diameter to form a constrictive neck. To avoid scratching the graphite coatings the charge was placed in the tube above the constriction. After a low-temperature bake, the evacuated capsule was sealed. On subsequent heating the charge melted down into the lower portion of the capsule. The crystals were grown by lowering the capsule through a Bridgman-Stockbarger furnace. The lowering rate was 1 in. per 8 hr. The upper portion of the furnace was set for 950°C and the lower portion for 800°C. In general the yield of single crystals was about 25 pct. The mixed compositions were, as expected, the most difficult to grow. The finished crystals were sectioned into 5/8-in. slices. The tip, end, and middle slices from each crystal were analyzed by X-ray fluorescence to determine the lead-to-tin ratio. The resulting values were used to plot a composition vs distance plot for each crystal. Slices were selected from each crystal, with the aid of the composition plots, to cover the complete range of compositions at 10-pct intervals. In general, the slices selected were taken from the seed end of the crystal where the longitudinal segregation (as determined from the X-ray fluorescence analysis) was a minimum. Laue single-crystal analysis and metallographic analysis was used to verify if a slice was single or polycrystal. Any grain boundaries were clearly visible in the as-cut and polished condition. In ad-

Jan 1, 1964

Arizona ROBERT E. TALLY, Chairman CARL E. ~IILLS, Secretary-treasurer, P. 0. Box 1462, Jerome. Ariz. W. S. BOYD THOMAS H. 0. O'BRIEN F. W. MACLENNAN Boston Meets first Monday each winter month GAL~N H. CLEVENG~, Chairman HOLCOMB J. BROWN, Vice-chairman F. I,EROY FOSTER Secretary-treasurer Room 8-219, Mass. lnst: of Tech., Cambridge Mass. A. E. WELLS H. A. WENTWORTH

Jan 1, 1928

By E. R. Hoskins

Results of a primary stress measurement investigation conducted on the 1100 copper ore body of the Mt. Isa mine, Mt. Isa, Queens., Australia, are presented in this chapter. The investigation started in September 1965, after discussion with the engineering staff at Mt. Isa, and consisted of both underground or in-situ tests at Mt. Isa and laboratory tests on Mt. Isa rocks and stress measurement techniques at the Australian National University in Canberra. Underground stress measurements were made in and adjacent to the 1100 copper ore body. The primary stress measurement site was in J 32 west crosscut on 14 Level. Approximate coordinates on the mine grid are 3000 north, 1650 east. The vertical depth below ground surface at this point is approximately 2180 ft. Some preliminary measurements were made in M 30 west crosscut on 13 Level, coordinates 3000 north, 2000 east, depth beneath the surface approximately 1990 ft. Additional flatjacks were installed on 11 Level in L 30 west crosscut, coordinates 3000 north, 2200 east, and depth beneath the surface approximately 1580 ft. All of the sites were in rock that from a mining engineering viewpoint must be considered extremely sound. The 13 and 14 Level crosscuts were approximately 14 ft on a side and nearly square and the 11 Level crosscut was approximately 10 ft on a side. All of the crosscuts had been standing open for several years and no artificial support of any type was necessary. Extraction openings hundreds of feet on a side have been made in this mine in similar rock and these have remained open also without additional support (see Davies 1 for a recent summary of mining techniques and conditions). The geology of the Mt. Isa mine has been most recently described by Bennett.2 Briefly, Mt. Isa is a silver-lead-zinc and copper mine in a series of Precambrian siltstones, shales, and bedded carbonates that strike north-

Jan 1, 1972

By P. Somasundaran

Flotation of minerals has usually been discussed in terms of solid-liquid interfacial phenomena. This paper discusses the relative importance of phenomena such as collector adsorption at other interfaces formed between the bubble, liquid and solid. Adsorption of collector ions of various chain lengths at liquid-gas and solid-gas interfaces has been obtained. The data have been analyzed under conditions corresponding to those of flotation to show the significant role of collector adsorbed on the bubble surface in determining the bubble-mineral attachment required for flotation, and consequently to suggest consideration of this role in the development of better flotation conditions. Vacuum flotation of quartz with alkyl ammonium acetate reported in the foregoing paper1 showed that the collector chain length has an effect on flotation even at concentrations below those necessary for hemi-micelle association of the hydrocarbon chains at a solid-liquid interface. This chain length effect might be explained by the following arguments: Hydrocarbon chains find it energetically favorable to be in a medium of low dielectric constant. Considering the possibility of an iceberg structure at the solid-liquid interface, such a structure would produce a region of lower dielectric constant at the solid-liquid interface than in the liquid phase, because the dielectric constant of ice is 2 to 3,2 while that of water is 80. Depending on chain length, this difference will certainly cause even individual ions to adsorb in higher quantities at the solid-liquid interface. Another mechanism to consider is the possible formation of dimers, trimers, etc and chain length would influence this formation. But, above all, the chain length effect on flotation at concentrations of low adsorption at the solid-liquid interface could be due to the significant but often-neglected role of the collector adsorption at the bub- ble surface. Collector ions or molecules are adsorbed both at the solid-liquid interface and the liquid-gas interface. Below the concentration for hemi-micelle association at the Stern plane adjacent to the surface, the bulk of the collector ions adsorbed at the solid-liquid interface are in the diffuse part of the double layer. If such systems, where there is a gas bubble coming in contact with the solid surface, are to achieve some degree of electroneutrality, those collector ions would have to migrate from the diffuse part of the double layer to the region directly adjacent to the surface during the induction period when the bubble is making contact with the solid. The time necessary for this migration would contribute to the induction period required for creation of the solid-gas interface. It seems reasonable that the induction period could be reduced sufficiently for flotation to occur if these collector ions were carried to the surface by the bubble. In an attempt to ascertain whether or not the bubble could possibly have sufficient collector ions at its surface to meet the requirement mentioned above, the adsorption density of the collector ions at the liquid-air interface was determined. For this purpose, the surface tension of alkyl ammonium acetate solutions was determined as a function of concentration. Adsorption densities of the collector at the liquid-gas interface were calculated using the Gibbs adsorption equation: where y is the interfacial tension and ri and pi are the adsorption density and the chemical potential, respectively, of the chemical species, i. Using the convention that the adsorption density of water at the interface is zero, the following relationship is obtained for the liquid-gas interface where lg refers to liquid-gas interface and RA+ refers to the alkyl ammonium ions. For dilute solutions, rf^-wri^&rfwW [3] where C is the concentration of the collector ions in solution. l?:: can now be evaluated using Eq. 3 and surface tension measurements.

Jan 1, 1969

By Kefton H. Teague

Olivine is a mineral containing a mixture of forsterite (Mg2SiO4) and fayalite (Fe2SiO4) in solid solution. The name olivine was first applied by Werner in 1790 (Hunter, 1941) because of the olive-green color of the mineral. Olivine is the principal component of the rock dunite, which itself is a member of the peridotite group of ultrabasic igneous rocks. European uses of the terms olivine and dunite are somewhat different than US usage. In commerce European usage defines dunite as containing 36 to 42% MgO, 36 to 39% SiO2, and loss on ignition of approximately 10%. The term olivine is used to designate a material containing approximately 85% forsterite, with a chemical composition of approximately 45 to 50% MgO, 40 to 43% Si02, 5 to 8% Fe2O3, and ignition loss of 1 to 2%. Uses The principal use of olivine is in various applications involving hot metal. Table I shows the best estimate available as to the amount of olivine consumed by various industries worldwide. In excess of 90% of world uses involve hot metal, with approximately 75% as a slag conditioner in the blast furnace production of pig iron. Approximately 15% of total olivine usage is as a special foundry sand in mold making for the brass, aluminum, magnesium, and manganese steel foundries (Schaller, 1957, 1958; Snyder, 1957; Anon., 1977). Olivine was first used as an industrial mineral in the early 1930s for a refractory material (Anon., 1970; Hunter, 1941). As a refractory raw material, olivine was first introduced in the United States as hand-cobbed, selected, shaped blocks of crude olivine. This use met with limited success. More recently, finely ground olivine blended with MgO and pressed into bricks, which are then fired, has found use in glass tank furnaces and open-hearth furnaces. Ramming or gunning mixes for basic furnace linings also utilize olivine. Olivine has been used in ladle linings with varied success. In Europe, substantial tonnages of olivine are utilized in refractory brick for night storage heaters (Anon., 1970). A limited amount of olivine has been used in the past as a fertilizer (magnesium source) and has been fused with rock phosphate to produce a magnesium phosphate as a plant food. The relatively high magnesia (MgO) content of olivine also attracted attention to it as a potential source of both magnesium compounds and as a source of metallic magnesium (Bengston, 1956; Hunter, 1941). The use of olivine as an additive in the blast furnace is relatively new, having been developed during the last decade. J.W. Currier (Private communication, 1978) describes the behavior of olivine in the blast furnace as follows: Olivine (Mg, Fe2, Si04) represents a unique lime-free source of magnesia and silica as a blast furnace charge component. Only recently has the magnesia-rich mineral been recognized as beneficial cleaner for blast furnace experiencing the problems associated with excessive alkali inputs and/or low coke stabilities. For some time it has been known that alkalis tend to recycle and accumulate in blast furnaces. In the high temperature region of volatilization the elemental alkalis formed attack the integrity of the graphite structure. This alkali attachment is enhanced when poor coke is used. Higher in the furnace stack volatile alkali cyanides condense and oxidize. This accumulation of alkalis tends to agglomerate the burden materials, producing scabs and scaffolds. These structures not only inhibit the downward movement of burden materials and the upward passage of wind, but also lead to erratic furnace performance

Jan 1, 1983

By L. W. Pommier, F. B. Brien

The Rheological properties of pulps are non-Newtonian in character and more than one viscosity parameter is necessary to describe their behavior, therefore, the single term 'apparent viscosity' which has been used in the past may be misleading. The study reported in this paper uses a dimensional analysis based on the Ostwald-de Waele shear stress-rate of shear model for non-Newtonian liquids to develop velocity and resistance equations for falling spheres. An electronic monitoring apparatus was assembled for determining the velocity of metallic bodies as they fall through opaque liquids and suspensions. By means of this apparatus the behavior of the viscosity parameters of the Ostwald-de Waele model and the applicability of the proposed equations were examined for a number of non-Newtonian liquids. The validity of the equations for these liquids was confirmed. Preliminary data collected using solid-liquid suspensions established the validity of the form of the basic equations for these systems. The differential movement of solid particles through solid-liquid pulps and suspensions is very important LO many branches of engineering, such as minerals processing, soil mechanics, ceramic slip processing, oil well drilling-mud technology, materials-handling in pipelines, and many others. There is a dearth of fundamental knowledge on the flow resistance encountered by immersed bodies moving through solid-liquid suspensions. The resistance offered by Newtonian liquids to the movement of free settling spheres is well described for laminar and turbulent conditions by Stokes' and Newton's Laws, respectively. However, problems are encountered when attempts are made to extrapolate these simple relationships into solid liquid suspensions. The rheological properties of pulps are such that they are non-Newtonian in character;'" that is, the applied shearing stress and resulting rate-of-shear are related by non-linear functions, and thus, in the simplest case two viscosity parameters are necessary to describe their rheological properties. For this reason the single term 'apparent viscosity' which has been commonly used to explain the flow resistance of suspensions and non-Newtonian liquids may be misleading. It is realized that a rigorous analysis of the rnechanisms of momentum transport of liquid-solid systems is complex indeed. There are many variables that affect the rheological properties of the systems such as density, size, shape, and surface energy of the suspended solid and density and viscosity of suspending liquid, as well as the solid to liquid ratio. However, it was felt that a useful contribution to the knowledge of the behavior of suspensions could be made by examining the systems in terms of the basic fundamentals of nowNewtonian flow. This has led to the development, by means of dimensional analysis, of velocity and resistance equations, using two viscosity parameters to describe the velocity of penetrating bodies and the flow resistance encountered by these bodies, as they pass through non-Newtonian systems. THEORY In order to examine the effects of the rheological properties of solid-liquid suspensions on the movement of immersed bodies it is appropriate to start with non-Newtonian liquids and develop equations, analogous to those of Stokes and Newton, for laminar and turbulent flow respectively, from which quantitative information may be obtained. Further investigation would then be directed at the complex suspension systems, and the effects of the many variables on the velocity and resistance equations. Liquids are classified on a basis of viscosity which may be defined as the relationship between applied shear stress and resulting rate of shear?-'* Pure single phase liquids composed of small light molecules behave as Newtonian liquids, having a single viscosity parameter since the shearing stress and rate-of-shear are related by a linear function. Bingham plastics are similar but have a yield stress. Of particular importance in our investigation are dilatant (shear thickening) and pseudoplastic (shear thinning) non-Newtonian liquids, with and without yield values.

Jan 1, 1968

By A. L. Barnes

A number of reservoirs have been partially invaded by bottom water. Water flooding such reservoirs can be especially inefficient if the oil has a high viscosity because injected water will under-run the oil and emerge at producing wells without having displaced much oil. A possible means of improving water sweep efficiency would be to precede the water flood with a slug of water purposely thickened with a chemical additive. This possibility has been studied with a scaled laboratory flow model. The investigation was carried out on a model representing a 20-acre five-spot with one set of reservoir condition~. Displacements were performed with water, with viscous-water slugs of 10 and 25 per cent of the pore volume followed by water, and with all viscous water. Displacement tests were made at several rates of injection. For all cases, compared at the same producing water-oil ratio, an increase in rate resulted in an increase in volumetric sweep. The larger the quantity of viscous slug injected, the greater the crossflow of oil ahead of the displacing front and, thus, the lower the WOR during that period of a displacement. This investigation indicates that the injection of aqueous viscous slugs in this type of system would give some additional benefit over conventional flooding by (I) reducing the life of the flood, (2) reducing lifting costs and (3) increasing ultimate recovery. The benefits of a viscous-slug displacement would warrant its use if the viscous water could be created for a few cents per barrel. INTRODUCTION The most appropriate method for water flooding oil reservoirs which have been partially invaded by bottom water has been a problem of considerable interest. Such reservoirs, having good vertical permeability and unfavorable mobility ratios, are difficult to produce efficiently under normal waterflood procedures. Even though the injection wells have been plugged back above the oil-water contact and the water zone has been squeezed off, injection water will enter the formation and not only displace oil, but also much of it will displace the bottom water, thus creating a high producing water-oil ratio at the start of a flood (see Fig. 1). Since the rate of injection and the viscosity of the displacing fluid are the more easily controlled physical parameters of the reservoir, it is quite natural to study their effects on the volumetric sweep of the oil zone and on the producing water-oil ratio. Increasing the viscosity of the displacing fluid has two disadvantages—it reduces the maximum rate of injection into the reservoir, and it costs more than water. It was thought that the injection of a viscous-fluid slug, followed by water, would minimize these two disadvantages, increase the volumetric sweep of the oil zone and reduce the producing water-oil ratio. Water with an additive to increase viscosity would probably be the most effective. The primary purpose of this investigation was to determine the feasibility of injecting viscous-water slugs followed by water to improve or hasten oil recovery while reducing the producing water-oil ratios. The effect of injection rate upon recovery was also investigated. A laboratory model, scaled to a 20-acre five-spot prototype with one set of reservoir conditions, was constructed. Laboratory studies of displacements with (1) water, (2) viscous-water slugs of 10 and 25 per cent of the pore volume followed by water and (3) all viscous water were performed at several rates of injection. THEORY OF SAND MODEL SCALING There are two conventional means of determining scaling criteria. These are dimensional analysis and inspec-tional analysis. Determining scaling criteria by dimensional

By Frank C. Appleyard

Gypsum, the dihydrate form of calcium sulfate, has a history of usefulness to man dating back several thousand years, and a worldwide industry has been built on the mining and processing of this versatile industrial mineral. However, anhydrite, the other principal calcium sulfate mineral has very limited use, so much so that separate statistics for it are not always kept, but are usually included with those for gypsum. Although often found in close association, the two minerals have important chemical differences in that anhydrite is the anhydrous form of calcium sulfate (CaSO,) whereas gypsum is the dihydrate (CAS0;2H20). These two molecules of combined water result in significant differences in hardness, density, and solubility of the two minerals. However, of most importance is the difference in thermal properties wherein gypsum, upon the application of a modest amount of heat, can be converted to the hemihydrate of calcium sulfate (CaS0;Vi H,O) or plaster of paris, an intermediate product upon which is based over 90% of the value of all calcium sulfate end products. Anhydrite, on the other hand, is inert at these temperatures and its uses have been limited to only those few cases where calcium sulfate in the anhydrous form may have an advantage. The earliest known use of gypsum plaster dates back some 5000 years to the time of the Pharaohs of Egypt who had discovered that gypsum rock, when exposed to fire, broke down into a powder which when mixed with water would form a putty that could be "plastered" on a rough mud brick or stone wall to make a smooth finish. It was used down through the centuries in a limited way for ornamental purposes, but did not achieve wide acceptance because of its quick (25 to 30 min) setting or hardening time which made it difficult to use. The first real understanding of gypsum chemistry was developed in France about 1755, and the gradual growth of its present utilization dates from that time. In the United States, the first utilization of gypsum was to grind it to a fine material for use as a soil conditioner at about the time of the Revolutionary War, and the term "land plaster" for ground gypsum has remained in use. Another cementituous material-lime or calcium oxide-had become the usual plastering material, but by about 1870 a method for retarding the set of gypsum plaster was discovered and it has today almost completely replaced lime as a plastering material. In recent years, gypsum products sold in the United States have reached a total valuation of approximately $500 million per year as illustrated in [Table 1].

Jan 1, 1975

By C. C. Harris

A critical literature review leads to a descriptive model of tumbling mill operation based upon energy partition concepts and the necessary requirements for particle fracture. As grinding proceeds into the ultra-fine region, conditions which are of little significance during normal operations gradually become controlling. These involve increasing resistance to fracture and an increasing tendency to aggregate as particles become smaller, and a growing fraction of the power input being consumed fruitlessly. The result is that fineness asymptotes to a maximum value as comminution proceeds indefinitely; thus where t is time, p and n are experimentally determined parameters, and Ø is a measure of fineness, which is presumed to be proportional to specific surface area, or proportional to the reciprocal of the size modulus (provided that the distribution modulus remains constant with time), or both. Ø, is the asymptotic value of Ø and is a measure of the grind limit. A method for its graphical determination is given. In a previous paper1 the physical and mathematical principles requisite to a study of the role of energy in comminution were reviewed. The micro-process of comminution — or the comminution event — can be investigated in terms of (a) the magnitude of the force-field localized around the individual particles which gives rise to the stresses generated in the particles, which in turn induces their fracture, and (b) the distribution of fragment sizes, should the event prove fruitful. The entire fragmentation operation can be considered to be the totality of its individual events, and in order to obtain a single independent variable of the process it is necessary to transform and sum the local stresses in terms of energy.1 This energy, however, will account for only a fraction of the energy input to the comminution process, the actual magnitude depending upon the kind of mill and several related factors. From the comminution viewpoint the primary function of a mill is that of stressing as many as possible of the individual particles of the charge to failure, with the maximum economy of energy expenditure. This is difficult indeed to achieve, for stressing a particle does not always break it, while the overwhelming portion of the energy input is involved with various internal mill processes which — almost incidentally — determine the magnitude, frequency, and manner in which the forces are applied to the particles. Essentially, these processes depend upon the mill dimensions, loading and speed, and they may be little affected whether fracture occurs or not. These processes must be delineated if a complete description of the role of energy in comminution is to be given; the energy account sheet1 (Fig. 1) in showing how the energy is partitioned for the requirements of the several functions it performs, provides a framework for the development of a model of the comminution process. Actual numerical values for the variables appearing in Fig. 1 will depend upon the mill, materials, and operating conditions. A possible general relationship between the variables will be suggested in this paper. Before proceeding further, a cautionary note must be issued. It was pointed out in an earlier paper' that while energy input is not changed by increasing the power and decreasing the time in the same proportion, and vice versa, the results of the process in terms of particle fineness may be different. Thus, although energy is chosen as the independent variable of a comminution process, it is not absolutely independent, and care must be exercised to ensure that it is used within its range of valid application. Time has the necessary independence, and it will be used in place of energy where it is appropriate. The residence time in a mill is usually of the order of minutes. Under these conditions the particles are subjected to "... a relatively constant fracture producing environment".2 However, under the more rigorous conditions of greatly extended time, which pertain in ultra-fine grinding, indications are that the fracture producing environment no longer remains constant; this is the major subject of this paper. At this extreme limit the mill is probably taxed to its utmost, and at the same time the bulk material properties are becoming closer to ideal, while the physico chemical effects associated with surfaces, edges and corners are multiplying. (The edge length per unit volume is proportional to the square of the specific

Jan 1, 1968

By David B. Brooks

Identified potential resources of lead and zinc are lower, relative to reserves, than the same ratio for other metals, Either there is little material below present grades or, if it exists, there are no data on it. The author examines both these factors in detail, and also introduces a third possibility. In their 1961 monograph, The Future Supply of the Major Metals, Bruce Netschert and Hans Landsberg noted that identified potential resources (that is, known but submarginal resources) of lead and zinc were much lower relative to reserves (that is, known and supermarginal resources) than was the same ratio for other metals.' Put another way, it seemed that for such metals as iron, manganese, copper, and aluminum, slightly more favorable economic conditions or modest advances in technology would greatly increase reserves by permitting the exploitation of vast quantities of leaner or deeper or otherwise less valuable mineral deposits. But for lead and zinc, Netschert and Landsberg concluded that either: "(1) there is relatively little material below present cutoff grades; [or] (2) such material exists, but for some reason there are no data.'12 This situation, which they called "the lead-zinc anomaly'' has been subsequently discussed by other authors. The purpose of this paper is to carry the discussion further by examining the evidence in favor of (1) and (2) and by advancing a third alternative. There are at least two reasons for devoting time to the lead-zinc anomaly. First, while it is unlikely that we shall have to turn to alternative lead or zinc resources in the near or middle-term future, the longer run resource picture for the two metals is not so certain.3 Both within the United States and for the world as a whole, new discoveries will have to come at a fair pace to keep up with growing rates of consumption. Thus, it is important to see whether there exist lower grade or nonconventional potential sources of two such useful metals that we could turn to at some time in the future. The second reason for studying the lead-zinc anomaly is also related to resource adequacy, but is of more general significance. Depending upon whether the anomaly is technologic, geochemical, spatial, or temporal in origin, we shall be able to draw some conclusions about the resource picture for other metals. Can we expect the apparent pattern of lead-zinc resources to be repeated? If so, will technologic advances in either exploration methods or mineral processing be able to alter the pattern? Or is the pattern unalterably set by geochemical distribution? Most important, are metals characterized by what seems to be an anomaly, different in any way from metals for which low-grade or nonconventional sources already have come to be exploited, as the porphyry deposits have for copper. In sum, investigation of the lead-zinc anomaly represents a case study combining both physical and economic aspects that may open up a neglected area in evaluating mineral resource adequacy. WHAT IS THE LEALLZINC ANOMALY? There are two dimensions to evaluations of the potential of any mineral resource? The first involves the degree of certainty that we ascribe to the estimate: how much do we know about the size of the resource as a result of geological mapping, exploration, and mine development? This dimension is expressed by the terms measured, indicated, and inferred reserves (and, if you wish, 'undiscovered reserves'), all of which terms carry with them the implication of exploitability under current cost-price conditions. The other dimension to evaluations of a mineral resource involves the economic limits of the estimate: how will the size of the resource vary with different (usually more favorable) cost-price conditions? (This economic dimension should be understood broadly to include all factors bearing on the cost-price relationship. In this sense it subsumes technology because any resource is exploitable at some cost; the role of technology is to bring cost down.) The latter dimension is expressed in the terms potential or sub-marginal 'ore,' and is logically quite independent of the former. For example, we have relatively good measurements of the tonnage of manganese in low-grade deposits in this country, though they are too lean to be considered reserves; on the other hand, we are much less certain of our measurements of new lead and zinc deposits in Missouri, though there is no question but that there is a sizable reserve. Thus, it may be uncommon but is not a contradiction to talk of measured submarginal ore or inferred potential ore.

Jan 1, 1968

By William E. Ford, Edward Salisbury Dana

1. Variations in the Forms and Dimensions of Crystals 2. Imperfections of the Surfaces of Crystals 3. Variations in the Angles of Crystals Internal Imperfection and Inclusions 264. The laws of crystallization, when unmodified by extrinsic causes, should produce forms of exact geometrical symmetry, the angles being not only equal, but also the homologous faces of crystals and the dimensions in the directions of like axes. This symmetry is, however, so uncommon that it can hardly be considered other than an ideal perfection. The various possible kinds of symmetry, and the relation of this ideal geometrical symmetry to the actual crystallographic symmetry, have been discussed in Arts. 14 and 18 et seq. Crystals are very generally distorted, and often the fundamental forms are so completely disguised that an intimate familiarity with the possible irregularities is required in order to unravel their complexities. Even the angles may occasionally vary rather widely.

Jan 1, 1922

By C. R. Pelley

Abstract-This paper describes the analytical characteristics of Western subbituminous coal and the manner in which these characteristics apply to their use in a utility-sized steam generator. It compares these characteristics with those of typical Midwestern coal and Eastern bituminous coal. The paper also reviews in detail the design considerations that must receive attention when various blends of these three coals, or any combinations thereof, are planned to be used. This research paper describes variations in analytical and utilization characteristics when coals from different origins are blended in order to achieve a predetermined sulfur content for the purpose of predicting sulfur oxides emissions as they affect environmental regulations and the resulting alterations in utilization characteristics such blending would cause, and how such blends of coal would affect a utility-sized steam generator.

Jan 1, 1978

By G. W. Thomas

A simplified mathematical model of underground conduction heating in a system of limited permeability is presented. The model applies to underground retorting of oil shale, or to reservoirs containing extremely heavy oils. We assume that heat is introduced at a constant rate into a horizontal fracture which communicates between wells. The radial temperature distribution along the fractured surface is approximated by a step-function. Heat transfer away from the fracture is assumed to be by vertical conduction, and all convection effects are neglected. The model also takes into account the possible temperature dependence of thermal conductivity. A general expression for calculating the growth of the step-function temperature distribution with time is derived. The use of this expression and solutions to the one-dimensional heat equation make it possible to construct isotherms. Expressions for calculating .oil recovery, well spacing and heat efficiency are also given. An example calculation is presented for the conduction heating process in oil shale. Finally, the effect of the heat transfer coefficient between the gas and the fracture boundaries is investigated. INTRODUCTION Thermal recovery processes of oil recovery fall into the four general areas of hot fluid injection, forward combustion, reverse combustion and conduction heating. The first three of* these processes have been rather extensively studied in the past decade from both the experimental and theoretical points of view. As a result, it is possible to make reasonable engineering predictions and analyses of these processes. Little attention has been devoted, however, to the conduction heating process other than to note its possible utility.I To a certain extent, conduction heating cannot be divorced from the other regimes cited above, insofar as these provide the source of heat energy. In the conduction heating process, heat is introduced (either by combustion in the forward or reverse mode or by hot fluid injection) into a small fraction of the total reservoir thickness. This fraction may be either a streak of high permeability or an interwell fracture. Heat penetrates by conduction into the adjacent, less permeable regions of the oil-bearing rock, where the direction of conduction is essentially perpendicular to the streak or fracture. The heated product then drains by gravity or is gas driven to production wells. Conduction heating is probably most applicable to systems containing immobile bitumens such as tar sands and oil shale deposits and perhaps to low-permeability reservoirs containing highly viscous crudes. The mechanism also acts in combination with other thermal processes where fingering or overriding of a bed occurs. It seems probable that in at least one field test, conduction heating of this type was very influential.2 In this presentation we give a first approximation to some of the quantitative aspects of conduction heating. Marx and Langenheim3 treated a similar problem where they focused attention upon the injection interval, which spanned the total reservoir thickness. In their model, conduction heat losses to the bounding media imposed a practical limit on the calculated heated area. In the present study, however, we shall confine the injection interval to a small fraction of the reservoir thickness and assume it has no heat capacity. We therefore direct our attention to regions outside the injection interval into which the conduction of heat is beneficial. In particular, we will endeavor to locate specific isotherms in the media bounding the injection interval. Furthermore, we will construct our model to allow the thermal conductivity to vary arbitrarily with temperature. Thus the model will be applicable to underground retorting of shale where variations in thermal conductivity may be important. THEORY We consider the rock matrix to have no or, at best, a very limited permeability; consequently a

Jan 1, 1965

By C. K. Ferguson, J. A. Klotz

This paper describes experimental investigations conducted at the California Research Corporation's model oil well. The first part describes filter loss from several drilling muds through bore hole walls during mud circulation and drill string rotation. The effect of mud properties and drill string rotation with mud circulation is described. Filtration from a bore hole full of drilling mud, not circulating, but under pressure for extended time periods, is also discussed. The second part describes filter loss to permeable formations from beneath a drilling bit where filter cuke has no opportunity to develop appreciable thickness. If potential flow theory is applied to predict filtrate invasion from this hole bottom, targe invasions arc calculated. But model well experimentation shows that filtrate invasion from the hole bottom is controlled by mud particles that penetrate the formation ahead of the bit. This experimentation provides data to estimate the effect of mud particle penetration on fluid loss to formation. The third part presents an estimate of mud filtration during drilling of a well. INTRODUCTION As oil wells are drilled by the rotary method, drilling mud circulates up the annulus between drill pine and well wall. Drillers adjust mud density so that the pressure at the bottom of the mud column is several hundred psi greater than the pressure of reservoir fluid. As a result of this pressure difference, the liquid part of the mud filters into the rock around the bore and mud solids deposit as a filter cake on the well wall. For many reasons the petrogleum industry, within the past 20 years, has spent much money and energy to determine the volume of mud filtrate that enters rock around the well bore and dedicated much research effort to reduce this volume. Among the reasons for attempts to determine the volume of mud filtrate and to reduce this volume are the following: 1. If filtrate damages the permeability of oil sand, the resultant damage to oil well productivity will depend on the distance that the filtrate invades the oil sand; reduction of filtrate volume may, therefore, increase well productivity. 2. Filtrate that penetrates shale sections may cause the shale to swell and to slough into the well bore. Uncontrolled sloughing may stick drill pipe. Reduction in filtrate volume may reduce drilling trouble. 3. Electric log resistivity curves are changed by invasion of a mud filtrate; the change depends on the depth to which filtrate invades. Knowledge of this depth is necessary before resistivity logs can be interpreted accurately. For these reasons, specifications the place an upper limit to drilling mud filter loss are now written into almost all drilling programs. These specifications are based on APT Recommended practice 29, Standard Field Procedure for Testing Drilling Fluids,' which describes a static filtration test operated at 100 psi filtration pressure and at ambient temperature. Although this test is adequate for mud control, it cannot be used to compare filtration properties of different muds. Schremp and Johnson' showed, for example, that mud with a low API filter loss does not necessarily have low filter loss at bottom hole temperature and pressure. Also, no information has been available about the effect of bottom hole mechanics (mild circulation, drill string rotation, and bit action) on mud filtration. This paper discusses filtration data measured in the California Research Corporation's model oil well, which models closely oil well bottom hole geometry and hydrodynamic conditions. The filtration processes that

Jan 1, 1955

By Milton E. Wadsworth, W. Martin Fassell, William H. Dresher

A study of the rate of dissolution of molybdenite (MoS2) in alkaline solution was carried out under carefully controlled conditions. Effects of temperature, oxygen over-pressure, and KOH concentration were evaluated. Studies were made in the temperature range 100°C to 175°C and in the pressure range 0 to 700 psia of oxygen. Under these conditions molybdenite was found to leach according to a linear mechanism. Both oxygen over-pressure and KOH concentration were found to control the rate of leaching. The mechanism has been explained in terms of adsorption of oxygen at the molybdenite surface followed by configurational rearrangement of the adsorbed molecules. The hydroxyl ion dependency is believed to be diffusion-controlled. Laboratory batch studies have shown that molybdenite can be readily dissolved in alkaline solutions under moderate conditions of temperature and pressure. Commercial application of this process to the production of ferro-molybdenum and molybdenum chemicals is promising in view of the ease of dissolution of molybdenite and the relatively noncorrosive conditions involved in the process.

Jul 1, 1956

By Betty J. Laswell, Gerald W. Laswell

If recent trends in the rotary drill market are indicative of future surface mining operating practice, then the move to scaled-up mining equipment by manufacturers may soon be over. Of the 48 different rotary drills currently produced by 12 manufacturers, over 60% were introduced within the past five years. By far, the new drills have been in the "small" class, capable of producing up to a 229-mm-diam (9-in.) blasthole with 222 kN (50,000 lb) or less of down pressure. New rotary drills in the "large" class, capable of producing a 311-mm-diam (12 1/4-in.) blasthole with up to 423 kN (95,000 lb) down pressure, have also been prominent. In the super-size category, new drills producing blasthole sizes to 444-mm-diam (17 1/2-in.) with up to 578 kN (130,000 lb) have been minimal.

Jan 7, 1978

TO THE BOARD OF DIRECTORS AND MEMBERS OF THE AMERICAN INSTITUTE OF MINING AND METALLURGICAL ENGINEERS GENTLEMEN: Submitted herewith are the report of the Treasurer for the year 1939 and reports for the same year of the following standing committees: Admissions, Membership, Papers and Publications, Mining and Metallurgy (Magazine), Library, Speakers for Local Sections and Student Societies, and Student Relations. These reports present additional details. Membership.-For the second year in Succession membership reached a new high level for all time, as indicated in the accompanying tabulation in which "Members" includes all categories except Student Associates. [END 1938 END 1939 NET GAIN Members9, 57 610, 163 587 Student Associates 2,898 3,760 862 12,474 13,923 1,449] Net gain in membership (aside from Student Associates) was 587 compared with 744 in 1938, despite the fact that applications received in 1939 exceeded those received in 1938 (1271 against 1162). The smaller net gain is accounted for in three ways: (1) A greater lag in enrollment of those elected in the last quarter of the year; (2) an increase in the number of applications involving change of status from Junior Member to Member; and (3) an increase of 167 in the loss by death by resignation and by suspension in 1939 as compared with 1938. Experience shows that at the end of a year of less prosperous conditions in the mineral industries, and, therefore, among engineers engaged in these industries, resignations and suspensions are more numerous. Business and industrial indexes all show 1938 to have been somewhat less prosperous than 1937; but the improvement in 1939 should be reflected in the record for 1940.

Jan 1, 1940

By M. R. Tek, R. L. Nielsen

The scaling laws as formulated by Rapoport relate dynamically similar flow systems in porous media each involving two immiscible, incompressible fluids. A two-dimensional numerical technique for solving the differential equations describing systems of this type has been employed to assess the practical value of the scaling laws in light of the virtually unscalable nature of relative permeability and capillary pressure curves and boundary conditions. Two hypothetical systems — a gas reservoir subject to water drive and the laboratory scaled model of that reservoir — were investigated with emphasis placed on water coning near a production well. Comparison of the computed behavior of these par ticular systems shows that water coning in the reservoir would be more severe than one would expect from an experimental study of a laboratory model scaled within practical limits to the reservoir system. This paper also presents modifications of the scaling laws which are available for systems that can be described adequately in two-dimensional Cartesian coordinates. INTRODUCTION Present day digital computing equipment and methods of numerical analysis allow realistic and quantitative studies to be carried out for many two-phase flow systems in porous media. Before these tools became available the anticipated behavior of systems of this type could be inferred only from analytical solutions of simplified mathematical models or from experimental studies performed on laboratory models. To reproduce the behavior of a reservoir system on the laboratory scale, certain relationships must be satisfied between physical and geometric properties of the reservoir and laboratory systems. Where the reservoir fluids may be considered as two immiscible and incompressible phases, the necessary relationships have been formulated by Rapoportl and others.2-5 Rapoport's scaling laws follow from inspectional analysis of the differential equation describing phase saturation distribution in such systems. It will be recalled that these scaling laws presuppose three conditions: (1) the relative permeability curves must be identical for the model and prototype; (2) the capillary pressure curve (function of phase saturation) for the model must be linearly related to that of the prototype; and (3) boundary conditions imposed on the model must duplicate those existing at the boundaries of the prototype. These three requirements seldom if ever can be satisfied in scaling an actual reservoir to the laboratory system because: (1) The laboratory medium normally will be unconsolidated (glass beads or sand) while the reservoir usually is consolidated. Relative permeability and capillary pressure curves are usually quite different for consolidated and unconsolidated porous media. (2) The reservoir usually will be surrounded by a large aquifer which could be simulated in the laboratory only to a limited extent. (3) Wells present in the reservoir would scale to microscopic dimensions in the laboratory if geometric similarity is to be maintained. In view of these considerations, rigorous scaling of even a totally defined reservoir probably would never be possible. The purpose of this paper is to assess the practical value of the scaling laws in the light of the unscalable variables. This has been done by carrying out numerical solutions in two dimensions to the differential equations describing the flow of two immiscible, incompressible fluids in porous media for a field scale reservoir and a laboratory model of that reservoir. While both the reservoir and the laboratory model were purely fictional, each has been made as realistic and representative as possible. The field problem selected as the basis for the investigation was an inhomogeneous, layered gas reservoir initially at capillary gravitational equilibrium and subsequently produced in the presence of water drive. The laboratory model of this reservoir was designed to utilize oil and water in a glass bead pack. The numerical treatment employed was similar to that of Douglas, Peaceman and Rachford6 and it included both capillary and gravitational forces as

By J. E. Sandor, P. F. Schmidt

A general review of the present knowledge of the semiconductor/oxide interface is given, with emphasis on silicon and germanium. The electrical properties of clean surfaces and the changes that occur upon oxidation are described. A brief disczcssion of the methods and mechanisms of oxidation of silicon is given, and the interaction between the semiconductor substrate and the oxide phase is considered. Physical properties of the oxide film, charge storage effects due to the dielectric, and some device applications of oxide films on semiconductors are discussed. THIS paper will be heavily preoccupied with the elemental semiconductors germanium and silicon. Undoubtedly some injustice is done thereby to other semiconductor-oxide systems, but it is not readily possible to cover all aspects of so vast a field in the present review. In considering the semiconductor/oxide interface, we may start out by discussing briefly an idealized clean semiconductor surface, and may then follow the changes brought about by oxidation, as the oxide is allowed to grow progressively thicker. The references given are not a complete list, but are to be taken as guides to the literature. Tamml suggested in 1933, based upon the study of a one-dimensional asymmetrical potential model, that localized surface states may appear at the surface of a crystalline lattice; it was pointed out by Fowler that these states should occur in pairs. shockley3 examined the origin of such surface states on the basis of a more general one-dimensional model and found that surface states may appear in the forbidden region between the highest filled and the lowest vacant band. This happens when the two bands overlap, as, for instance, the "s" and ('p" bands of the diamond structure. In a three-dimensional model these levels would produce a surface band which is half-filled for diamond, and the number of surface states should be approximately equal to the number of surface atoms. This picture of the surface has been refined by more recent theoretical work, like Handler's4 and Koutecky and Tomasek's~ without introducing essential modifications. When these concepts were applied to semiconduc-

Jan 1, 1965