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By C. B. Clark, W. H. Bruckner

Since the end of World War II 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. Mun-roe 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 concerning cavity liners:1'2 I. The optimum wall thickness of a conical cavity liner is dependent upon the apex angle of the 'One as well as On the base diameter of the charge. Acute apex angles require thinner walls for optimum perfmnance and more obtuse angles require thicker walls for the same base diameter' 2. 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, tensile 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 C. B. Clark, W. H. Bruckner

Since the end of World War II 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. Mun-roe 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 concerning cavity liners:1'2 I. The optimum wall thickness of a conical cavity liner is dependent upon the apex angle of the 'One as well as On the base diameter of the charge. Acute apex angles require thinner walls for optimum perfmnance and more obtuse angles require thicker walls for the same base diameter' 2. 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, tensile 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 Dr. O’Neil Thomas J., Donald W. Gentry

The greatest of all gifts is the power to estimate things at their true worth. LaRockefoucauld INTRODUCTION The primary reason for performing a feasibility study on a proposed mining venture is to investigate all phases of the proposal in as much detail as necessary to justify either dropping the project or continuing expenditures through the next stage. The economic evaluation component of the feasibility study, therefore, must ultimately be based on information which provides an answer to the question, "What is it going to cost?" Unfortunately engineers preparing feasibility studies never have all the engineering or economic information they would like or need. Consequently, the economic portion of the analysis can only be performed if estimates of the various costs associated with the project are made. Project cost estimates, in turn, require estimates of all the physical factors affecting cost components, including anticipated performance of plant and equipment as well as all pertinent geologic, mineralogic, and metallurgical variables. Before useful cost estimating procedures can be applied considerable data must be collected, compiled, and organized. Preparatory work typically includes organization of cost data available for estimating purposes, development of techniques for updating historical costs, and establishing methods of forecasting prices and costs over the duration of the project. Cost estimates for mining and mineral processing projects involve so many features and variables that it is absolutely essential to have some means by which the vast amount of detail can be organized. It is very important to identify, in as much detail as possible, all the cost data available (historical and developed) to the estimator. These costs, after being properly identified in detail, should be com- piled, stored, updated regularly, and made readily available for use in developing new cost estimates Accessing files of current cost information requires a standardized numerical system of classifying cost data. When uniform definitions and procedures are used, every project record contributes to the common store of estimating data.

Jan 1, 1984

By J. W. Lacey, F. H. Brinkman, J. E. Faris

This paper presents an analysis of the high-pressure, gas-driven LPG-slug process, based on fluid flow tests in areal models. Two types of tests were made. One series was made in low-pressure models which permitted observation of fluid movement. Three completely misci-ble analog fluids were used. A second series of tests was made in high-pressure models using methane, propane and a light refined oil saturated with methane at room temperature and 1,550 psig. Under the test conditions of room temperature and a pressure level of 1,550 psig, the phase diagram for the fluids used is similar to those for many of the field systems where the process is considered for use. A method for using these laboratory data to calculate field performance of the process is outlined. As a result of this work, it is concluded that small banks of LPG (5 per cent HV or less) are not effective in increasing oil recovery in horizontal reservoirs. Znstead, where small banks are used, the driving gas quickly penetrates the LPG bank because of fingering and channeling; and from this point on, the process behaves essentially as an immiscible gas-injection project. The validity of this conclusion was substantiated by: (1) laboratory studies of the effect of rate, model size and mobility ratio on miscible displacement in areal models; and (2) calculation of field recovery, which compared closely with actual field recovery. INTRODUCTION Field applications and pilot tests of the gas-driven, LPG-bank, oil-recovery process are on the increase. Most of these tests are employing small banks (2% to 5 per cent hydrocarbon volume) of LPG, which is miscible with both the driving gas and the oil in place, in an effort to attain an effective yet economical miscible displacement of oil by gas. The expectation of miscible displacement with small banks is based on the concepts that: (1) lengths of solvent-oil mixed zones, measured during miscible displacements in long slim cores, are representative of those that will occur in the field; and (2) areal sweep efficiencies5 measured in electrolytic model studies are applicable to miscible displacement in reservoirs. Our experimental evidence indicates that the mixed-zone lengths and sweep efficiencies mentioned are not applicable to miscible displacement in reservoirs. In this paper we present an evaluation of the gas-driven, LPG-bank oil-recovery process based on fluid flow experiments in areal models. These results are used to predict the performance of a field pilot test of this process, and the results are compared with the actual test results. THE EFFECTIVENESS OF LPG BANKS The effectiveness of LPG banks of various sizes in accomplishing miscible displacement of oil by gas was determined by displacement tests in a model representing one-quarter of a confined five-spot pattern. The model, 12 X 12 X 1/4 in. in size, was packed uniformly with glass beads. It was operated at a pressure of 1,550 psig and at room temperature; the fluids used were methane, propane and refined oil saturated with methane at 1,550 psig. The saturated oil had a viscosity of 1.2 cp at room temperature. The results of these tests are shown in Fig. 1, where recovery is plotted as a function of the volume of fluid injected for: (1) an immiscible-gas drive with an oil-to-gas viscosity ratio of 85; (2) three sizes of LPG banks; and (3) two completely miscible displacements with mobility ratios of 85:1 and 10:1. (The miscible displacement data plotted are the averages of several tests.) The results show that a 2½ per cent bank of LPG does not increase oil recovery over that obtained by immiscible-gas drive. The 7 and 17 per cent banks are, respectively, about 30 and 50 per cent effective (with reference to the M = 85 miscible-displacement curve) in increasing oil recovery at the point where 2½ hydrocarbon volumes (HV) of fluid have been injected. The percentage effectiveness of the banks at a given volume of fluid injected is defined as Recovery by Bank — Recovery by Gas Drive Recovery by Miscible Recovery by Flooding Gas Drive We conclude from these results that banks of LPG smaller than about 5 per cent HV in an individual stratum will cause from little to no increase in oil recovery. This finding was substantiated by work in low-pressure models, which permitted visual observation of fluid movements. In these tests, three completely miscible fluids having the same viscosity ratios as those used in

K. W. Turner, Sail Francisco, Cal. (communication to the Secretary*): The recent papers in the Transactions by Vogt,' Lindgren2 and Weed: on ore-deposits that have formed as a direct result of igneous intrusions, show that deposits of this class are widely distributed over the world, and are occasionally of commercial value. This is especially true if we consider under this head all deposits in the zone of contactrnletamorphism, the origin of which may be ascribed to the gases and vapors generated by the heat of the intrusive rock. Mr. Smith's description of the Chillagoe garnet-formations containing copper, leads one to regard these depoaits as of contactrmetamorphic origin, although he gives certain reaeons for supposing them to be of igneous origin.

Jan 1, 1904

By F. S. Young, K. E. Gray

Drilling tests with a 11/4-in. diameter roller bit were performed on Berea and Bandera sandstones and Leuders limestone using water and two conventional drilling muds as circulating fluids to evaluate the influence of dynamic filtration on penetration rate. The muds possessed widely differing API fluid-loss properties. Mud filtrate was constrained to flow beneath the bit; no filtrate flowed radially through the borehole wall. Rock pore pressure at three different locations ahead of the bit, cumulative filtrate volume, borehole pressure and bit location were monitored during drilling. The rock samples, cored in three orientations with respect to bedding planes, possessed a wide range of liquid permeabilities. and were drilled at borehole-to-formation pressure differentials of 0, 250, 500 and 1,000 psig. The effect on penetration rate of API fluid loss, borehole pressure and rock permeability was studied. Rock permeability damage and pore pressure gradients beneath the bit were evaluated. The importance of borehole-to-formation pressure differential was illustrated for each drilling fluid and rock permeability combination. Penetration rates decreased with increased borehole pressure and reduced fluid loss. The observed penetration rate reduction due to changing fluid Ioss was attributed to decreased filtrate flow and improved mud cake plastering hy the low fluid-loss mud. The reduction in filtrate flow could not be related to spurt-loss phenomena. Rock permeability influences penetration rate through particle invasion ahead of the hit, which damage leads to high pressure gradients. Penetration rate variance with sample orientation was evident for water-drZled samples but less obvious for mud-drilled rocks. Permeability damage beneath the bit ranged from 1 to 3 cm. Maximum damage occurred in the first 0.1 cm. Pressure gradients varied with API fluid 10.s.s and could be correlated with penetration rate. The pressure gradient was found to influence penetration rare in rocks of all permeabilities tested. INTRODUCTION Early microbit and small-scale drilling experiments proved to be invaluable contributions to understanding the mechanics of drilling at depth. For example, the effect of borehole-to-pore pressure differential on drilling rate was demonstrated conclusively by Murray and Cunningham', Eckel' and others .' However, the effects of various drilling fluid properties on drilling rate, particularly filtration, have not been studied extensively on a laboratory basis. Microbit correlations of penetration rate with different viscosity and API fluid-loss muds led EckelV o conclude that viscosity and density. more than API fluid loss, were the most important fluid properties in controlling drill bit penetration rates. Ferguson and Klotz6 studied filtration beneath the bit and stated that the maximum amount of filtrate which could conceivably flow beneath a drilling bit could be described by a potential function associated with flow from a moving disc source. and be characterized by a depth-of-filtrate invasion. Invasion depth is a function of penetration rate, formation porosity and permeability, flooding efficiency, pressure difference between borehole and formation and borehole radius, assuming that no filtrate flows through the borehole walls. Electric analog and experimental measurements were obtained, assuming no plugging of the formation pores. Theoretically, filtrate invasion was predicted to extend from 1- to 15-hole radii beneath the cutting surface; experimental results indicated that the extent of invasion was only Y2 in. Comparing these data with results of core-plugging experiments by Norwak and Krueger' led Ferguson and Klotz to state that the drilling operation apparently contributes to higher filtration rates than are observed in nondrilling core filtration tests in which the core face is jetted and scraped. Glenn and Slusser: in describing a linear filtering system in which a rotating bit continuously scraped mud cake from the surface but did not penetrate Alundum cores, stated that mud-solids invasion and permeability damage of the cores were most severe in the first 2 to 3 cm. The filtrate flow rate through the core was found to stabilize after sufficient time had elapsed for the formation of an internal mud cake whose effective permeability was estimated to be 50 to 300 times as high as that of bulk filter cake. Krueger and Vogel reported core permeability damage depths up to 12 in. during a 5-day exposure period in which filter cake buildup was prevented. Havenaar pointed out that the discrepancy between reported and calculated values of filtrate volume obtained in the experiments of Ferguson and Klotz was due, among other things, to failure of the reported API fluid loss to truly represent filtration beneath the bit. Williams," Pro-koplz and others"" have shown that dynamic filtration tests (where a flow of fluid parallel to the filter surface continually erodes the deposited filter cake until a dynamic equilibrium between wall-shearing forces and normally directed compaction forces is attained) yield higher filtration rates than do static tests. Cunningham and Goinss reported results of drilling tests in impermeable shales. They found that by reducing

By William P. Blake

The Rainbow Lode is situated at Walkerville, in the Summit Valley mining district, Silver Bow County, Montana Territory, about one mile from Butte City. It was so named ill 1876 by Mr. J. E. Clayton, in recognition of the broadly-sweeping curve of the outcrop across the rounded surface of the eastern slope of a granitic mountain, at an elevation of about 6000 feet above the sea-level. It is on the western side of the range which divides the waters of the Missouri from those of the Columbia. History.—The history of the district is an instructive one. The water-courses and flanks of the hills were worked for years for placer gold. Millions of dollars' worth of low-grade gold have been washed out of the surface gravels below the veins of the district. Missoula Gulch and Silver Bow creek, just below Butte, are noted for their rich placers, and they continue to yield largely, producing within narrow limits from $50,000 to $100,000 dollars' worth of golddust yearly. It is ragged vein-gold, and evidently is near its parent source. It is no doubt derived from the disintegration of the veins of the district, and this conclusion was soon forced upon the miners. The veins which were seen outcropping boldly upon the slopes above them were located, and prospecting commenced. These outcrops were found heavily stained and blackened with oxide of manganese, and were porous and honey-combed in places, showing that the quartz was formerly filled with pyritous ores, and that these ores had decomposed and dissolved away, leaving, however, portions of the precious metal behind, especially at and near the surface of the ground. Assays of the croppings gave variable and often contradictory results; but the fact. that these were the outcrops of lodes bearing gold and silver in depth was patent to any experienced observer of mineral veins. The lodes of the district were first brought prominently to notice by Mr. Clayton in 1876, and in October of that year the Alice mine, upon the central portion of the lode, was opened by Mr. Marcus Daly, now so well known as the superintendent of the Anaconda Copper mine, upon another extremely interesting lode, in the same region.

Jan 1, 1888

By W. F. Boericke

THE recent completion by the United States Aluminum Company of a $4,000,000 addition to its plant at Massena, N. Y., consisting of a large blooming mill and structural mill, gives this organization, a subsidiary of the Aluminum Company of America, the distinction of possessing the largest aluminum rolling mill in the world, as well as the first mil1 in this country to roll aluminum exclusively. The plant is located near the international boundary line between Canada and the United States, about 3 miles from the St. Lawrence River, to take advantage of the development of cheap hydroelectric power which is needed not only for the manufacture of structural shapes from the ingots, but in the reduction of alumina to the metal by the well-known Hall process as well. A power canal from the St. Lawrence River to the power house on the Grasse River at the plant provides for the waterflow, which, coupled with a drop of 47 ft. in 2% miles, generates 80,000 hp. through vertical turbines. An additional 60,000 hp. is purchased.

Jan 1, 1930

By J. E. Hilliard

Various methods are given for estimating the number per unit volume and average size of convex particles from measurements on a projection through a slice of the structure. The determination of the size distribution is considered specifically for spherical particles. The results are applicable to any type of transmission microscopy and also to the correction of measurements made by reflected light on semitransparent materials. WITH the advent of electron transmission microscopy, the metallurgist is confronted with the problem of relating a projected image to the three-dimensional properties of the structure. This paper deals with the estimation of the number per unit volume and size of particles dispersed in a matrix. The case of convex particles will first be treated (the results will be applicable as approximations to particles of more general shape) and then spherical particles will be considered specifically. The latter represent a special case frequently encountered in practice and one which is also amenable to a calculation of the effect of overlap on the observed particle-size distribution. Although the present treatment was prompted by the needs of the electron microscopist, the results are applicable to transmission studies with any type of radiation. In addition, they can be used in the analysis of semitransparent materials by reflected light, the depth of light penetration corresponding to the thickness of the slice or section used in the transmission studies. 1) CONVEX PARTICLES 1.1) General Expression for N,. We will suppose that a "center" (such as the center of mass) is assigned to each particle. The convention used for defining the center is immaterial providing it does not depend on the orientation or location of the particle. Consider a slice through the structure having a pair of parallel faces a distance t apart. It will be assumed that the slice is randomly located with respect to its perpendicular distance from some fixed point, but it is not necessary to assume that its orientation is random. Our problem is to deduce the relationship between the number of par- ticle images seen on an orthogonal projection through the slice with the number, Nv, of particles per unit volume in the original structure.* *Symbols are listed in the Table. The expected number of particles with centers lying within the slice is Nvt per unit area. In addition, there will be elements in the slice contributed by particles whose centers lie without. The number of such elements will be the same as the number of intersections occurring on a two-dimensional plane through the structure; namely N~K, where K is the mean distance, Fig. 1, between tangent planes to a particle averaged over all particles, i.e., Where Ni is the number of particles of class i having the same shape and size, and pi (4, 8) is the probability that an i particle will have a given orientation with respect to the slice. If the particles are randomly oriented, then K is independent of the orientation of the slice and equal to the mean cali-per diameter. The total number of particle elements in the slice is therefore Nv(t + K) per unit area, but fewer will be seen as separate images on the projection plane because of overlap. If MA is the number of elements "lost" by overlap, the number of images per unit area will be NA = Nv(t + K) -MA 121 MA is a function of the slice thickness and must vanish at t = 0. As t increases, NA at first increases, reaches a maximum, and thereafter decreases as the overlap term MA becomes predomi-

Jan 1, 1962

By S. K. Asunmaa, W. D. English, N. A. Tiner, W. A. Cannon

This paper discusses the reaction of metal surfaces with fluorine. Fluorination reactions result in the formation of metal fluoride films which are "passive" toward further reaction of the metal with fluorine. These films are very adherent, and do not easily detach from the substrate metal by mechanical flexing or thermal shock. Exposure of passive films to a humid atmosphere produces hydrated metal fluorides which cause secondary fluorination reactions upon reexpo-sure of the metal surface to fluorine. The surface films formed range from 10 to 30A in thickness and they pow at the expense of surface oxide films. The apparent film formation is completed rapidly in 15 to 30 min on stainless steel and nickel surfaces. On copper and on Monel surfaces, the film at first grows rapidly, then increases slowly over an extended period of time. Passive films are formed at all fluorine pressures in the range from 0.1 to 1.4 atm at room temperature. ALL metals react when exposed to fluorine. These reactions generally produce surface films which consist of metal fluorides. The rate of reaction is largely determined by the extent to which these films are protective. Although there is an extensive literature concerning reactions of oxygen with metals, there are very few investigations reported concerning fluorine-metal reactions. Brown, Crabtree, and ~uncan' investigated the kinetics of the reaction of gaseous fluorine with copper metal which had been freshly reduced in hydrogen. The reaction rate was independent of pressure over the range from 6 to 60 torr. A logarithmic rate law was obeyed in the temperature range from 25" to 300" ~. There was some deviation at higher temperatures which could have been the onset of a parabolic law. The calculated film thicknesses ranged from about two molecular layers, 10A, for 5 hr exposure at room temperature to thirty-five molecular layers for 5 hr exposure at 200" . The authors concluded that no single mechanism could explain all the observations. O7Donnell and spatkowski2 studied the reaction of fluorine with copper at 450°C at pressures from lo to 133 torr. The reaction was found to be pressure -dependent and followed a logarithmic rate law. It was not entirely diffusion-controlled, and fluorine was thought to be the migrating species in the reaction. Miscellaneous metal-fluorine reactions were investigated by Haendler et ~1.~ Reaction products were identified but no rate data were determined. Air Prod- ucts and Chemicals, Inc., have conducted an investigation of reactions between fluorine and various metal powders at room temperature and 85° C. Fluoride film thickness as a function of time of exposure was reported on the assumption that the reaction takes place between fluorine and metal to form the normal metal fluoride. Surface areas of the powders were only estimated so the relative film thicknesses may not be exact. The data showed reaction rates which were generally logarithmic in character, the rate of film growth virtually ceasing after a few hours exposure time for some alloy powders. The effect of moisture on fluoride films was also investigated by measuring additional reaction with fluorine after exposure of passivated powders to atmosperic moisture. The fluorination of iron was studied by 0'~onnell~ at temperatures from 225" to 525" ~ and at pressures ranging from 20 to 200 torr. In all ranges, the reaction followed a logarithmic rate law and was dependent on the square root of the gas pressure. The author concluded that fluorine gas passes through pores in the film. As the film grows, the blocking of pores leads to a rapid decrease in reaction rate; hence a logarithmic rate law is observed. Jarry, Fischer, and Gunther' investigated the mechanism of the reaction of fluorine with nickel at about 600" to 700°C. On the basis of the metallographic examination of fluoride scales growing on the nickel and from separate radioautographic data, it was claimed that fluorine is the migrating species in the reaction. This is in sharp contrast to the growth of oxide films on nickel where it has been shown that nickel ions migrate through the scale to the gas-solid interface to react with oxygen. Few investigations have been reported of the reaction of fluorine with metal oxides. Such investigations should be of great significance for a better understanding of passivation in view of the ubiquitous oxide films on technical alloys. Haendler et al.3 studied the reaction of fluorine with oxides of copper, tin, titanium, zirconium, and vanadium. Copper (I) oxide reacted as follows in the temperature range 150" to 300"~: temperature above 300" ~ was required for the CuO to react to form additional copper fluoride. Ritter and smith7 also investigated the reaction of fluorine with copper (11) oxide. An oxide powder comprised of spherical particles with a fairly high surface area was reacted with fluorine, starting at room temperature and increasing to 100° C over a period of 3 or 4 hr. The initial reaction was slow until the fluoride film thickness reached about to or 15R at which time the reaction rate accelerated, then decreased again. Most of the kinetic data was obtained during this final phase of reaction. The authors conclude that the film grows slowly at first until the stresses developed in the distorted lattice are sufficient to rupture the initial

Jan 1, 1969

By Fred C. Bond

AN improved method of measuring the surface area of a comminution product down to any desired particle size has been developed. The method is largely graphical, and requires relatively little calculation. It can be used with materials containing large amounts of clay, or excess fines of any kind. The surface area S is expressed in terms of square meters per100 c.c. of solids. This expression is based upon volume rather than weight, and is considered to be more suitable for crushing and grinding problems, where the machines ordinarily are operated under constant volume conditions. It has the advantage that surface areas of different materials can be compared directly, even though their specific gravities may be unknown. The "specific surface" of a material, or the number of square centimeters of surface area per gram, is equal to 100S divided by the specific gravity. Particle diameters are expressed in microns, K being the diameter of the largest particle present and L the grind limit, or lower size limit of the particles formed directly by grinding. The value of K does not always coincide exactly with the diameters of the largest particles retained on the coarsest testing sieve, since the largest particles formed in crushing and grinding are often slabby, or have other irregular shapes. L has been chosen as 0.700 microns, or number 27.5 in the size number series,1 for reasons to be explained later. S is the total surface area of all particles larger than L microns in diameter. When a homogeneous comminution product is separated into fractions whose diameters bear a constant geometrical relationship [p] to each other, and the log per cent weight retained upon each size and passing the next larger size is plotted against the log diameter, a straight line results, which is called the distribution line, and which has a slope in called the distribution modulus. The distribution line can be extended to any desired limiting size, and the total surface area of all particles larger than that size can be calculated. The equation of the distribution line is w = Cxm [I] where w is the per cent weight retained on each successive sieve; x is the particle diameter; and C is the per cent weight retained on an opening of unit diameter.2 Theoretically, the distribution line can be extended to include infinitely small particles. When it is so extended, and the assumption is made that no fine particles are present other than those accounted for by the equation; the log per cent cumulative weight passing any series of sizes, plotted against the log diameter passed, will result in a straight line lying parallel to and above the plotted distribution line.

Jan 1, 1941

By B. W. Howlett, M. B. Bever, Somnath Misra

The heats oj- formation at 0°C of the compounds AuSn,, AuSn2, AuSn, and the £ phase were measured in a metal -solution calorimeter with liquid tin or a liquid Sn-Bi alloy as solvent. The melting point, heat of fusion, and heat capacities near the melting point of- the compound AuSn in the solid and liquid state were measured in a constant temperature gradient calorimeter. The free energy and entropy of formation of the compound AuSn at its melting point and at 298 °K were calculated from the experimental results and published data. The heats of formation are discussed in relation to the nature of the compounds. The heat capacity below the melting point, heat of fusion, and entropy of fusion of AuSn are interpreted in terms of processes oc-curring before melting. The atomic arrangement in liquid Au-Sn alloys and the bonding in the intermediate phases of. the Au-Sn system are discussed in the light of the measured thermodynamic properties. THE available thermodynamic information on the intermediate phases in the Au-Sn system consists of the heats of formation of the compounds AuSn4, AuSn2, and AuSnly2 and of one composition of the < phase2 besides values of the heat content of the compound AuSn from 0" to 635".&apos; However, the heats of formation refer to different temperatures ringing from 90" to 450°C. Also, the reported error limits of some of the values are large and several inconsistencies are apparent. In the investigation reported here the heats of formation of the compounds AuS-, AuSnz, and AuSn and of three compositions of the < phase were determined for a single reference temperature of 0°C by liquid metal-solution calorimetry. The compound AuSn, which is the only congruently melting intermediate phase in this system, was further investigated in a constant temperature gradient calorimeter by measuring its heat of fusion, melting point, and heat capacity in the solid and liquid states near the melting point. From these data and published free energies of the liquid of composition Au~n,&apos; the free energies of formation of the compound AuSn at the melting point and at 298°K were calculated. The results shed light on the solid-liquid transition of AuSn and on the atomic bonding and state of association of gold and tin in the solid and liquid phases. 1) EXPERIMENTAL PROCEDURES 1.1) Preparation of Samples. Stoichiometric amounts of gold and tin, each 99.99+ pct pure, were melted in evacuated Vycor capsules (12 mm ID). The melts were maintained approximately 150°C above the liquidus for about 12 hr and shaken repeatedly. Samples of the compound AuSn were cooled slowly to room temperature. Melts of the other phases, all of which solidify by peritectic reactions, were transferred to the narrow end (5 mm ID) of the capsule, which was then quenched into iced brine. The solidified samples were annealed in the unopened capsules for 10 days at 30" to 50° C below the respective solidus temperatures. The absence of microsegregation and second phases was confirmed by metallographic examination. At least two batches of each composition were prepared. 1.2) Solution Calorimetry. The heats of formation were determined by liquid metal-solution calorimetry. In this technique, the difference between the heat effects on dissolution in a liquid metal, or alloy bath, of the compound and a mechanical mixture of its annealed components, adjusted for changes in composition of the bath, is the heat of formation of the compound at the temperature from which the samples are added. Details of the equipment and technique have been described."&apos; A tin bath at 300" or 350°C was used with the compounds AuSn,, AuSnz, and AuSn. The high gold content of the £ phase would have caused it to dissolve with an appreciable exothermic heat effect. In order to achieve thermal compensation, the samples were added from 0°C to a bath at 350°C consisting of 66.2 wt pct Bi (99.999+ pct pure), balance Sn (99.99+ pct pure). This solvent gives thermal compensation because gold dissolves exothermically in tin and endothermically in bismuth. The calorimeter was calibrated by adding from 0°C approximately 0.015 g-atom of the solvent.

Jan 1, 1965

By Hokuichiro Ohmachi

INTRODUCTION Metallic minerals have been formed only through complex geologic processes which took place at certain stages of the earth&apos;s histrory. Their concentration, abundance, and distribution are, therefore, restricted geologically, and very small in global scale. Ore is a mineral deposit or mineral concentration from which metals can be economically extracted by the contemporaneous technology. By this definition, several factors should be considered before any mineral deposit is regarded as an ore. The grade of mineral concentration and the scale of the reserve are most important. Demand for the metal and its price are the other factors. Advancement of technology in mining and extraction are also vital. Copper, for example, is now commonly extracted from the ores containing less than 0.3% of the metal. However, in the 1700&apos;s the common minerable grade was about 13%, and in the 1900&apos;s between 5 to 2.5%. This decrease in minerable grade is a function of not only the demand for copper, but also technological progress in mining and metal extraction in this case. Availability of ores has recently been subject to political factors, which were not the primary concern in the past. The petroleum of the Middle East is the prominent example. The metallic minerals are classified into three categories. The first one is the minerals free from these factors mentioned above. Iron and manganese belong to this category. The second category include aluminum, copper, nickel, cobalt, titanium, lead and zinc. These metals can be provided by the future progress in technology which enables the use of lower grade deposits. The third one represents the metals whose occurrence is geologically limited, and, thus, subject to the political factors. Niobium and tantalium are the example. In this article, I discuss these minerals in detail to give an outline of the factors which brought their concentration, distribution and availability. SELECTED MINERAL CONCENTRATIONS Iron Major iron ore deposits are the features of the relics of ancient continental crusts. They are found in all the continents where the Precambrian rocks expose. They do not occur in the oldest rocks (3,000my old) nor in the youngest ones (600my old). They are sedimentary rocks, normally, exhibiting alternations of bands of iron oxides (magnetite and hematite) or iron silicates (especially greenalite), and bands of silica, variously described as jasper, quartzite and chert. The best known banded iron ore deposits exist in the Lake Superior region of the North America, and their distribution extends at intervals to Labrador of Canada. Other examples occur in the U.S.S.R. Brazil, Venezela, India, the mainland China, and southern and western Africa (Liberia and Guines) (Table 1). Recently large deposits have been discovered in the Hammersley region of the western Australia, and northern and central region of Brazil. These ore deposits were originally formed in shallow seas where simple but abundant life existed. After the deposition, enrichment processes , related to tropical weathering, have brought about wholesale removal of silica to produce the deposits of best quality. Ores with 50-60% iron represent the best products in the Precambrian fields. Since local reserves of this high grade ores approach to exhaustion, benefication processes have been used effectively to upgrade much leaner ores (for example, taconite with 20-25% iron in Minesota, U.S.A.). There are two other types of iron deposits. Ironstone, a sedimentary rock containing goethite, chamosite and siderite, first appeared in early Paleozoic times in the stratigraphic record, and reached its Zenith in the Jurassic. Similar bedded iron deposits are found in the belt from the Cleveland Hills to Oxford in England, and in the "minette" oolitic ores of Alsace-Lorraine in Luxenburg and France. The iron content of these ironstones seldom exceed 30%, but they usually contain calcite and are self-fluxing. They also have phosphorous as undesirable impurity. Because of the grade and impurities, they require more fuel than the Precambrian ores. The third type of iron ore is associated with igneous activity and consists of magnetite and some hematite, and apatite. This deposit is believed to be a product of magmatic differenciation. It occurs in Kiruna of Arctic Sweden. The iron ore, therefore, present no global shortage problem. They extend to considerable depths. Their concentration is largest among the metals. If low grades were treated, the resource can be stepped up much substantially. Manganese Manganese is a ferro--alloy metal, thus, essential to the manufacture of sound steel. Manganese comes from manganese oxide and silicate ores. Many minerals contain manganese, but only a few oxides, silicates, and, in some places, carbonates (rhodecrosite) are mined as ore. Types of manganese deposits are bedded, massive,

Jan 1, 1982

By R. L. Slobod, H. A. Blum

A semiquantitative method for measuring the wettability of reservoir rocks has been developed. These data are needed for reservoir analysis and for interpretation of laboratory displacement studies. The wettability of a core sample is measured by the contact angle for the system oil-water-solid. These contact angles are calculated from the displacement pressure (threshold pressure) obtained by use of the centrifuge, using first oil-water and second air-oil in the same core sample. This method is based on the assumption that the air-oil and oil-water interfaces occupy similar positions in the porous medium when desaturation of the wetting phase is initiated. The assumption is also made that the Contact angle for the air-oil-solid system which is close to zero in value does not change appreciably even when the contact angle for the oil-water-solid system experiences marked changes. "Apparent contact angles&apos;&apos; for five different solids ranging from 31" to 82" have been determined, and changes irr the "apparent contact angle" of a given sample with laboratory use from 33" to 53&apos; {lave been observed. INTRODUCTION Reservoir rocks vary in their wettability, 1,2,3,4 some being preferentially water wet while other are apparently preferentially oil wet. The degree of wettability, in theory, is measured quantitatively by the contact angle for the system solid-oil-water, hut in 1)practice this quantity is extremely difficult to determine." The need for obtaining some measure of this quantity has become obvious in recent years as a result of both laboratory. and field observations. Several reservoir.: such as the Bradford Sand in Pennsylvania and the Wilcox&apos; at Oklahoma City are reported to be oil wet. If these report:: correctly reflect the true nature of the surface of the rock in the ground, then these reservoirs probably will not perform as predicted on the basis of a water wet rock. In the laboratory many core samples have been Observed to be oil wet. These samples, while perhaps not correctly representing the reservoir, have markedly different properties from water wet rock. The location of the phases is different (oil is in contact with rock instead of water), and other quantities such as the connate water, the capillary pressure curve; residual oil. relative permeabilities. and the recovery of oil by water flooding are markedly affected by the value of the contact -4 A further complication observed in the laboratory is the chang-ing of the wettability of a rock specimen with use. such changes mean that repeat runs on the same core are not the duplicate tests desired, but represent new experiments on a more oil wet material. The changes in surface characteristics are sometimes so rapid that by the time an experiment requiring several days is completed, the results may not be representative of the core as originally described, The, rock material itself (Silica. carbonates. etc.), whell Clean and uncontaminated, is water wet. There seems b( : little evidence of the presence of oil wet minerals such as heavy metal sulfides. The oil wetness of reservoir samples, therefore, is believed to be caused by the accumulation of an adsorbed film in which the polar group of a large organic. molecule is adsorbed on the surface leaving the organic or hydrocarbon part of the molecule projecting out from the solid. Such a surface is much more readily wet 17" oil than by water. These considerations indicate the need for a method which will provide some measure of tile wettalbility (Contact(angle if possible) for reservoir rock ..samples) The method should be capable of (1.1 distinguishing between tile wettalility of dif. ferent formation,.. (2) detecting (change. ill wettalbility of a core with use. and (3) measuring the changes in Wettability which may be accomplished with cleaning operations. such as the use of sodium silicate for increasing water wrettalbility." A preliminary report on such a method is preseted below. not with the idea that this procedure alone will Solve the wettabil-ity problem. but rather that it may provide encouragement to

Jan 1, 1952

By Fred L. Morritz, Harold M. Manasevit, Richard Nolder, Arnold Miller

Experimental evidence is presented which confirnis the epitaxial relationship between the deposited silicon and the sapphire substrate. Four distinct modes of orientation relationships have been established. These have been shown to be Single-crystal gvowth retention as a function of surfaces oriented off ideal has been qualitatively indicated. Both full-circle goniometer X-ray techniques and replica electron microscopy have indicated varying amounts of microtwinning in the silicon. film, which may he caused by the mode of silicon formation. Parameters have been found where twin density is less than I pct. The early stages of&apos; epitaxy of silicon m sapphire have been examined by electron-microscope techniques... and mechanisms have been proposed. THE first report of the deposition of single-crystal silicon on sapphire (single-crystal aluminum oxide) was made at the American Physical Society Meeting in Canada&apos; by one of us and was subsequently published in the Journal of Applied physics.* This paper summarizes some of the work carried on in this area since that time, in addition to reviewing some of our earlier observations. The initial single-crystal deposits of silicon on sapphire reported were obtained on sapphire planes produced by cutting a sapphire rod perpendicular to its fastest growth direction, which is approximately 60 deg from the C axis. Direct correlations between the microstructure and X-ray data as to the single crystallinity as shown in Fig. 1 are evident. These deposits were identified as (111) silicon on the substrate oriented near the (1123) of sapphire. (Sapphire notations are designated according to the c over a ratio of 2.73.) It became evident that substrate quality and surface play an important part in successful epitaxy. For example, in Fig. 2 we observe an interesting

Jan 1, 1965

By C. B. Alcock, M. G. Hocking

The kinetics of the growth of sulfate layers on blocks of Cu20 has been studied between 688" and 800°C. At 788c the over-all weight increases followed the parabolic rate law, with k = 216 30 sq mg per cm4 min, using a 1:1 entering gas mixture of SO2:02. At 757 after an initial linear period the parabolic rate law was followed, with k = 57.8 10 sq mg per cm4 min. The gas mixture required a platinum catalyst to produce the maximum SOs pressure. The sulfation rate at 757&apos; and 788c was high until all the CUZO had changed into a core of CuO, when it became very much lower. At 757°C marker experiments showed that the sulfates (CuO. CuS04 and CuSO4) grow outwards from the oxide surface, but CuO. CuS04 mixed with CuO was found beneath the markers. At 688 markers were found at the CuO. CuS04/CuS04 interface. Visual observations at 757 showed a liquid eutectic moving beneath the sulfate surface. causing very rapid sulfation and extruding to solidify as thick &apos;needles" up to 8 mm long. Marker experiments have shown conclusi.cely that CuO grows on Cu20 in air by the outward migration of copper. ThermODYNAMIC measurements on the sulfate and basic sulfate of copper, reported recently,&apos; are followed here by measurements of the rates of formation of these sulfates on cuprous oxide, in order to provide a background for the understanding of roasting processes. peretti2 and McCabe and Morgan3 have shown that the phase Cu20 lies next to Cu2S when the sulfide is roasted under conditions where sulfates will be formed. Since this would present too complex a system for kinetic study, the present work4 has been based on the kinetics of sulfation of the oxide phase. The results of a study of the kinetics and mechanism of the sulfation of cobaltous oxide have recently been reported.4,5 Results on the sulfation of cuprous oxide have also appeared,6 but are at variance with those to be reported here. This seems to be because the previous workers6 did not obtain constant SO3 pressures from the SO2/O2 sulfating gas mixtures used, as will be discussed later. Wadsworth, Leiter, Porter, and Lewis found that the sulfates produced when SO2/O2 mixtures are passed over Cu20 at red heats are CuS04 and the basic sulfate CuO.CuSO4. When the decomposition of CuS04 was followed&apos; by differential thermal analysis, a stage corresponding to CuO .CuS04 was reached before decomposition into the oxide occurred. APPARATUS The vertical furnace used for quantitative studies was a conventional resistance-heated and propor- tionately controlled furnace with an even zone (1 deg) which was 4 cm long. The gas mixtures of SO2 and 02 were made by mixing measured flows from capillary flowmeters and drying over phosphorous pentoxide before passing them into the Pyrex top-piece of the furnace assembly. A mullite tube of bore 2% cm was used as reaction vessel and at the bottom of this tube was a trap for SO3, which condensed as a colorless liquid. The residual gas was led into a fume cupboard for ventilation to the atmosphere. The furnace used for visual observations of needle growth and other phenomena consisted of a transparent silica reaction tube of bore 3 cm, having an optically flat silica window sealed into its wall. The reaction tube was clamped vertically, inside a mullite tube of bore 4 cm and length 42 cm which was heated by Kanthal windings. The window in the silica reaction tube was arranged opposite a hole 3 cm wide and 2 cm tall which had been cut in the wall of the mullite winding tube 19 cm from its top end. A binocular microscope was used to look through the window, illumination being provided by a focusing microscope-lamp offset sideways and downwards. The oxide block to be sulfated was suspended from the removable Pyrex top-piece to the reaction tube, by means of which it was inserted at the start of the experiment, and through which entered the S02/02 gas mixture. The variation of the temperature inside the reaction tube with horizontal and vertical displacement from the window was investigated, and, while it can be said that the temperature was constant 1 deg, its value at a given position was known only to 12 deg. In both furnaces, the oxide block to be sulfated was suspended from a small silica hook immediately downstream from a platinum thimble used as catalyst, which was held on a long silica rod from a Pyrex spring attached to the removable Pyrex top-piece of the furnace. The spring was only included in the quantitative sulfating furnace; its sensitivity was 1.4 cm per g and it was found to be free from creep in a 16-hr test when carrying the working load. The extensions were followed by a cathetometer which could be read to 0.001 cm, corresponding to i0.7 mg. Extensions of the spring were measured on adding weights between 5 and 500 mg to the working load (thimble + oxide block), and Hooke&apos;s law was closely obeyed. SAMPLES Cuprous oxide blocks were prepared by oxidizing Johnson Matthey "Specpure" copper sheet of 1 mm thickness (impurities: iron at 3 ppm, silver at 2 ppm, lead, nickel, sodium, and silicon each at 1 ppm, calcium, chromium, magnesium, and manganese each at less than 1 ppm) for 6 days in air at 1000°C in a re-crystallized alumina boat. It has been reported7 that when Cu20 is prepared by heating copper sheet for 1 day the central plane of the blocks produced consists

Jan 1, 1967

By Helmut Thielsch

METALLOGRAPHIC specimens whose surfaces are to be investigated are too thick to allow either light or electrons to pass through them for microexamination by transmission. This difficulty is overcome with optical microscopes by illuminating the surface through the objective lens. For electron microscopes best results are obtained by preparing thin replicas of the surface of the specimen, placing them in the microscope and passing the electron beam through them. Since electron microscopes represent a rather recent invention, they have found little application as compared with optical microscopes. This is true because, aside from the cost of new equipment and development of new techniques, some of the older replica methods necessitated the destruction of the surface from which a thin transparent replica was obtained. In other processes in which the surface is preserved, either too tedious a procedure is required, unsuited to "mass-production " requirements of industrial laboratories, or replicas of insufficient contrast and sharpness are produced. In general, investigations with the electron microscope involve five steps: (I) polishing the surface of the metal specimen, (2) proper etching of the surface, (3) preparing the suitable replica from the surface, (4) examination and photography in electron microscope and (5) interpretation. PREPARATION OF METAL SURFACES Usual metallographic polishing is generally satisfactory. It is important though that the final polish be applied very care- fully, since otherwise evidence of a small amount of deformation might show up even on relatively deeply etched surfaces. A high-power microscope should be used to determine the suitability of the polish and etch. This, of course, is not different from optical examinations, but in these, if a deep etch is used, the problem is less serious. It is frequently difficult to detect with optical microscopes poor polishing aside from superficial scratches before etching. Figs. I and 2 show micrographs of "well" and "poorly" polished nickel etched by immersing the same for 20 min. in a solution containing 8 grams cupricsulphate in 40 C.C. of concentrated HCl and 40 C.C. of H20 (Marble&apos;s reagent). The sample shown in Fig. I was polished in its final stages for 5 min. on a carborundum wheel followed by 10 min. on a rouge wheel, whereas the sample shown in Fig. 2 was polished only I min. on the rouge wheel. Generally, this procedure does not guarantee that the surface of the specimen will be either undistorted or deformed. It was applied here merely to show the effects of good and poor polishing. To the experienced investigator, plastic deformation is

Jan 1, 1946

By G. R. Gohn, S. M. Arnold

The results of stress-corrosion tests upon several non-ferrous sheet metals are presented in this paper. The metals include tough pitch copper, five binary brasses, two leaded brasses, one copper-silicon alloy, two tin bronzes, and two nickel-silver alloys. The tests indicate that for most of these sheet metals, externally applied bending stresses below the yield point (0.01 per cent offset) do not result in stress-corrosion cracking as determined by the A.S.T.M. Tentative Method of Mercurous Nitrate Test for Copper and Copper Alloys (B 154-41T).~ Only in the cases of low brass, high brass and medium leaded brass, all cold-worked 4 B & S numbers hard, was any corrosion cracking observed below the yield strength, and in all cases such failures occurred at stresses above the proportional limit for these materials. However, when some of the same materials which showed no evidence of stress-corrosion cracking at stresses below the yield strength, are stressed beyond the yield point, stress- corrosion cracking is quite apt to occur. Since experience has shown that some of these materials, particularly the brasses, are susceptible to stress-corrosion cracking under service conditions, these tests would indicate that, besides externally applied stress and corrosion, plastic deformation in addition to that resulting from the original cold working of the material is also required to produce conditions conducive to stress- corrosion cracking.

Jan 1, 1945

THE Copperton mill in reality was a sort of proving ground. It was. designed to serve three purposes: (1) to verify the accuracy of the mine sampling by actually treating substantial tonnages of ore, (2) to demonstrate on a reasonably large scale the percentage of the copper in the ore that could be recovered, and (3) to permit the testing of various kinds of machines and devices for crushing and concentrating the ore, so as to guide the engineers in designing the proposed 6000-ton milling plant at Garfield. As a matter of fact, it contained a lot of second-hand equipment sent by MacNeill and Penrose from the works of the United States Reduction &Refining Co. in Colorado; and it was by no means a model installation. Probably it would have been even less efficient, except for the skillful work of George O. Bradley and-Frank-G, Janney, both of whom had worked with Jackling at Mercur. Bradley was a mechanical engineer employed to design the plant. Later he directed the design of the concentrator at Garfield and remained as consulting mechanical engineer to the company until 1915. Janney, who afterwards became manager of mills, a position that he retained until his death in 1916, was a skilled mechanic at the Golden Gate mill at Mercur when Jackling built the plant in 1897. His flair was making machinery do what it was intended to do. He was not an ore-dressing engineer in a technical sense; but Jackling him- self was a specialist in this respect as well as in designing and construction and Janney&apos;s mechanical aptitude made him a particularly valuable man in the Utah organization. John McDonald, another of Jackling&apos;s Mercur associates, was the first mine superintendent. With practically all of the available funds earmarked for construction of the Copperton

Jan 1, 1933

By B. Russell, J. R. Tuffley

The stability regions of the normal sulfate and the various basic sulfates of lead in 02-SO2 and PhS-SO2 gas atmospheres were calculated from available thermodynamic data over the temperature range 600o to 1200oC. Roasting experiments were carried out on samples of synthetic lead sulfide at various temperatures and for various roasting times. Compounds in the oxidized surface layers were identified by X-my techniques. The order in which the various reactions occurred was determined by considering the experimental results in conjunction with the thermodynamic calculations. The results of these investigations were applied to the sintering of lead sulfide concentrates, and the extent to which each of the various reactions occurred in a sinter bed was determined. PRODUCTS which may be formed during the roasting of PbS are PbS04, PbSO4. PbO, PbSO4 . 2PbO, PbSO4 . 4PbO, PbO, and Pb.1, 2 The formation of some sulfates has been studied by a number of investigators3-&apos; whose experiments have mostly been confined to the temperature range between 500" and 850°C. Culver, Gray, and spooner3 were able to isolate the reactions which formed PbSO4 and PbSO4. PbO by carefully controlling the compositions of the roasting gases. The kinetics of these reactions were studied within the temperature range 673" to 807°C. Gardner4 and Merrick5 also studied the kinetics of oxidation of PbS. Gardner disregarded the existence of basic sulfates and, as a result, misinterpreted some of his experimental data. Merrick recognized that most of the products of oxidation were mixtures of basic sulfates, but was unable to identify the individual components. Hoschek6 oxidized PbS in air at temperatures up to 800°C. The products were analyzed after roasting had proceeded for some minutes, but no attempt was made to follow the reactions in the initial stages. Consequently, no roasting mechanism was derived. He also showed that PbSO4 and PbSO4 - 4PbO decomposed slowly in air at temperatures in the region of 800°C. The stability regions of sulfates in the temperature range 500" to 850°C have been only partially determined, while practically no information is available for higher temperatures. In the lead sintering process, PbS concentrates are roasted at temperatures within the range 1000o to 1200°C. In order to investigate sulfate formation, it is necessary to determine the effects of temperature and gas composition upon the various oxidation reactions and upon the regions of stability of the various lead sulfates. Kellogg and Basu2 introduced an equilibrium diagram similar to those in Figs. 1 to 3 which provides a convenient medium for represent-

Jan 1, 1964