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By J. L. Fitch, B. G. Hurd

The presence of gypsum in samples subjected to standard core analysis introduces serious errors in the measurement of water saturation and porosity. The magnitude of these errors, depending upon the type of analysis procedure used, has been evaluated experimentally and theoretically. Water-saturated pore volumes determined by vacuum distillation or retort procedures may be too high by as much as 48 per cent of the volume of gypsum present. The maximum error in this value determined by Dean-Stark extraction with toluene is 36 per cent of the gypsum volume. If pore space is measured by a Boyle's law type porosimeter the maximum erorr due to gypsum is 38 per cent of the original gypsum volume present. The conscientious core analyst may eliminate the errors caused by gypsum by either of two methods. He may apply suitable corrections for the water of crystallization removed from gypsum, or take special precautions to prevent dehydration of gypsum during core cleaning and alzalysis procedures. These alternatives are discussed and methods for obtaining reliable core analysis data are proposed. Gypsum (CaSO4 . 2H2O) occurs as a common mineral in many of the world's sedimentary basins. In addition to its presence as primary bedded evaporitic deposits, it is often found as secondary replacement zones and pore-fillings in host rocks. That it may cause false indications in porosity, both on neutron logs and in standard core analysis, has been generally recognized. False porosity interpretations from neutron logs result because the chemically bound water in gypsum attenuates neutrons as effectively as free water. Errors in core analysis result when gypsum is dehydrated prior to or during the analysis. Vacuum retort procedures used by many laboratories to determine fluid saturation and porosity effect a complete removal of water of crystallization from gypsum. The crystal water, distilled and collected with free water from the sample, is counted as water-sat11rated pore space. Dehydration of gypsum results in a decrease in volume occupied by calcium sulfate and a corresponding increase in pore volume. Thus, if gypsum is dehydrated by sample cleaning and drying procedures, subsequent porosity measurements with gas expansion or compression instruments will be high. The qualitative effect of gypsum on porosity determinations by retort procedures was discussed in a recent article by Bynum and Koepl3. They concluded that since false porosity was interpreted as being water saturated, determinations of oil content were not affected. Others in the industry, however, have pointed out that porosity values are often used with values of water saturation determined independently, e.g., from electric resistivity logs in making reserve estimates. Values of water saturation calculated from the formation resistivity using the Archie equation, S4= are actually low if values of are high due to gypsum. In this case, false porosity values due to gypsum could cause serious errors in calculations of oil-in-place. This investigation was made to determine quantitatively the effect of gypsum on porosity values determined by different core analysis procedures. EXPERIMENTAL PROCEDURES Dehydration of Gypsum The extent and rate of removal of water of crystallization from gypsum under conditions encountered in core analysis procedures were studied. Taken for the experiments were three types of relatively pure, naturally occurring gypsum, viz. selenite, satin spar and massive gypsum. Although all samples probably contained trace chemical impurities, each type lost the theoretical amount of water upon complete dehydration. An automatic recording thermobalance, similar to one described by Mauer2, was used to obtain dehydration rate data for samples heated in dry air. Water

By R. T. Keyes, R. B. Clay, L. L. Udy, V. O. Cook, M. A. Cook

Based on compressibility and stress wave velocity in rock, initial explosive loading conditions, the thermochemistry of the explosive and reasonable description of the pressure-distance relations behind the shock front, the distribution of energy between the products of detonation and the burden are estimated as a function of time for various loading conditions. These include 'powder factor', loading density A (fraction of borehole occupied by explosive), and the explosive itself. Factors responsible for rock fragmentation are discussed in terms of: 1) 'release wave fracturing', 2) 'shear wave fracturing', and 3) 'release of loading fracturing' or 'rock bursting'. Release wave fracturing appears to occur only in the immediate vicinity of free faces, and shear wave fracturing only adjacent to the borehole under normal blasting conditions. Rock bursting is thus considered to be the most important means of rock fracturing in blasting. Means for maximizing it are considered. The most important factors to consider include maximum available energy A, explosive density p1, loading density A and 'powder factor'. Maximum efficiency is attained in general by maximizing the A . p1 product. This is achieved by using high density explosives at a loading density of unity (A = 1.0). Ways for achieving this condition are discussed. The bulk-handled aluminized slurry blasting agents have the desired properties for achieving optimum conditions for high blasting efficiency based on the theory outlined herein. Factors considered most important in the blasting of rock are: 1) The maximum available energy A, determined by the heat of explosion Q and the mechanical efficiency ?, a factor intimately associated with the mode of application (A = Q at highest gas concentrations). 2) The 'borehole pressure', pb, or the maximum pressure developed in the borehole after passage of the detonation wave and before the burden has had time to move or become compressed appreciably. (Owing to the short duration of the detonation wave at any particular point in the borehole, the fact that the explosive may not always fill the borehole completely and the further fact that the burden may not actually see the detonation pressure, the borehole pressure is considered more significant than the detonation pressure p2 as a performance factor in borehole blasting.) The borehole pressure is determined by the explosion or adiabatic pressure, p3 , and the loading density, A, or the fraction of the borehole filled by explosive. 3) The physical conditions important in the application of the explosive are: a) The 'powder factor,' (We/Wr), or the ratio of the wt of the explosive to that of the rock being blasted expressed as lb per ton or more generally in lb/cu yd. b) The bulk density, p1 ?. c) The 'burden' or 'line of least resistance,' the spacing between boreholes, the geometry of the borehole pattern and sequence of firing. d) The physical and chemical properties of the rock, most significant of which are possible heterogeneties, such as faulting, prefracture, and greater than micro-scale chemical heterogeneities. (This factor is not considered here but deserves a great deal of careful consideration.) All of these factors need to be carefully considered in the most economical engineering of a blast. Here is considered firstly an outline of the present status of dynamic rock mechanics, particularly as it pertains to blasting. The factors pertaining to the most efficient application of blasting agents are also considered, followed by a discussion of methods of application to achieve optimum explosives performance. ROCK MECHANICS Dynamic rock mechanics is currently a rapidly developing science contributing greatly to a better understanding and consequently the more effective application of explosives in blasting of rock.1-22 Basic to the development of the science of dynamic rock mechanics were the advances of Goransen23 and the Los Alamos and NOL groups24-28 concerning rock and stress wave phenomena and the transmission and reflection characteristics of stress waves at interfaces between different media. Basing considerations on this new knowledge as well as new experimental methods of study (ultra-high speed streak and framing cameras and electronic timers) the theory of fracture and failure of solids under impulsive loading by stress waves developed rapidly.14,16,27-29 Also the

Jan 1, 1967

By Orville R. Lyons

THE relative performance of coal washing equipment, or the effectiveness with which any type or make of equipment removes impurities from coal, has been most difficult to evaluate in the past. The most widely used yardstick is the Frazer and Yancey efficiency formula developed in 1922,1 but Yancey in a later article states that "washers treating coals of different density composition or operating at different densities of separation cannot be compared directly on the basis of this criterion."' Prior to and since 1922, a variety of other methods has been used for comparison purposes, including the distribution curve, the error area, and the "ecart probable" or probable error. Yancey and Geer in discussing these methods conclude, "Performance can be evaluated in a number of different ways, with the choice of the proper method to use being dictated by the objectives of the investigation and the data available."' It is true that performance can be evaluated in a variety of ways, but if the equipment is to be evaluated on an effectiveness basis, there should be only one universal comparison method. Varying methods have been used because one universal comparison method has not been found or developed. In the article previously quoted, Yancey and Geer state in clear terms the primary concept for a universal comparison method: "One of the simplest, and certainly one of the most obvious evaluations of washery performance is the quantity of sink material in the washed coal and the float material in the refuse. If the washery products are tested at the density at which the washing unit is operated, the sink in the washed coal and the float in the refuse represent material that has been misplaced." The quantity of misplaced material was used as a criterion of washery performance by Lincoln in 1913,8 by the United States Bureau of Mines in 1938,4 by Hancock in 1947,3 and by the national French research agency Cerchar in recent years.2 In 1950 Anderson' proposed the use of this criterion as an efficiency value to replace the Frazer and Yancey formula. However, none of the above-mentioned investigators used the misplaced material concept in a manner that would provide universal coal-cleaning equipment comparisons. The Correlation Theory The ideal coal cleaning process would treat all sizes and would make a perfect separation at any given specific gravity. All material lower in density than the desired value would report in the coal product and all material higher in density would report in the refuse product. Unfortunately, no known cleaning process achieves this goal and there seems little likelihood that any process yet to be invented will do more than approach it. When coal is treated in volume under operating conditions, it is impossible to avoid mechanical entrapment, fluctuations in throughput and effective gravity of separation, and the creation of turbulent currents, even when a true heavy-liquid bath is used and the feed is closely sized and contains little intermediate gravity material. This being so, it is possible to appreciate the difficulties inherent in trying to obtain a perfect separation when treating a wide range of sizes and a feed containing high percentages of intermediate material, using turbulent currents to help create the effective separation gravity, under operating conditions which normally tend to be on the overload side. When coal is separated from refuse in any coal cleaning equipment, some refuse always reports to the coal and some coal to the refuse; the writer therefore assumed that there should be a relationship between the total amount of misplaced material produced by any given piece of equipment and the difficulty of separation as represented by the percentage of near gravity material in the feed. With small amounts of near gravity or ±0.1 material in the feed there should be less misplacement of material than would occur with large amounts of near

Jan 1, 1952

By George M. Fowler, R. E. Illidge

Part I. Developing BY GEORGE M. FOWL INTRODUCTION The Tri-State district comprises an area of about 2000 square miles in southwestern Missouri, southeastern Kansas, and north [ ] eastern Oklahoma. The part that is in and contiguous to Missouri is still sometimes designated as the Joplin district (Fig. I). EARLY OPERATIONS Mining operations in what is now the Tri-State district date from about 1848 and have been continuous to the present. Apparently the first discoveries of ore were made about the same time near the present sites of Joplin, Oronogo, and Granby. Lead minerals were found at grass roots, probably in shattered rock in shallow excavations, then these minerals were followed in shear zones to deeper horizons. The mining of zinc followed. Before 1874, zinc ore was worthless and discarded as waste. According to published records, the total production of lead to that date was 49,000 tons of metal from 70,000 tons of concentrates. PRODUCTION The aggregate ore production from the Tri-State district was recorded at interval

Jan 1, 1943

By J. N. Ong, J. P. Ratledge, J. H. Boyce

SINCE German operators opened the Tsumeb mine in the early 1900's, continuous operation has been interrupted only by enforced shutdowns during two world wars and the depression of the 1930's. Original metallurgical practice was blast furnace smelting. This was applicable only to low zinc ore, leaving large tonnages of high zinc ore to be stockpiled on the surface. A gravity concentrator using tables, buddles, and jigs operated for several years, but differential flotation of the ore did not get beyond the experimental stage. When the property was put up for sale by the South African Custodian of Enemy Property there was an estimated 434,000 tons of ore on surface dumps. The dump material, assaying 4.48 pct Cu, 15.8 pct Pb, and 10.9 pct Zn, had become highly oxidized during a stay of many years on the surface. But these dump ores had to be used in evaluating possible metallurgy because the shaft became flooded after the 1940 shutdown and underground ore was unavailable. Many companies examined Tsumeb but quickly lost enthusiasm because of the formidable metallurgical problems presented by the dump ore. However, on the basis of extensive test work, the present company decided that differential flotation would be successful and purchased the property after competitive bidding. Geology and Mineral Association is Complex The Tsumeb mine lies near the northern boundary of South West Africa at an altitude of 4200 ft. The village of Tsumeb is 335 air miles northeast of Wal-vis Bay, territorial port of entry. The orebody is a hydrothermal replacement deposit associated with an irregular intrusion of aplite cutting folded pre-Cambrian dolomite beds. In plan the deposit is a lens of 250x600 ft maximum dimensions. In section the orebody dips 55" south from the surface to 2000 ft, below which there is a reversal in dip to 75" north. Mineralization is localized in the aplite and in the adjoining brecciated dolomite. In the upper levels the ore is largely confined to a single lens, but below the 1890 level massive sulphide ore forms north and south lenses that partially enclose a pipelike body of medium to low grade disseminated ore, part of which is of too poor a grade to mine. Drilling below the 24th, or bottom level, has disclosed that a high percentage of the mineralization from the 3000 to 3300-ft horizons is comprised of copper and lead oxides. The deep oxidation may be local, since it appears due to circulating waters in a major fault cutting the orebody. Tsumeb ranks as one of the highest grade base metal deposits in the world. It is geologically and mineralogically famous for 41 copper, lead, zinc, vanadium, and germanium ore minerals, but its complex mineral assemblage is not attractive to metallurgists. In addition, there is a gradual change in oxidation intensity from the upper levels to the lowest level now operating, which is the 24th. This is well illustrated by the copper minerals. In the upper levels malachite and azurite are predominant, in the intermediate levels chalcocite, and in the lower levels tennantite. Throughout the mine there are sufficient heavy metal soluble salts to activate zinc, and large amounts of depressants are required even for so-called clean sulphide ores. When the same sulphide ore is exposed to prolonged oxidation aboveground, as was the case with the dump ores, reagent requirements become fantastic. Plant Construction First staff members arrived at Tsumeb in March 1947, and by May essential services had been restored and mine unwatering began. In 2 1/2 months company employees built a temporary jig and sorting plant for treating existing dumps to provide a saleable product during high metal prices. Meanwhile, concentrator design and construction was contracted to a South African firm, with subcon-

Jan 1, 1956

By Herbert Clark Hoover, Lou Henry Hoover

We give the following brief notes on early works containing some reference to mineralogy, mining, or metallurgy, to indicate the literature available to Agricola and for historical notes bearing upon the subject. References to these works in the footnotes may be most easily consulted through the personal index. GREEK AUTHORS.-Only a very limited Greek literature upon subjects allied to mining or natural science survives. The whole of the material of technical interest could be , reproduced on less than twenty of these pages. Those of most importance are : Aristotle (384-322 B.c.), Theophrastus (371-288 B.c.), Diodorus Siculus (1st Century B.c.), Strabo (64 B.c.-25 A.D.), and Dioscorides (1st Century A.D.). Aristotle, apart from occasional mineralogical or metallurgical references in De Mirabilibus, is mostly of interest as the author of the Peripatetic theory of the elements and the relation of these to the origin of stones and metals. Agricola was, to a considerable measure, a follower of this school, and their views colour much of his writings. We, however, discuss elsewhere1 at what point he departed from them. Especially in De Ortu ct Causis does he quote largely from Aristotle's Meteorologica. Physica, and De Coelo on these subjects. There is a spurious work on stones attributed to Aristotle of some interest to mineralogists. It was probably the work of some Arab early in the Middle Ages.[ ]

Jan 1, 1950

By P. Bolsaitis, L. Skolnick

A model of metallic solutions is postulated which explains the energy of formation of alloys on the basis of changes in electron density around solute and solvent atoms and changes in pairwise interactions between atoms. The model is based on the Wigner-Seitz cell model of metals, with the electronegativities of the metals as the parameter for the electron-attracting power of the constituent atoms. In contrast to models based on the description of cohesive energy in terms of pairwise interactions only, which require an empirical, adjustable correction parameter to the Berthe-lot relations in order to predict negative energies of formation, the electron cell model accounts for both negative and positive energies on the basis of parameters of the pure components. Calculated heats of mixing based on published parameters of the pure metals are found to compare favorably to experimental values, despite the absence of any adjustable parameters in the model. THE formulation of an "exact" quantum mechanical model for the energy of cohesion of metals reduces ultimately to the many-body problem and for a complete solution would require the knowledge of wave functions and energy levels of all the particles in the system. The case of alloys is further complicated by the fact that the potential fields around the constituent atoms are different and the matching of boundary conditions in terms of the resulting wave functions is still an unresolved mathematical problem. It appears that in spite of the numerous investigations that have led to an elucidation of many properties of the metallic state, the formulation of the Hume-Rothery rules in 1931 marks the lone accomplishment toward simple, qualitative prediction of the energy of formation of alloys. More recently Friedel'' and Arafa have utilized the modern concepts of the electronic structure in metals in combination with the Hume-Rothery rules to arrive at quantitative estimates of the energy of formation of alloys with low solute contents. The relative success of the Hume-Rothery rules and Friedel's and Arafa's studies encouraged broaching the subject of formulation of a model based on realistic physical parameters and of conceptual and mathematical simplicity that could be applied to alloys regardless of concentration. On the basis of the free-electron theory, the cohesive energy of pure metals can be expressed as a function of "valence" (number of free electrons per atom), lattice parameter (or density), and the ioniza-tion energy. In addition to the electronic contributions to cohesion, one has to consider the pairwise exchange interaction energy between neighboring ion cores and the contribution from van der Waals forces. The energy changes upon alloying are viewed as resulting primarily from a redistribution of electron densities around the ions (a simplification of the more basic concept of a change of the wave functions of the electrons in the presence of a perturbing potential field). In addition there is a change in the pairwise interactions between neighboring ions which is usually the only factor taken into account in commonly used adaptations of the quasichemical theory. The electronegativities of the metals forming the alloy are used as the measure of the electron-attracting power of the ions in the alloy and the difference in electronegativities as the driving force for changes in electron energy on alloying. The interplay of pairwise interactions and electronic forces results in positive or negative energies of formation of alloys. Results obtained for systems to which the free electron model is best applicable are in good agreement with experimental values. 1) COHESIVE ENERGY OF METALS IN TERMS OF THE ELECTRON CELL MODEL The simplest physical model of a metal is that of a lattice of positive charges immersed in a sea of uniform, negative charge distribution represented by the

Jan 1, 1969

By Donald K. Weaver

THERE have been eight different oil zones identified and produced at Santa Fe Springs, of which three or four are in turn divided into two or three parts. These zones are, from top to bottom, the Foix, difference of opinion over this nomenclature, with reference to the different zones referred to as Clark, it has no particular bearing on the water problems. Each of these oil zones has had waters of varying salinity associated with it, either within or at the bottom of the 'zone. Table 1 is a tabulation of the zones, their maximum thicknesses, salinity and heads of various waters. Surface waters are fresh, and of high head, giving artesian flow in some instances.

Jan 1, 1930

By C. S. Matthews, P. Hazebroek, F. Brons

A method has been developed for calculating the average pressure in a bounded reservoir. The reservoir is first divided into the individual drainage volumes of each well, by using the criterion that at steady state each individual drainage volume is proportional to a well's production rate. The average pressure in each drainage volume is then calculated by a method developed in the report. By volumetrically averaging these individual drainage volume pressures, the average pressure in the entire reservoir is obtained. To calculate the average pressure in each drainage volume, a correction is applied to the ordinary extrapolated pressure, i.e., the pressure obtained by extrapolating to infinite time the linear portion of the graph of closed-in pressure versus log[?t/(t + ?t)], where At is the closed-in time and t the production time. The correction, which is a function of the production time, is presented in graphical form for different shapes of the drainage area (horizontal cross section of the drainage volume). INTRODUCTION It is important to be able to find the volumetric average pressure in a reservoir so that the size of the reservoir may be determined from material balance calculations. It is also desirable to be able to find the approximate distribution of pressure within a reservoir for detection of fluid movement. 'The purpose of this paper is to present a method for calculating both the average reservoir pressure and the approximate distribution of pressure within a bounded reservoir — that is, a reservoir with no water drive. In reservoirs where the pressure builds up rapidly after wells are shut in, the determination of average pressure generally poses little problem, for one often need only average the final buildup pressures. It is when pressure buildup is slow that difficulties arise. For practical and economical reasons, the time allowable for closing in wells is limited. If at the maximum allowable closed-in time the pressure has not reached a con- stant value (and this is more often the case than is generally realized), calculation of average pressure presents difficulties. One method which has been used in the past for obtaining an "average" pressure involves the extrapolation to infinite closed-in time of curves of pressure as a function of closed-in time. Contour maps of these extrapolated pressures are used in arriving at an average pressure. In some cases wells are shut in for arbitrary Lengths of time, and contours of these arbitrary shut-in pressures are used for calculation. All these methods are somewhat arbitrary and suffer from lack of fundamental theoretical basis. For example, no precise meaning can be given either to the extrapolated or to the arbitrary shut-in pressure. Furthermore, there seems to be no reason why either set of pressures should be contourable. It was because of the vagueness of these old methods and their lack of a sound theoretical basis that, the present method for determining average reservoir pressure was developed. SYMBOLS A = drainage area of a well, cm' A, = drainage area of well j, cm2 A , = total drainage area of all wells in a reservoir, cm2 c = coefficient of compressibility of fluid at reservoir temperature, atm-1 f = hydrocarbin-filled porosity, fraction h = net thickness of formation, cm k = permeability of formation, darcy p = pressure at a well, atm p0 = initial reservoir pressure, atm p* = pressure obtained by straight-line extrapolation of linear portion of plot of p versus log [At/(t+ At)] p = volumetric average pressure inside drainage volume of a well q = volume flow rate at a well, cc/sec a: prevailing reservoir conditions q, = total volumetric flow rate from a reservoir, cc/sec at prevailing reservoir conditions rw = radius of well bore, cm T = kt/fµcA t = corrected time of production of a well, seconds, defined by

Jan 1, 1955

By C. W. Hall

Owing to its isolation and comparatively small tonnage, the Yoquivo district is not widely known; though financially important and, geologically, quite interesting. San Francisco dc Yoquivo, the center of the mining district, is in the western part of the state of Chihuahua, Mexico; about 35 miles west of. San Juanito, on the Kansas City, Mexico & Orient R. R. The town can be reached from the railroad by a good trail over a rugged country. The elevation of Yoquivo is 6500 ft., and peaks surrounding the town are 2000 ft. higher. The mining towns of Concheno and Ocampo are 25 miles northwest, and Uruachic is 20 miles southwest. The climate, temperate and healthful, is almost ideal. The rainy season begins in July and ends the latter part of September. There is usually, though not always, some precipitation in all months except April, May, and June: The mountains are covered with pine and scrub oak. Water, wood and lumber are plentiful for all ordinary purposes, and hydroelectric power is available for. about six months of the year, when wood for steam, power is utilized as an expedient. The district has been worked: recurrently for over 60 years. The Yoquivo province lies on the steep western-slope of the Tara-humara division of the Sierra Madre range of mountains. The province is traversed by many deep canyons, most of which flow west. The town is situated on the San Francisco arroyo, which makes a confluence with the Huevachic stream 212 m. southwest; the Huevachic in turn joins the Candemeña river farther down and these two drain the western flank of the Tarahumara mountains and form the headwaters of the Mayo river. The claims of the Yoquivo Development Co., which, is the only organization in the district with a record of any considerable production,: lie within an area roughly 112 m. square. The area extends from the, San Francisco arroyo north, and from the Dolores arroyo west, and is confined to the andesitc formation.

Jan 2, 1926

By D. N. Dietz

A method for determining average reservoir pressure is presented, which is simpler to apply than that devised by Matthews. Brons and Hazebroek. For bounded reservoirs, identical results are obtained if stabilized-flow conditions prevail. The present method yields inferior results in the transient state. The method can, with a slight modification, also be used for water-drive reservoirs. INTRODUCTION In the method proposed by Matthews, Brons and Haze-broek' for determining average reservoir pressure in a multi-well reservoir, the cumulative production (the production time of each well) enters twice: once when the buildup is plotted against In (t + t)/At to arrive at p*, and a second time when the correction, p*-p is determined with one of the several formulas for differently shaped drainage areas. Once a steady state has been attained, however, the previous production history should be immaterial. The same pressure distribution could have been arrived at after different cumulative productions of the individual wells. In principle, therefore, it should be possible to determine average pressures without referring to cumulative productions. In the following paragraphs an expression is presented for the difference between the pressure in a producing well and the average pressure of its drainage area. Then the build-up time needed to overcome this difference is indicated. CASE OF A CIRCULAR DRAINAGE AREA AND A CENTRAL WELL PRESSURE DISTRIBUTION BEFORE SHUT-IN The general differential equation of radial flow (see Muskat, Eq. 10.2) may be written In the steady state, the rate of production of the well is equal to the rate of expansion of the fluid contained in the the drainage area; thus

Jan 1, 1966

By Carl Swartz

IN the course of a recent investigation1 to develop a more satisfactory white-metal. bearing alloy, a number of alloy systems were studied. The cadmium-nickel system showed characteristics desirable in a bearing alloy, and the system was therefore studied in some detail. EXPERIMENTAL METHOD Alloying cadmium with nickel offered no serious difficulty. After melting the cadmium, clean sheet nickel was added while the temperature was maintained at 500° to 600° C: A few crystals of ammonium chloride2 served to clean the nickel when the latter did not "wet" readily. In preparing the individual alloys for thermal and microscopic investigation, a "hardener" containing about 10 per cent nickel was used.

Jan 1, 1933

Jan 1, 1938

By Ihor A. Kunasz

Introduction Lithium minerals occur predominantly in pegmatites which contain mineral assemblages derived from the crystallization of postmagmatic fluids or from the metasomatic action by residual pegmatitic fluids. They have been the traditional sources of raw materials for ceramic and chemical industries. With the discovery of Searles Lake, brines became new sources of lithium. Indeed, the 1960s may well be referred to as the "brine decade" because several brine bodies of significant economic importance were discovered. In the United States, the brines of Clayton Valley, Nevada, are presently exploited by Foote Mineral Co. The brines of the Great Salt Lake of Utah, the Smackover formation, and the Imperial Valley geothermal field, have been defined as important resources of lithium. In South America, new occurrences have been identified in Bolivia and Argentina. At the Salar de Atacama, Chile, new production capacity is scheduled for 1984. Following the termination of the AEC purchase program in 1959, several companies such as Maywood Chemical Co., American Lithium Chemicals, and Quebec Lithium Corp. were forced to close their operations. Nevertheless, with the development of new applications in glass ceramics, air conditioning systems, synthetic rubber, and metallurgy (aluminum potlines), the lithium industry grew steadily, and with the potential application of lithium metal in batteries and nuclear reactors, a healthy growth can be foreseen. New products and new applications are likely to stimulate exploration for expanded, reserves as well as the search for new sources from which lithium could be extracted economically. Geochemistry of Lithium Lithium is the third element in the periodic table. It is the lightest of all the metals, having an atomic weight of 6.938, an ionic radius of 0.68Å and a charge of +1. The geochemistry of lithium has been extensively studied and has been summarized by Rankama and Sahama (1950), Goldschmidt (1937), and Hortsman (1957). The distribution of lithium in igneous rocks is controlled by its size and its charge, and by the (MgO+FeO) / Li2O ratio. In the early stages of crystallization of a magma, that ratio is very large. Consequently, both magnesium and iron are removed by ferromagnesian minerals in preference to lithium which is then concentrated in the residual magma. This results in an enrichment of lithium in silicic rocks and pegmatites (Strock, 1936). Pegmatites are coarse-grained igneous rocks formed by the crystallization of postmagmatic fluids. Minerals within pegmatites may also form by metasomatism (Jahns, 1955). Genetically, the pegmatites are associated with neighboring intrusives. Mineralogically, granitic pegmatites contain feldspar, quartz, and mica as the main constituents and a variety of exotic elements such as lithium, beryllium, tantalum, tin, and cesium, which may or may not occur in economically significant concentrations. Detailed studies by numerous investigators (Cameron et al., 1949, 1954; Hanley et al., 1950; Jahns, 1953, 1955; Page et al., 1953) indicate that pegmatites often exhibit an internal zonal arrangement, with each zone containing a specific suite of minerals. The lithium minerals are usually found in the intermediate zones, and although as many as 13 zones have been recognized by Cameron, et al. (1949), a complete zonal arrangement is rarely found. Zoning of pegmatite bodies has also been observed on a regional basis. The regionally zoned pegmatite sequences exhibit mineral assemblages and complexity according to their re-

Jan 1, 1983

By D. G. Westlake, U. F. Kocks

WHILE single crystals of most materials with cph lattice structure show essentially unlimited ductility, polycrystalline specimens of the same materials exhibit the entire range of ductilities. A difference between the ductility of single crystals and polycrystals may be associated with the special stress concentrations to be expected, for example, at the intersections of slip bands or twin lamellae with grain boundaries. Whether such stress concentrations prove catastrophic depends on the cleavage strength of the material, the size of the stress concentrations, and the speed with which they are formed. Thus, the ductility may vary in degree from material to material. Another possible reason for differences in ductility between single crystals and polycrystals is that a sufficient number of independent deformation modes must be available to insure compatibility between the macroscopic strains in neighboring grains.''2 This criterion is often taken to be a necessary condition for any polycrystal ductility whatsoever, not as one that determines different degrees of ductility; thus, a material with an insufficient number of independent deformation modes would have to be brittle as a polycrystal. The "sufficient number" is five if every grain is to accommodate arbitrary shape changes ("von Mises criterion "). We should like to argue that fewer than five independent modes may be sufficient to satisfy compatibility conditions; and that the internal stresses set up when the plastic strains are not compatible reach the theoretical fracture stress only after a significant amount of macroscopic strain has taken place which may vary in magnitude from case to case, allowing an influence on the degree of ductility. Experimental evidence for these statements is taken from the following review of the number of independent deformation modes observed in the various cph

Jan 1, 1968

By D. J. Hawthorn

The widespread interest shown during the past year in the study of subsurface pressures warrants brief reference to its early development. Though it is impossible to set an exact date when constructive thinking on the subject first began, nevertheless, evidence is available that thought was given to the problem as far back as 16 or 1.7 years ago. There is record in one of the foreign journals of actual subsurface tests made by crude methods in one of the Rumanian fields in 1918 and 1919.' These tests were performed in conjunction with studies made on wells produced by bailing and, incidentally, the final outcome of the work led to the development of the so-called "duplex bailer" which is reputed to have trebled volumetric bailing efficiency. From this time on to 1927 a few scattered bottom-hole pressure determinations were made with makeshift instruments of one form or another, but probably not until 1927 was any great amount of concerted effort directed to the subject. At this fall meeting of the Petroleum Division four years ago was presented one of the first papers2 to appear in this country written for the express intent of advocating the value and importance of subsurface pressure determinations. It is thought to have been the first to present direct data on subsurface pressures obtained through the use of a specially designed recording instrument. As might be expected, the instrument had its limitations, but reasonably accurate results were obtained and, to say the least, it constituted a progressive step in the right direction. During the period from 1927 to 1931, many noteworthy improvements were made in the design and perfection of subsurface pressure instruments suitable to meet all conditions. Because of the magnitude of this task much credit is due the men who pioneered this work. They should feel a keen sense of satisfaction in the thought that their efforts have paved the way for the continuation of this most valuable study. At the present time more than a dozen companies are operating subsurface pressure instruments in the Mid-Continent field. Engineers in

Jan 1, 1933

By Jasper Stuckey

THE object of this paper is to record and interpret field and laboratory observations made by the writers during five years of study of the barite deposits of North Carolina. Deposits of barite are known to occur in three localities in North Carolina (Fig. 1) two of which-the Hot Springs and Kings Mountain -contain material of economic value. The Hot Springs area begins near Bluff, some 6 miles south of Hot Springs, and continues northeast by Stackhouse; a total length of 7 miles. The Kings Mountain deposits lie along a belt that extends from the north end of Crowders Mountain in a southwestward direction, along the east side of this and Kings Mountain, to Kings Creek, South Carolina. The third locality is 3 1/2 miles southeast of Hillsboro, Orange County, a short distance west of the highway leading from Hillsboro to Chapel Hill. It is not known when barite was first discovered in North Carolina, but production from the Hot Springs area began some 50 years ago. The state has never produced large quantities of barite-usually there have been less than three producers-and definite figures are not available, but reasonably reliable estimates indicate a total production of 300,000 tons. From 1901 through 1920 barite mining was on a seemingly prosperous basis and a large tonnage. was shipped from the Hot Springs and Kings Mountain areas. With the depression of 1920 the industry began to decline and production practically ceased in 1926.

Jan 1, 1933

By O. J. Huber

HYDROGEN effects in titanium alloys have been the subject of extensive research in recent years. Lenning, Craighead, and Jaffee1 showed that hydrogen embrittles a titanium and, at the same time, elevates the temperature at which the transition from brittle to ductile failure occurs during impact testing. In later work: the same investigators concluded that several all-ß alloys tolerate large amounts of hydrogen without serious damage to mechanical properties, but two-phase alloys suffer varying degrees of embrittlement, depending upon the specific ß-stabilizing addition used and whether or not an a stabilizer is also present. The mechanism of hydrogen embrittlement has not been clearly established. Strain rate has been shown to be an important factor and, therefore, a strain-aging phenomenon is suspected to cause the effects that hydrogen has produced on mechanical properties.3-5 Ripling6 has pointed out that ductility damage varies inversely with strain rate in a-ß alloys and directly in a alloys. This effect in a alloys can be associated with transition-temperature behavior, but the embrittlemeat mechanism in two-phase alloys remains in question. During the course of research conducted for the U. S. Air Force, a dark-etching phase has been observed at the grain boundaries of certain two-phase titanium alloys after duplex (solution plus aging) heat treatments.5-7 An example of the dark-etching interface phase is shown in Fig. 1. Decrease in ductility accompanies the appearance of the minor phase but has not always been attributable solely to the presence of the phase. Although the dark-etching phase has been observed in alloys under a rather narrow range of heat-treatment conditions, it is of general interest since it is always associated with the presence of hydrogen. The known embrittling effect of hydrogen makes any facet of its behavior of particular importance. The intergranular phase has been observed in titanium-base alloys with relatively high amounts of the ß-stabilizing elements. Specific examples of such alloys include Ti-5 pct Mn-2.5 pct Cr, Ti-3.5 pct Cr-3.5 pct V, Ti-8 pct Mn, and Ti-3 pct Mn-1

Jan 1, 1958

By J. E. Dorn, L. A. Shepard

LOW and Gensamer' demonstrated a number of years ago that the yield point phenomenon in mild steels was associated with the presence of fer-rite soluble carbon or nitrogen. More recently the yield phenomenon in body-centered-cubic metals containing interstitials was rationalized by Cottrell' in terms of a simple dislocation model. Interstitial atoms interact with dislocations in two ways; they cause not only local expansions but induce local tetragonality in the lattice. Consequently, interstitial~ interact with the hydrostatic tension and shear components of the stress about dislocations. They tend to migrate toward the expanded regions of edge dislocations and to assume sites that relieve the shear stresses of screw dislocations. Thus, a dislocation saturated with solute atoms constitutes a lower free energy state than that obtained when the dislocation threads through the average composition regions of the matrix. A greater stress will be required to separate the dislocation from its atmosphere than to move the dislocation through the matrix. This factor gives rise to the upper yield stress, which is required to unleash a series of dislocations in a localized region. This local yielding is propagated across the specimen to form a thin band of plastically deformed material known as a Lueder's band, making an angle of about 45" to the stress axis. Once the band has formed, deformation continues at the lower yield stress by the spreading of the Lueder's band in the direction of the applied stress. Undoubtedly the spreading of Lueder's bands at the lower yield stress is accomplished by the high stress concentrations at the band fronts, which serve to induce continued unlocking of new dislocations in advance of the migrating band fronts. Cottrell and Bilby have shown that the dependence of the yield point on temperature can be deduced by assuming that thermal fluctuations aid the stress in unlocking small dislocation loops from their solute atmospheres. Once a loop that exceeds a critical size has been nucleated, the entire locked diqlocation is released and can migrate. Fisher4 simplified this analysis by assuming that the locking forces were short range, so that if the dislocation loop were displaced only one Burgers vector from its atmosphere, it would be unlocked. Applying his model to the special case of delayed yielding under a constant stress of the order of the upper yield strength, he demonstrated that the delay time 7 for yielding should depend on stress and temperature according to where A and B are constants, G is the shear modulus, and u and T are the resolved shear stress and absolute temperature, respectively. Cottrell and Bilby, Fisher, and Fisher and Rogers' have shown that the above deductions are at least in qualitative harmony with the experimental facts. A number of investigators5-0 have shown that the yield point phenomenon can also be induced in sub-stitutional alloys of face-centered-cubic metals. In general such yield points are not as pronounced as those encountered in body-centered-cubic metals containing interstitials. The yield point phenomenon in these materials is usually enhanced by prestrain-ing at low temperatures and aging at intermediate temperatures. Undoubtedly the yield point phenomenon induced by strain aging substitutional alloys also results from locking of dislocations. But the locking of dislocations in substitutional alloys of face-centered-cubic metals differs somewhat from interstitial locking of dislocations in body-centered-cubic metals. Substitutional elements in face-centered-cubic lattices cause only radial displacements of the adjacent lattice points. Consequently, only the edge components of dislocations can be locked by the mechanism suggested by Cottrell. Additional locking, however, can be obtained by the Suzuki mcchanism.10 In face-centered-cubic metals, dislocations exhibit lower energies when they are present in the

Jan 1, 1957

By M. J. Mullikin, J. B. Conway

Several different equation forms were studied to determine the extent to which each particular equation type yielded an accurate representation of a given set of first-stage creep data. Specially developed least-squares computer programs were employed to obtain unique solutions for the creep-equation constants. In studies of creep data for lead at 14.5"C, nickel at 70OCC, and arc-cast tungsten at 2400°C consistently good representations were afforded by a third-degvee polynomial in t113. Other effective correlations were obtained with the Andrade, Cottrell-Aytekin, and de Lacombe equations along with a third-degree polynomial in t112. A newly proposed creep equation involving a hyperbolic-sine term in t1'3 was also found to yield very satisfactory results. This appears to be the first use of such a functional relationship in the analysis of transient creep behavior. In general, the deformation behavior of a material subjected to a tensile load is described in a strain-time plot. Experiments have shown that, following the instantaneous elongation which results on loading, the instantaneous slope (i.e., creep rate) of the strain-time curve decreases gradually with time and approaches what appears to be a constant value. Equations, therefore, which are proposed to provide an analytical representation of such first-stage or transient creep behavior must be consistent with these observations. In other words, at time zero, these equations must yield a finite deformation value corresponding to the elongation on loading. Furthermore, the first derivative of these equations must exhibit a fairly high although finite value at time zero, and then values which decrease with time. It is also preferable, in general, that the derivative eventually assume a constant value at high time values. Although many studies of first-stage creep behavior have been made and numerous equation forms have been proposed for expressing this type of deformation behavior, it is still not possible to state with any assurance which functional relationship will be adequate for a given set of measurements. Parabolic relationships have been employed most extensively although logarithmic expressions have been shown to be applicable in some instances. Combined forms1 have been studied in considerable detail and have on occasion been found to be very effective. One such expression is that of iXndradea and involves a modified parabolic expression: where 1 is the instantaneous length, lo is the length immediately following load application, t is the time, and p and k are constants. Another combined form has been proposed by weaver3 as follows: where E is the instantaneous strain, is is the linear creep rate, t is the time, and a and b are constants.

Jan 1, 1967