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By W. A. Nagel, R. P. Alger, H. Sherman, J. Tittmann

A sidewall epithermal neutron tool has been developed to substantially reduce environmental effects that have previously complicated neutron log interpretation. Designed for operation in uncased wells, the device provides increased accuracy in both liquid-filled and empty holes. A brief discussion of neutron moderation, diffusion and capture shows that logs using epithermal neutron detection depend on a smaller number of formation-characterizing parameters than those using thermal neutron or capture gamma ray detection. Thus, they come closer to providing an unambiguorls determination of hydrogen content. In this new device a directionally sensitive epithertnal neutron detection system has been incorporated in a side-wall source-detector skid to minimize borehole effects. The effects of variations in borehole size and shape, mud type, temperature and salinity are greatly reduced. Small residual borehole effects are then computationally accounted for in the surface control panel to provide a borehole-corrected neutron log. The log presents a direct recording of neutron-derived porosity on a linear scale. With corrections for borehole effects already applied, this direct recording of porosity simplifies log interpretation. Furthermore, comparison with a linear porosity presentation of a formation density log permits sandstones, limestones and dolomites to be readily identified. Thus, in complex or variable lithology, porosity is determined with greater accuracy and reliability than heretofore. Laboratory data and field results demonstrate the improvements in neutron logging afforded by this new side-wall epithermal neutron logging device. INTRODUCTION The new Sidewall Neutron Porosity (SNP) logging system, designed for use in uncased wells, provides reliability and accuracy never before achieved with neutron logs. The effects of variations in borehole diameter and shape, fluid salinity, mud weight and temperature—parameters that have long complicated neutron log interpretation— are suppressed or corrected for by this sidewall epithermal neutron detection system. Furthermore, to simplify interpretation the SNP log presents a direct recording of computed porosity on a linear scale. The performance improvements achieved by this new system arise primarily from the combination of two im- portant design features. First. though not unique to this new tool, an epithermal neutron detection system is used,',' Epithermal neutron detection substantially reduces the perturbing influences of the thermal neutron absorption properties of rock matrices and water salinity. Second, the neutron detection system is mounted in a directionally sensitive sidewall skid to greatly minimize borehole effects. The purpose of this paper is to explain briefy the advantages offered by the detection of epithermal neutrons, to describe the SNP equipment and the log, to present calibration and correction data and to give examples of interpretation methods made especially convenient by this new system. ADVANTAGES OF EPITHERMAL NEUTRON DETECTION Epithermal neutron detection, of all the neutron methods in current commercial use, provides the simplest determination of formation hydrogen content. Advantages of epithermal neutron detectors, as compared with thermal neutron and gamma ray detectors, are probably best explained by a brief review of the life of a source-emitted neutron. A fast neutron from the source will eventually be cap-tured by the nucleus of an atom. However. before capture is likely to occur, the fast neutron (energy of 100,000 electron volts (ev) or more) will be slowed down until it is in thermal equilibrium with its surroundings. The neutron is then considered to be a "thermal" neutron (average energy of 0.025 ev at 25C). The overwhelming majority of the slowing down thus occurs in reaching epithermal energies (energies just above thermal—0.5 to several ev). After reaching thermal energy. the neutron will "diffuse" through the formation with, on the average, no further energy change until capture. Upon the capture of the thermal neutron, relatively high energy gamma rays arc usually emitted. Hydrogen plays a very important role in the process of slowing down fast neutrons. On the other hand, the absorption effects of water salinity and low concentrations of other strong thermal neutron absorbers—relatively unimportant in the moderation process-—are very important in thermal diffusion, capture and the production of gamma rays. Thus, by detecting only epithermal neutrons with the SNP, spurious effects due to these thermal neutron absorbers are greatly minimized as compared to the effects on tools using thermal neutron or gamma ray detectors. The epithermal neutron detection system affords another important advantage. Log response in various litho-

Jan 1, 1967

By Mayumi Someno, Kazuhiro Goto, Masahiro Kawakami

The apparent rates of decarburization of liquid alloys of Fe-C, Fe-C-S, Ni-C, and Co-C systems and the rate of oxidation of solid graphite with pure carbon dioxide gas and with gas mixtures of carbon monoxide and carbon dioxide have been measured in the temperature range of 1000° to 1600°C. The cotnposition of carbon dioxide and carbon monoxide gas at the reaction surface has been measured by oxygen concentration cells with the ZrO,-CaO solid electrolyte. 1) The apparent rates of the carbon removal are essentially the same for all the cases of solid graphite, Fe-C, Fe-C-S, Ni-C, and Co-C systems under the same experimental conditions. 2) The apparent rates are independent of the carbon content in the high carbon concentration range but very much affected by the flow rate and the gas composition of the CO-CO2 reactant gas mixture. The ratio of the gas consumed by the reaction to the total quantity of the supplied gas is very large under the present experi~nental conditions. 3) There is a concentration gradient of' carbon dioxide in the vicinity of the reaction surface and the content of CO, becomes extremely small at the reaction surface. 4) A large time fluc-tuation of the gas composition was observed. This jluctuation implies the presence of unstable flow in the gas phase in the vicinity of the reaction surface. THE decarburization of molten steel by an oxidizing gas or by slag may be one of the most important chemical reactions in steelmaking processes. Nevertheless, the kinetics of this heterogeneous chemical reaction do not seem to be well-solved even with the previous studies. Although the conditions for the reaction in steelmaking processes are quite different from those in the laboratory scale, some critical experiments may give information on the mechanism of the decarburization. From the previous work,'-' it is known that the rate of the decarburization is independent of the carbon content in liquid iron with more than about 0.2 wt pct C when the oxidizing gases are supplied to the surface of liquid Fe-C alloys on a laboratory scale. Two rate-controlling steps have been proposed for the decarburization of liquid iron with the high carbon content: one is the surface reaction control proposed by Swisher and Turkdogan;' the other is that the rate is controlled by the gaseous diffusion through the gaseous stagnant layer. proposed by Baker. Warner, and Jenkins.7 and also by .Ito and Sano.2 In the present study, some experiments have been carried out for the evaluation of these rate-controlling steps in the decarburization of liquid iron with high carbon content. The apparent rate of decarburization of liquid iron has been compared with the rates of carbon removal of liquid Ni-C, Co-C, and solid graphite under the same experimental conditions. The composition of carbon dioxide and carbon monoxide gas at the reaction surface has been measured by oxygen concentration cells. I) EXPERIMENTAL PROCEDURE Fig. 1 shows the schematic diagram of the reaction chamber. Solid graphite and liquid metals were contained in an alumina or magnesia crucible of 32 mm ID and 35 mm in height. The samples were heated by high-frequency induction and the temperature was measured by the calibrated optical pyrometer. The temperature was held constant to within 10°C. The re-actant gases were supplied to the surface of the samples through the quartz tube of 8.0 mm ID. The distance from the end of the quartz tube to the surface was 20 mm. The block of high-purity graphite was cut and shaped to the inner profile of the crucible. The height of the shaped graphite was 18 mm, which corresponded to the depth of the liquid iron of 100 g. About 100 g of Fe-C alloy (4.20 to 4.40 pct C), Ni-C alloy (1.84 pct C), Co-C alloy (1.85 pct C), and Fe-C-s alloy (4.35 pct c, 0.5 or 1.0 pct S) were melted in the crucible. The reactant gases were pure CO, and gas mixtures of CO-CO,: the flow rates were controlled by capillary flowmeters with bleeders.

Jan 1, 1970

By R. E. Barnes

An overall view of the perlite industry is concisely presented. The geology, mining, milling, processing, and applications of perlite, as well as the present status of the perlite industry are treated. Perlite, in strict petrological usage, describes a specific variety of volcanic glass in which strain, incident to cooling, yielded a concentric structure of fracturing which may be visible either to the naked eye or under a microscope. In commercial usage, the term perlite includes any naturally occurring acidic glass of volcanic origin that will expand when heated to a suitable temperature. The name perlite is a derivation of perlstein which originally defined "certain glassy rocks (hyaloliparites, hyalo-rhyolites) with numerous concentric cracks, from the fancied resemblance of broken out fragments to pearls."1 While perlite has been known to geologists for many years, it was not until 1941, while investigating perlite for use in enamel, that an assayer in Superior, Ariz., noted the unusual expansion characteristics of the ore. Further investigations were delayed until following World War II when many small plants were built and experimentation in the treatment and uses of perlite began. The Perlite Inst. was organized in 1949 to promote the development of the new industry, establish commercial standards through research, and to explore new uses and markets. The Institute, located in New York, represents some 50 producers in the U.S., Canada, Australia, England, France, Germany, Greece, Japan, Mexico, and New Zealand. In 1949, 71,l002 short tons of crude perlite were produced, sold or used by U. S. producers, and this figure increased to 325,0003 short tons by 1959. Such a rate of increase indicates the rapid and continuing growth of the perlite industry. GEOLOGY Perlite ore in its crude form has been found in seven of the mountainous western states, since un-devitrified siliceous volcanic rocks are limited to this section of the U. S. Commercially operated perlite deposits are normally of Eocene and Oli-gocene age.4 These deposits are often several hundred feet thick and may extend over hundreds of acres. In 1959, 13 companies in six states produced crude perlite, although the output in New Mexico comprised 79 pct of the total domestic crude output. Other states in order of their production were: Nevada, Arizona, California, Colorado, and Utah.5 Foreign deposits of perlite which are either producing or under exploration are Australia, Canada, Greece, Hungary,6 Iceland, Ireland, Japan, Mexico, New Zealand, and Sardinia. The ore may exhibit a variety of characteristics depending partially on its water content and eruption history and may range through many shades from black to white. While these characteristics may vary slightly among deposits, perlite ore from a particular source is normally quite uniform. Available chemical analyses of perlites from a large sampling of domestic deposits were recently assembled by the Technical Committee of Perlite Institute and are presented in Table I. While the ranges given do not apply to a particular perlite, they are an indication of the chemical analysis which may be expected from any presently commercially operated deposit. The specific gravity of the perlite ore ranges between 2.2 and 2.4, and its bulk density when crushed and sized is 75 to 90 Ib per cu ft. MINING AND MILLING Perlite ore is quarried from open pits by conventional power equipment, although blasting has been occasionally employed. The rock is then stock-piled until needed. While the milling of perlite may seem a simple process compared to that required for basic metals, or even other nonmetals, the need for accurate control of particle size becomes extremely important in further processing. The first step in this operation is the primary crusher, which is normally a jaw crusher. Following crushing, the material is dried, if necessary, in a rotary dryer and conveyed to a secondary grinder which may be a rod mill, hammer-mill, or cone crusher. However, the crushing characteristics of the perlite, caused by incipient cooling fractures, requires it be removed from the grinding operation once it is reduced to the required size so as to prevent overgrinding. Following the grinding operations, various size screens are used to separate the ore according to particle sizes required for particular uses. Most plants use two or more stages of crushing with perhaps four stages of screening.

Jan 1, 1961

By B. H. Kear, S. M. Copley

Stress-stvain curves are presented for Ni3Al (y') cvystals in several ovientations, deformed in tension and compression at constant displacement rate, at temperatures from 70° to 2000°F. Both the yield stress and wovk havdening increase with temperature, with the magnilude of the effect dependent on ovientation. The yield stress maximum occurs at 1500°F in [001], at 1400°F in [011], and at 1200°F in [111]. The suppression of the yield stress peak in [011] and [111] orientatiorzs is due to the onset of cube slip, rather than octahedval slip, a1 elerated temperatures. The temperature and orientalion dependence of work hardening in nominal single slip orientations corvelates with changes in the CRSS ratio for octahedral slip and cube slip, in agreement with a model for work hardening based on pinning of screw dislocalions by cross slip from an octahedral plane into a cube plane. It is concluded that the unique plastic properties of y' have a decisive influence on both ductility and strength characleristics of y +y' nickel-base superalloys. It has long been recognized that the strength of y + y' nickel-base superalloys depends on the precipitation of the y' phase [basically Ni3(Al,Ti)]. This paper presents new data on the strength characteristics of single crystals of simple y' (Ni3Al), and forms the first step in a systematic program aimed at elucidating the mechanisms of hardening in the complex commercial alloys. 1) EXPERIMENTAL PROCEDURE Single crystals of off-stoichiometric NiA1 were grown from the melt under vacuum by a modified Bridgman method. The melt was poured into a preheated alumina mold and crystal growth was promoted from one end by gradient cooling. The crystals were homogenized by annealing in hydrogen at 2400° F for 72 hr followed by furnace cooling. Chemical analysis of samples taken from several crystals gave an average composition of 88.2 wt pct Ni. Spectrographic analysis gave as the principal impurities in weight percent— Si (0.02), Mg (0.01), Fe (0.02), Ti (0.002), Cu (0.008), and Co (0.03). Tensile specimens with specifications as in Fig. 1 were prepared by a series of operations involving electrical discharge machining, precision grinding, and electropolishing. Compression specimens with dimensions 1/4 by 1/4 by -3/4 in. were prepared in a similar manner, except for the initial shaping operation using a precision cut-off wheel/two-circle goniometer unit to give selected crystal orientations. Specimens were deformed in a Baldwin-Wiedemann testing machine with furnace attachment, using a strain rate of 5 x 10-4 sec-1. The strain measuring device consisted of extension arms attached to the tensile grips (or compression plattens) at one end and leading out of the furnace to an LVDT at the other. Temperature was controlled by a thermocouple placed in contact with the specimen. According to the known phase diagram for the Ni/A1 system,' when an alloy of the specified composition is cooled from the melt, primary y (nickel solid solution) dendrites grow at the expense of the liquid phase, which becomes enriched in aluminum. At the eutectic composition the remaining liquid freezes as a two-phase mixture of y + y' (Ni3Al). Upon further cooling, a solid state transformation occurs, involving the precipitation of y' in the primary dendrites, and the complete transformation of the eutectic mixture to massive y'. The as-cast structure consists, therefore, of y + y' dendrites with interdendritic regions of massive y', i.e., transformed eutectic, Fig. 2. 2) DISCUSSION OF RESULTS 2.1) Stress-Strain Curves. Fig. 3 shows tensile stress-strain curves for crystals in orientations close to [001] deformed at temperatures from 70° to 2000°F. Both the yield stress and total elongation are strongly temperature-dependent. At 70°F, easy glide is absent, and the work hardening coefficient BIT - G/300. At T > 1500°F, the negative slope of the stress-strain curves is due to pronounced necking in the crystals. The yield stress maximum at 1500° F corresponds with a minimum in the ductility, Fig. 4. The extensive duc-

Jan 1, 1968

By J. Chipman, N. J. Grant, H. L. Bishop, H. N. Lander

Data of several studies on the equilibrium between molten iron and open hearth-type slags have been combined to determine some of the chemical reactions involved in steel-making. Effects of slag composition and temperature on the iron oxide activity, distribution of sulfur between slag and metal, and the carbon content of the metal are discussed. Also, an overall reaction for the equilibrium between sulfur and oxygen is presented. DURING the past 15 years, a number of significant equilibrium studies have been carried out between liquid iron and simple basic and acid slags in an effort to throw light on the chemical reactions involved in steelmaking. This paper is a summary of the experimental reports on investigations which have been conducted at the Massachusetts Institute of Technology, and of related work in other laboratories. The investigations summarized in this paper include the works of Fetters and Chipman1 and Taylor and Chipman,' which dealt with simple slags that are similar to those found in the open hearth. The sulfur determinations of the slag-metal tests of Fetters and Chipman as reported by Grant and Chip-man" are included. Also, the investigations by Win-kler and Chipman' and Grant and ChipmanQ f more complex slag systems are included in this summary. The experimental procedure is described in detail in each of these papers and will not be discussed. Since the previous reports have been somewhat independent, it is desirable to review and combine the data of the various investigations to determine, as accurately as possible, the reactions in the slag-metal systems of the open hearth. It is the object of this report to present the combined data in such a way as to enhance their utility and applicability. Oxidizing Power of Slags of the System (CaO+MgO)-Si0,-FeO in Equilibrium with Carbon-Free lron The slags selected to determine the iron oxide activity in equilibrium with pure liquid iron were those containing less than 2 pct each of P,O,, MnO, or A1,0, on a weight percentage basis. The method used to calculate activities of iron oxide in liquid slags was that developed by Taylor and Chipman.' The solubility of oxygen in molten carbon-free iron under pure iron oxide slags can be expressed by the following eauation —6320 log (pctO)-------------— + 2.734 [1] where T is the absolute temperature. The oxygen solubility values as determined from Eq. 1 were used throughout this study to calculate the iron oxide activity. The iron oxide activities of slags of various iron oxide contents are plotted in Fig. 1 as a function of the basicity, which is defined as the ratio (pct CaO + pct MgO)/pct SiO,, and are based on molecular percentage values of the components. The percent (FeO), is the total iron content in the slag calculated to FeO. Fig. 1 shows that as the basicity increases at constant mol pct (FeO),, the iron oxide activity increases rapidly and reaches a plateau which extends on the basicity scale from about 1.3 to 2.3; the iron oxide activity then decreases rapidly until a basicity of about 3.0 is reached, where it tends to level off. The solid portions of the curves represent the experimental data of Fetters and Chipman and Win-kler and Chipman. Their experimental heats were made in magnesia crucibles, and hence the slags were saturated with magnesia. The broken lines on the left represent the experimental data of Taylor and Chipman, who used a rotating crucible. In general, these slags contained less than 3 pct MgO. The absence of data for slags containing less than about 40 mol pct (FeO), and basicity ratios greater than about 2.5 made it necessary to calculate curves using ionic concepts of slags. The broken lines on the right, which disregard the solubility limits of di and tricalcium silicate and lime, were obtained by following the treatment of Flood and Grjotheim,"

Jan 1, 1957

By G. L. Tufford, R. L. Bleifuss

Low-grade manganiferous iron ores of Minnesota's Cuyuna Range, in general, do not respond to conventional mineral dressing techniques because of their fine-grained texture. Reducing these ores to magnetite with subsequent magnetic separation and flotation have not given satisfactory results because, in many instances, concentrate grade and manganese recovery are low. Metallization of iron and concurrent reduction of higher manganese oxides to MnO, as in the R-N process, followed by recovery of iron by magnetic separation and manganese by leaching, seems to be a technically feasible process. High-temperature x-ray diffraction studies show that solid-state reactions between iron and manganese, with the formation of intermediate iron-manganese oxides, occur during reduction and affect recovery of both iron and manganese from the final product. Solid state reactions also occur between FeO, MnO, and SiO, at temperatures as low as 900°C. The kinetics of these reactions are such that they become an important factor in the treatment of ores by the R-N process. These investigations suggest a temperature and gas composition cycle that would maximize both iron and manganese recovery. During the past ten years, iron ore shipments from the Cuyuna Range of Minnesota have decreased sharp1y. Because of adverse grade, structure, and cost, many Cuyuna ores are no longer competitive with high-grade foreign ores and domestic pellets. The low-grade manganiferous iron ores from the Cuyuna Range, in general, do not respond to conventional mineral dressing techniques because of their fine-grained texture. Reducing these ores to magnetite for subsequent magnetic separation and flotation has not given satisfactory results because concentrate grade and manganese recovery are often low. However, a technically feasible process appears to be metallization of the iron and concurrent reduction of manganese oxides to MnO with recovery of metallic iron by magnetic separation and extraction of manganese from the tailings by leaching. In 1962 the R-N Corp., with a grant from the Area Redevelopment Administration, conducted an amenability study of the metallization of manganiferous iron ore from the Cuyuna Range. The results of this preliminary investigation were sufficient to interest the Economic Development Administration in sponsoring further studies of the process with emphasis on secondary recovery of manganese from the nonmagnetic tailings. Inasmuch as the metallization process has considerable influence on the final form of the manganese - its texture and distribution between the magnetic concentrate and nonmagnetic tailings-the investigation included a study of metallization of the ore as well. Therefore, the investigation conducted at the Mines Experiment Station covered three interrelated phases: (1) laboratory R-N roasting studies and magnetic separation tests, (2) laboratory chemical extraction experiments of the nonmagnetic tailings, and (3) a mineralogical study of the crude ores and their various roast products. High-temperature x-ray diffraction investigation of the Fe-Mn-Si0,-0, system is the main topic of this paper and an extension of the mineralogical work. GENERAL GEOLOGY The Cuyuna Range is known for its complicated geologic structure, complex orebodies, and generally indifferent response to attempts at conventional beneficiation. Several geologists have made intensive studies of the Cuyuna Range, including Leithl (1907), ~darns' (1910), Zapffe3 (1925), Grout and Wolff4 (1955), and schmidt5 (1963), whose study was the most comprehensive of all. The Range is covered with glacial deposits - till, out-wash, and lake sediments -up to 250 ft thick. Bedrock stratigraphic units of the Cuyuna Range consist of three tightly folded Precambrian sedimentary formations. The lower unit is the Mahnomen formation, composed of 2000 or more feet of argillite, slate, siltstone, and quartzite. The middle unit is the Trommald formation, which varies from 45 to 500 ft in thickness and comprises the major iron-bearing formation. The upper unit is the Rabbit Lake formation, consisting of over 2000 it of argillite, slate, and interbedded lenses of lean iron formation. In the central part of the Cuyuna Range, the units have been folded into a series of

Jan 1, 1969

By B. C. H. Steele, C. B. Alcock

In choosing solid oxide electrolytes for use in the measurement of thermodynamic quantities at high temperatures, the two most important criteria are the values of the partial ionic and electronic conduc tizities. Measurements of these conducticities have been made for some Group IVA oxides and solid solutions of these oxides with CaO, Y2O3, and La2O3. The total conductivities as a function of temperature. oxygen partial pressure, and composition were determined, as well as the electromotive forces of cells in which the oxygen partial Pressures of the electrodes were between 10-7 and 10-29 atm at 1000°C. Additional factors that influence the experimental arrangements, such as the operating temperature, the appropviate cell atmosphere, and electrode kinetics, are also discussed. IT has long been recognized that galvanic cells incorporating solid electrolytes can possess many advantages for the measurement of high-temperature thermodynamic data. Unfortunately, the electrical-transport properties have only been established for a few solid electrolytes, although attempts have been made, and are still being made, to use such materials as porcelain' and magnesia.' Kuikkola and Wagner have discussed3 and demonstrated4 various applications of solid electrolytes, and, in particular, their work stimulated the electrochemical measurement of oxygen activities using cells incorporating the solid oxide electrolyte, Zr0.85Ca0.15O1.85 The excellent characteristics of this oxide electrolyte have been confirmed by the investigations of Kingery et al.5 (oxygen ion diffusion), Carter and Rhodes6 (zirconium and calcium ion diffusion), and Weissbart and Ruka7 (electronic transference number). However the observations of Peters and Mobius,8 later confirmed by Schmalzried,9 indicated that the electronic component of zirconia-based electrolytes could become significant at low oxygen chemical potentials. Under these conditions, thoria-based electrolytes have obvious advantages arising from their superior thermodynamic stability. It was known that certain thoria solid solutions possessed defect fluorite structures containing anionic vacancies (cf. Zro.85Cao.l50O1. 85), although data on their electrical properties were conflicting. Kiukkola and wagner4 concluded that thoria-based electrolytes exhibited appreciable electronic conductivity, whereas Peters and Mobius8 mentioned that the electronic conductivity only became important at high oxygen partial pressures, but gave no further details. In addition, both Kiukkola and wagner4 and Peters and Mann'" had determined the oxygen chemical potentials associated with the Fe-FeO, Co-COO, Ni-NiO, and Cu-Cu2O equilibria, and it was not known whether discrepancies in their results could be attributed to the different cell design, or the thoria-based electrolyte used by Peters and Mann. These uncertainties have been resolved during the present investigation into the measurement of low oxygen chemical potentials, and transport properties of the relevant oxide electrolytes are presented and discussed. Other experimental difficulties associated with low oxygen chemical potential measurements are also described, with particular reference to the Nb-O system. 1. THEORETICAL CONSIDERATIONS Oxide systems of potential use as solid electrolytes possess a large energy gap between the valence and conduction bands. Little is known about the defects present in these wide-gap metal oxides as a function of impurity content and deviations from stoichiom-etry, or the mechanisms by which electronic charges move in these solids. For these materials it is convenient to represent the measured conductivity as the the sum of three terms: where a, is the conductivity due to positive hole conduction (p type), and oe is the electronic conductivity due to electron conduction (n type). U there is a large concentration of ionic vacancies fixed by composition then the ionic contribution will not be a function of oxygen pressure. Although the possibility of a pressure-independent electronic component also cannot be ignored, it is likely that such a term would only become significant at very high temperatures, and in general the positive hole conduction will increase with increasing oxygen pressure, and the electron conduction will increase with decreasing oxygen pressure. It follows that the total conductivity is related to oxygen partial pressure as follows:

Jan 1, 1965

By W. F. Hower, W. Brown

Large-scale sand consolidation tests were conducted in an effort to determine the reasons for the successes and failures of this method of sand control. Several different consolidating materials were used in treating both clean and bentonitic sands that were packed in a chamber having a capacity of 3.3 cu ft. The results were essentially the same for all of the different consolidating materials, The data show that low-viscosity consolidating materials pumped at a relatively slow rate gave the best results. Where the formation has produced sand, the treating fluids can compress the formation, thus permitting the channeling of fluids to another horizon. Pressure-packing these zones before attempting to consolidate is recommended. Sands containing more than 4 per cent of water-swelling clays are not good candidates for consolidation. It is indicated that loose sand, particularly when it is bentonitic, can be fractured during the placement of the treating fluids. INTRODUCTION Sand production in oil and gas wells has plagued the industry for many years, and numerous cures for this problem have been suggested. Most methods have been successful to a certain degree, but the great variety of well conditions that exist in the different areas has magni- fied the problem and limited the successful use of the various systems. Four review papers1-4 present a wealth of information concerning the degrees of success that have been obtained by the different sand-control methods. The bridging of sand grains by the use of gravel packs and screens has been quite successful. However, these methods do not leave the casing clear for all types of multiple completions, and the cure does not last for the production life of the well in some instance:;. The control of loose sands by sand consolidation with resins has never been as successful as desired. It has always been hoped that such a treatment would eliminate all sand problems for the life of the well, but. initial applications, starting in the middle 1940's, were only moderately successful. Lott, et a1,3 reported a success ratio of approximately 50 per cent and made the following conclusions. The highest percentage of successes were obtained where: a. Consolidation of a zone was made at the time of initial completion or prior to the production of sand. b. The interval treated was less than 12 ft in length. c. Between 30 and 50 gill plastic/ft of producing interval was displaced through the perforations. REASONS FOR SAND CONSOLIDATION FAILURES Our own experiences in the field of sand consolidation point toward the following conditions as the major reasons for the failure of sand consolidation attempts. 1. Mud-plugged perforations and mud invasion of the formation. 2. Sand in the casing covering all or part of the perforations. This sand could be either formation sand or one of the coarser sands used as propping agents in hydraulic fracturing. 3. Holes in the casing. 4. Channels behind the casing. 5. Attempting to treat too long a perforated section. 6. Too high a percentage of water-swelling clays in the formation. 7. Formations that have produced sand. Recent attempts were made to treat perforated sections ranging from 10 to 30 ft, in wells that have produced sand, by using a straddle packer that was raised and lowered through the perforations as the consolidating material was being pumped. In most instances, the pressure required to pump fluid into the formation varied considerably as the tool was raised and lowered. This suggested the possibility that significant differences in permeability were present or that only part of the formation had produced sand. There were times when a sudden break in pressure indicated that a fracture was being formed. Research conducted several years ago concerning the problem of the control of water in air and gas drilling indicated that shale sections could be fractured quite easily. In addition, it was determined that it was easier to pump fluids into shale bodies by fracturing the shale itself, or the interface between the shale and sand, than to pump into a fluid-saturated formation. Formations that produce sand are usually adjacent to shale bodies and frequently have shale streaks of various thicknesses inter-bedded in the sand. Therefore, where shale is exposed to fluid pressure it

By M. V. Lowry

This paper outlines the economic considerations that led to the recent installation of a thickener at St. Joseph LeadCo.'s Balmat, N.Y. mill. To incorporate storage of concentrates, they decided upon a single, unusually deep tank to be used for both storage and thickening. The abnormally high rake lift required was achieved by the novel feature of having the entire drive platform raise and lower. Initial operating problems are described along with the satisfactory solutions. Total costs for concentrate handling before and after installation of the storage thickeners are compared. In Northern New York State, the St. Joseph Lead Co. conducts a 2100 tpd zinc mining and milling operation at its Balmat Plant. Conventional crushing, grinding, and flotation is used to produce a zinc concentrate. For 32 years, from 1930 through 1962, the plant operated with the concentrates going directly from flotation to the filtering, drying, and loading facilities. All of the concentrate handling equipment, therefore, had to operate 24 hrs per day. It also had to accommodate wide fluctuations in tonnage, due to variations in the grade of ore. Many problems were thereby encountered in filtering and drying, but it was never concluded that the cost could be justified for installing a conventional, large diameter thickener. Finally, in 1963, they installed an unconventional thickener that is unusual in several respects. The tank depth is 16 ft instead of the normal 8 ft. The rakes are raised and lowered by having the main drive gear located on a movable platform. Automatic controls are programmed to raise the drive platform and rakes during one shift of storage. During the next two shifts of withdrawal, the controls are programmed to lower the drive platform and rakes. After three years of operating this unique storage-thickener, the conclusion is that a correct choice was made from several alternative schemes for storing concentrates. The various considerations involved in the final selection will here be analyzed, and the design features and installation details will be de- scribed. Operating problems and modifications made to the equipment will next be considered, and finally the effects upon filtering, drying, and loading will be reported. SELECTION CONSIDERATIONS Even without a thickener, concentrate handling had become reasonably efficient at the Balmat Mill by the year 1962. A tonnage that varied between 6 and 25 tph was being handled fairly satisfactorily. The filter cake moisture of 8%% seemed quite respectable, except that two large filters were usually in service. Three filters often had to be operated in order to prevent excessive filter overflow with consequent loss of values. This situation occurred when zinc concentrates from flotation exceeded 20 tph and when filter cloth blinding developed. Over the years, numerous small improvements had been effected, such as: selection of a filter cloth with better flow characteristics; addition of flocculant to the filter feed; and, in 1953, the smallest of three drum filters was replaced by a five disc, 8' 10" diam filter with a bottom agitator and snap blow. As another example of fairly efficient operation, the oil-fired dryer was doing a seemingly satisfactory job of further reducing the moisture content to an average of 3%. However, there were often considerable dust losses when the tonnage suddenly dropped off to 6 tph. At high tonnage rates, the resulting high moistures of 4% and 5% caused difficulties due to concentrates sticking and freezing in chutes leading to the box car loaders. (Drying of concentrates is justified because of the high freight rate for the long shipping distance to the company owned smelter at Josephtown, Pa. near Pittsburgh.) It was long realized that installation of a thickener would permit the subsequent steps of concentrate handling to proceed more smoothly and would alleviate the problems existing in the filtering, drying, and loading operations. It was also realized that even a slightly lower filter cake moisture could mean considerable savings in fuel oil. However, all these factors were never quite sufficient to warrant the expense of a thickener until three more considerations were added to the picture. First, the advent of flocculants meant that a thickener of relatively small area could now be considered. Secondly, a complete renovation of the zinc flotation circuit was made between 1957 and 1961. The

Jan 1, 1967

By C. S. Matthews, M. J. F. Rosenbaum

The purpose of thir work wax to lcarn it~lzut infori~lation could he obtained from various typs of pilot water floods and to attempt to find the optunum pilot patter11, for a revervoir which had previously been depleted by a solution gas drive. The study was made in the laboratory with mathemetical methods a dynamic analog and a potentiotnetric analog. Results werp tested against the field llistorics of a nrrnlber of pilot water floods. At a reasonable valrre of currzulative injection, the total production rate for the one-injector five-spot should reach about 6.5 per cent of injection rate, and for a four-injector five-spot, about 9 per cent. Accurate estimates of ultimate recovery cannot be made on the basis of such snzall prorluction rates. However, with a pilot composed of nine ir1jector.s and 16 producers the production rate is approximately 50 pcr cent of injection rate at a reasonable value of camulative injection. Sonle inforn~ation for extended performance predictions might he obtained from such a large pilot. These conclusions were drawn on the basis of results obtained for unit mobility ratio, and a sturly using tlre potentiometric analog was made of the effect of other mobility ratios to determine the range of applicability of these predictions. For the four-injector, five-spot pilot with the ratio of production to injection rate (before water breakthrough) is about twice that for with it is about two-thirds; and with M0= 10, it is about one-third For high mobility ratios, it was found that the production rate increased considerably as water-cut increased. These result can be used to modify, qualitatively, the inter.pretntions based on curves for the unit rnobilit\. ratio CaSeS. It was found that the maximum ratio of production rate to injection rate obseriled in field pilot floods was of rhe scime order as that prerdicted by these methods. The time required to reach thisr maximum did not generally agree with the time predicted for a homogeti~orir reservoir. The differcrlce between predicted and observed time of response gives an indication of the permeability profile and of the condition of the producin,g wells. Pilot water floods of the pattern type are generally carried out in reservoirs which have been depleted by solution gas drive and are at low pressure. Under these conditions, oil and water can be considered incompressible. It is assumed that, as the water is injected, an oil bank forms ahead of it and that there is a distinct interface between the water zone (or bank) and the oil zone (or bank) and between the oil zone and the region ahead of the oil zone. It is further assumed that only gas is mobile in the unflooded (gas) region, only oil is mobile in the oil bank and only water is mobile in the water bank. The saturations and the mobilities associated with each zone are assumed uniform. We idealize our reservoir to be homogeneous, horizontal and of constant thickness. Effects of gravity within the producing layer are assumed negligible. If the actual time-dcpendent flow problem is approximated by a acries of steady-state problems. the potential and stream function in the oil bank and water hank satisfy Laplace&apos;s equation in two dimensions. We can therefore use a poteiitiometric analog of this system. Potentiometric models have yielded uscful results in this laboratory&apos; and clsewhere in the study of a variety of secondary recovery problems. For the case where M = I, we generally prefer to use theoretical mcthods as well as a simpler dynamic analog. Except where otherwise noted, the ratio, side of five-spot/wellbore radius. is taken to be 3,600. a figure which corrcsponds to a normal-size wellbore in a 10-acre well spacing. THEORETICAL EVALUATION OF VARIOUS PILOT PATTERNS, Mw0 = 1 <&apos;he theoretical models which we used to examine the performance of various pilots are shown in Fig. 1. Image theory was used to determine the ratio of production rate to injection rate as a function of the volumc of the flood. The ratio of production rate to injection rate was chosen because this is an easily measurable quantity which is characteristic of a pilot

By C. S. Matthews, P. Hazebroek, H. Rainbow

It ha been suggested that lormation fractures created by well stimulation treatments will adversely affect sweep-out efficrency in injection operations. Fluid-flow model studies involving vertical fractures of various lengths and fluid systems of various mobility ratios have been carried out to study this subject. In addition, limited data have been obtained on one model containing a horizontal fracture. It was found that relatively long and highly conductive fractures (not generally obtained fracturing operations) were required to affect the sweep-out efficiency substantially. In a given case in the field an approximate distinction can be made between the presence of long conductive fractures and shorter or less conductive ones. This is done with pressure build-up analyses along with data on the relationship of fracture length and conductivity to well productivity. This type analysis shows that usually the fractures induced are either short or of limited conductivity and therefore do not damage sweep-out efficiency. INTRODUCTION Improved well productivity and in-jectivity can frequently be exploited in injection operations. Higher total throughput can yield improved economics. On occasion, the achievement of an increased productivity or injectivity in specific wells can bring about a more uniform sweep of the reservoir. Higher rates can be exploited particularly in water floods of "depleted" reservoirs where a rapid "fill-up" is desired and where low pressures contribute to low well productivity. The creation of fractures local to the wellbore is an excellent means for achieving these objectives. Even though fracturing has been employed in some floods with success,1"3 there still seems to be some reluctance to employ this tool for fear of undue damage to the flood pattern and ultimate recovery. We therefore need to examine the influence which fractures of varying length may have on flood performance and then determine the length of fractures which obtain in the field with conventional fracture treatments. A substantial influence of fractures on the recovery obtained at breakthrough of the injected fluid has been presented by Crawford and Collins for equal fluid mobilities for the line-drive pattern.4,5 In addition, the influence which a fracture has on the production performance after breakthrough and on the ultimate recovery warrants consideration in reaching a conclusion concerning the use of induced fractures in flooding operations. This report presents this type of data for the five-spot injection pattern for several fluid mobilities. In arriving at some conclusion concerning the fracture lengths obtained in field operations we must examine the performance characteristic most affected by the fracture. This is the change in the flow system as reflected in the change in productivity and pressure build-up behavior. A study of these changes is also presented in this report. RESERVOIR ANALOGS The X-ray shadowgraph technique, employing miscible displacement in porous models, has been used in the study of the influence of fractures on pattern sweep-out efficiency. The X-ray shadowgraph procedure is described in detail in an earlier report8. Fractures were represented by leaving the proper portion of the model surface exposed to either injection or production. This assumes the fracture resistance to be negligible compared to that of the formation. Actually the flow resistance in propped fractures obtained in the field is sometimes not negligible so that the results with this model indicate the maximum influence of the fracture. Two types of models were necessary to represent vertical fractures in a five-spot flood. These pattern elements are illustrated in Fig. 1. In studying the influence of the horizontal fracture, only one well spacing length to thickness ratio of 50 was used. The pool unit of a Carter Electric Analyzer was used in studying the influence of fractures on productivity and build-up behavior. The square drainage system of a well was represented by a network of 576 elements of equal volume and resistance. One-fourth of this drainage area was studied as a model unit using a network of 144 condensers and resistors. Vertical fractures were represented by a shunt directed from the well perpendicular to the drainage boundary. Horizontal fractures were represented by a circular shunt. Resistance of a shunt was varied in representing different conductivities for the fractures. FRACTURE DIRECTION AND LENGTH The direction at which a vertical fracture extends into the formation and its length and conductivity influence the sweep behavior. The two

By C. Gatlin, N. E. Garner, A. Podio

Experimental data from single chisel blows on Leuders limestone are presented. A pressure chamber, similar in design to well known microbit drilling chambers, was utilized to impose variorcs stress states on the sample. Confining pressure of zero to 10,000 psi and borehole pressures from zero to 5,000 psi have been used in the studies. Pore pressure was zero and the rock samples dry in all instances. Force-displacement records and visual examination of the craters indicate that the mode of failure depends on both confining and borehole pressure in certain ranges, ranging from brittle, through a transition, to near plastic. The mode of failure is reflected in the observed blow force and energy data, as well as the shape of force-penetration curves. INTRODUCTION A previous paper&apos; presented initial data from the project on which this paper is the second report. While the first paper dealt with impact studies on synthetic rocks, the literature cited there is also pertinent to this paper, but will not be listed again in order to avoid needless repetition. This paper presents experimental data from single chisel impacts on limestone at certain simulated wellbore stress states. Specific variables investigated were combinations of borehole and confining pressure, crater geometry, a narrow range of impact velocity and the forces required to drive the chisel into the specimens under the varying conditions. EXPERIMENTAL PROCEDURE The same basic apparatus described in our earlier paper, except for the pressure vessel, was used in this study. Fig. 1 shows the complete experimental system. Fig. 2 shows details of the pressure cell, which is quite similar to the well known microbit drilling chamber. The confining (overburden) pressure system provides independent pressure control over the sample except for two, 21/4 in. diameter areas located on the sample ends. These two areas provide a pore pressure entrance on the bottom and a striking surface on the top where borehole pressure can be controlled. The ends are isolated from the confining pressure by O-ring seals. The borehole and pore pressures are related through the striking surface; they will be the same unless a seal is deposited on the borehole surface, either a mud cake or some other impermeable membrane. In these studies pore pressure control was not used, as the rocks were dry and unsaturated in all cases. Rock samples were prepared from 4-in. cubes as illustrated by Fig. 3. The circular disks of adhesive vinyl plastic protected the impact surface from the resin coating (Scotchcast No. 2) and were removed just prior to each test. This procedure insured a fresh uncontaminated surface for the impact. Fig. 4 shows the dimensions and loading of the sample, including the concentrations around the "borehole" periphery (O-ring seal). The rock used in this study was Leuders limestone, of Permian age (Leonard), quarried near Leuders, Tex. Geologically, Leuders limestone is a light gray, fossili-ferous limestone (oolitic foraminifera1 biosporite). Its fossil content is 80 to 90 per cent and consists primarily of calcitornellid, ostracods, pelecypods and oolites with the remaining part intraclasts. There are hematite or limo-nite rims on some of the intraclasts. The porosity is approximately 20 per cent, but the permeability is less than 1 md. There is no apparent orientation in the structure. Triaxial tests have been conducted to determine the variation of the physical properties of Leuders limestone in three orthogonal directions&apos;, and it is known to be unusually isotropic and uniform. Physical parameters for this rock are: uniaxial compressive strength = 9,700 psi; F = 32 and C = 2,700 psi; where + and C are Coulomb equation values (t = C+u tan +). Impact tests were run under the combinations of confining and borehole pressures shown in Table 1. Samples were dry with atmospheric pore pressure in all cases. Tests, in which elevated borehole pressures were applied, used a single layer of household Saran-Wrap to prevent horehole fluid invasion into the sample. This proved to be simple and reliable. The blunt wedge used in all the tests was 0.75 in. long and had an included angle of 60" with a 0.05-in. flat. In addition, a sharp 60" wedge was used for all confining pressures at zero borehole pressure. The chipper speed

By C. E. Hottman, R. K. Johnson

Fluid pressure within the pore space of shales can be determined by using data obtained from both acoustic and resistivity logs. The method involves establishing relationships between the common logarithm of shale transit time or shale resistivity and depth for hydrostatic-pres-sure formations. On a plot of transit time vs depth, a linear relationship is generally observed, whereas on a plot of resistivity vs depth, a nonlinear trend exists. Divergence of observed transit time or resistivity values from those obtained from established normal compaction trends rinder hydrostatic pressure conditions is a measure of the pore fluid pressure in the shale and, thus, in adjacent isolated permeable formations. This relationship has been empirically established with actual pressure measurements in adjacent permeable formations. The use of these data and this method permits the interpretation of fluid pres.rure from acoustic and resistivity measurements with an accuracy of approximately 0.04 psilft, or about 400 psi at 10,000 ft. The standard deviation for the resistivity method is 0.022 psi/ft, and for the acoustic method 0.020 psi/ft. Knowledge of the first occurrence of overpressures, and of the precise pressure-depth relationship in a geologic province, enab1es improvements in drilling techniques, casing progroms, completion methods and reservoir evalzmtions. INTRODUCTION CENKRAL STATEMENT Operators engaged in the search for and production of hydrocarbon reserves in Tertiary basins are more and more frequently confronted with complications associated with over pressured (abnormally high fluid pressure) formations. This is particularly true in the Texas-Louisiana Gulf Coast area. The problems associated with these formations are of direct concern to the combined activities of all phases of operations, i.e., geophysical, drilling, geological and petroleum engineering.&apos; - Knowledge of the pressure distribution of a given area of operations would greatly reduce the magnitude of many of these complexities and in some cases would completely eliminate specific problems. his pape; presents techniques developed for estimating formation pressures from interpretations of acoustic and electric log data. Specifically: the acoustical and electrical properties of shales, reflected by conventional acoustic and electrical surveys, can be used to infer certain reservoir properties, such as formation pressure, at any level in a well. It has been possible to develop these techniques because of a firm understanding of the basic principles that govern and apply to such overpressured provinces. NORMAL PRESSUKES Normal pressures refer to formation pressures which are approximately equal to the hydrostatic head of a column of water of equal depth. If the formations were opened to the atmosphere, a column of water from the ground surface to the subsurface formation depth would balance the formation pressure. On the Gulf Coast, the shallow, predominantly sand formations contain fluids which are under hydrostatic pressure. These formations are said to be normally pressured or to have a normal pressure gradient.* Experience has shown that the normal pressure gradient on the Gulf Coast is approximately 0.465 psi/ft of depth. OVERPRESSURES Formations with pressures higher than hydrostatic are encountered at varying depths in many areas. These formations are referred to as being abnormally pressured, abnormally high pressured, or overpressured. Formation pressures up to twice the hydrostatic pressure have been observed. These formations require extreme care and much expense to drill and to exploit. COMPACTION-FLUID PRESSURE RELATIONS THEORY The generation of overpressured formations in Tertiary sections of the Gulf Coast and several other Tertiary sedimentary basins is, in general terms, considered to be primarily the result of compaction phenomena.&apos; This portion of the paper presents a brief review of the theory which associates compaction and fluid pressure relations, and should thus provide the necessary background for an understanding of the techniques presented. See Hubbert and Rubey&apos; for a more comprehensive treatment of this subject. The theory of the consolidation of a water-saturated clay&apos; has been well established by workers in soil mechanics. The concept is explained by a model with perforated metal plates separated by metal springs and water and enclosed in a cylindrical tube. Fig. 1 is a schematic representation of such a model (see Ref. 5, Fig. 27, page 74). The springs simulate communication between clay particles, and the plates simulate the clay particles. Mano-

Jan 1, 1966

By H. J. Levinstein, H. J. Guggenheim, C. D. Capio

An optical incestigation of the phase transformations in RbFeF, has been conducted. Details of the ferromagwetic phase transition and the metamagnetic state are disczrssed. The three-dimensional magnetic domain structure existing in bulk crystals of RbFeF3 is described, as well as the effect of the magnitude and direction of the applied magnetic field on the domain struclure. The strong magnetoelastic interaction in RbFeF, is demonstrated. The results of the direct observation of the role of dislocation subboundaries and slip bands as nucleation sites and as pinning sites for magnetic domain walls are reported. THE perovskite compound RbFeF, has recently been shown to exhibit three magnetic states.&apos;&apos;&apos; Above 102°K it is paramagnetic, between 102" and 87°K it is antiferromagnetic. and below 87°K it is ferromagnetic (i.e., exhibiting remanence) with a modification of the magnetization occurring at 40°K. The changes in magnetic structure at 102o, 87°. and 40°K are accompanied by shear transformations to successively lower crystal symmetry classes.3 At 102°K a second-order phase transformation to a tetragonal crystal structure occurs. The c/o ratio increases with decreasing temperature to a value of 1.0034 at 87°K where the crystal undergoes another shear transformation to an ortho-rhombic crystal structure. The magnetic modification at 40 K is also accompanied by a shear transformation to a lower crystal symmetry. RbFeF3 is unique in that in the ferromagnetic state it is transparent in the bulk to visible light, has a low saturation magnetization, a large magnetic rotation. and has good optical properties.&apos; All these features make it an ideal material for the investigation of magnetic domain structures in bulk crystals. In addition a dislocation etch has been developed which reveals the point of emergence of dislocations with the (100) surfaces of RbFeF3,5 making it possible to determine the dislocation arrays in the material. As a result domain wall dislocation interactions can be observed in the bulk crystal. In this paper we report on 1) the crystallography of the phase transformations in RbFeF3. 2) the domain configurations as a function of magnetic field and crystal orientation. 3) the interaction of dislocations and magnetic domain walls in RbFeF,. EXPERIMENTAL PROCEDURE Since the temperature range of interest is below room temperature the dewar shown in Fig. 1 was employed. It was designed to fit on the stage of a Leitz panphot metallograph, and permitted examination of the sample at a magnification up to 150 times. The dewar consists of a double-walled glass cylinder bent into an L shape. The space between the walls is evacuated. The viewing wirldows were made of four optically flat quartz discs aligned parallel to each other and sealed to the sides of the concentric cylinders. The specimens were mounted in a holder attached to a flexible plastic shaft. Various holder designs were employed depending upon the type of observations to be made. For studies of the phase transformation between the antiferromagnetic and ferromagnetic state the holder shown in Fig. 2(d) was employed. This holder permitted accurate temperature control at 82" to 88°K by balancing the heat input from the carbon resistance heater against the heat loss to a heat sink immersed in liquid N2. Magnetic field studies were conducted by employing the holders shown in Figs. 2(a) and (b). The holder shown in Fig. 2(n) has a solenoid imbedded in it. such that the magnetic field direction is in the same direction as the incident light. The magnetic field provided by the holder in Fig. 2(b) is perpendicular to the incident light direction. The holder in Fig. 2(r) was employed when observations of the specimen were desired while an elastic bending stress was applied to the sample. The stress was applied to the sample by pulling a wire from outside of the dewar. The wire was attached to a lever pivoted on the holder. which caused the knife edge of the lever to push against the sample. The crystal growth and the sample preparation were described previously.&apos; PHASE TRANSFORMATIONS The first phase transformation in this system is from the cubic perovskite structure to n tetragonal

Jan 1, 1970

By Peter Tegart

The discovery of gold in the Toodoggone River area is credited to Charles McClair who mined placer deposits in 1925, reportedly valued at $17,500. After he and his partner went missing in 1927, efforts to relocate their workings resulted in the formation of Two Brothers Valley Gold Mines Ltd. in 1933, in which the legendary Grant McConachie (first president of CP Air) played an active role. This was the age when the prospector first utilized the airplane to reconnoitre remote areas. What greeted the observer from the air was an area rich in orange and yellow colours characteristic of gossans formed by the oxidation of sulphides. However, Samuel Black, a Hudson Bay Company fur trader, had also noted in his diary as early as 1824, the unusual and many gossanous colours in the headwaters of the Finlay River. These gossans, coupled with white limestone bluffs and the presence of placer gold, attracted the first reconnaissance of the area by Cominco in 1929. Cominco was ever active in remote areas at this time. They staked and worked several base-metal showings hosted by limestone at the margins of intrusive stocks. These early workers also obtained erratic high gold assays from chalcedony float samples found in creeks draining into the Toodoggone River. However, because the samples gave inconsistent assays, no concerted effort was made to locate their source. Except for the occasional horse-supported prospecting party of the late 1940s and early 1950s, the area did not receive much attention until 1968. Work until this time focused on the base metal lead-zinc showings which contained attractive silver credits. Gold was not an attraction because of the set price established by the US government. The late 1960s saw the northward expansion of porphyry copper exploration into the Toodoggone. A program of gossan soil sampling (gossans which had attracted the early workers) was carried out by Kennco Explorations (Western) Ltd. in 1966-1967. They analysed for base metals in the field, using a cold extraction method. The Kemess copper- gold prospect was staked as a result of anomalous copper values from this early geochemical program. In 1968, Kennco continued the program of silt traversing and field geochemical testing. The samples were further subjected to multielement analysis consisting of copper, molybdenum, lead, zinc, cobalt, nickel, and silver at Kennco&apos;s North Vancouver laboratory. Several anomalous creeks, high in combinations of copper, molybdenum, and silver, were outlined. Some initial soil grids were also established. The fall of 1969 saw the return of Kennco prospector Gordon Davies and geologist Bob Stevenson to check out a well-defined molybdenum, scattered copper and silver anomaly in soils from a grid on the Chappelle claims. The subsequent analysis of several selected quartz felsenmeer floats yielded one assay which ran in the order of 0.25 kg/t (8 oz per st) gold and 2.2 kg/t (70 oz per st) silver. Subsequent trenching on the Chappelle claims exposed the source of float in a 4- m (134) wide vein of high grade gold-silver mineralization. These results led quickly to the realization that the district had precious metal potential. Subsequent exploration in the period 1969-1974 by Kennco resulted in the discovery of most of the gold and silver occurrences on the Chappelle and Lawyers properties. Several other gold and silver occurrences were found in this district by Cordilleran, Cominco, and Sumitomo, working the district during this period. Conwest optioned the Chappelle in 1973 and explored underground by adit entry as part of a one-year program. In 1974, Du Pont of Canada Exploration Ltd. optioned the Chappelle claims and in March 1980, using reserves developed on the A vein, placed the Baker mine into production at a rate of 90.7 Vd (100 stpd). The Amethyst zone on the Lawyers property, 8 km (5 miles) north of Chappelle, was found in 1973 by Kennco using continued, persistent followup prospecting of silver silt geochemical anomalies. A silt anomaly in the order of 3.4 ppm silver occurred in a stream flowing 300 m (984 ft)

Jan 1, 1985

By A. S. Odeh

This paper analyzes the effect of limited entry to flow at the wellbore on the steady-state productivity of a well. Wells that have been opened to flow along a fraction of their productive interval are termed wells with limited entry. Previous work treated the cases of a partially penetrating well, a well producing from the central portion of the productive interval and a well in which several intervals equally spaced were open to flow. In this paper the open interval can be located anywhere within the productive interval. Thus, in a sense, it generalizes previous work. The finite cosine transform was used to arrive at a solution for steady-state flow of a slightly compressible fluid. The solution was programmed for a CDC 1604 computer. Numerical vaIues for rd = 660 ft, r, = 1/4 ft, and range of sand thickness of 20 to 200 ft are presented in graphical form. The effect of rd and r, values on the result is shown in a table. The correct calculation of skin and damage ratio in the presence of limited entry to flow is explained and illustrated by examples. Moreover, the paper shows how to calculate the net decrease in productivity due to the combined effect of limited entry and perforations. INTRODUCTION In some wells only a fraction of the productive interval is open to flow. Location of this fraction is usually dictated by formation characteristics and reservoir behavior. For instance, if a gas cap exists, the open interval is located away from the gas-oil contact to prevent any possible gas coning. Wells that intentionally have been opened to flow along a fraction of their productive formation are tened wells with limited entry. Obviously, unintentional completions of this type also exist. Limited entry to flow decreases well productivity. Magnitude of the loss depends on the fraction of the formation open to flow, on the thickness of the sand, on the location of the open interval and on the ratio of rd /r, where r , is well radius and rd is the drainage radius of the well. The use of pressure buildup data on producing wells to calculate the condition of the formation around the wellbore is an accepted practice. van Everdingenl and Hurst2 introduced the concept of she skin factor s considered to be due to a thin layer of different permeability immediately around the wellbore. These authors dealt with the case of a well of complete radial geometry, i.e., a well with open-hole completion that completely penetrates the formation. The presence of a low-permeability skin results in a loss of productivity, as does limited entry. Therefore, if pressure buildup data obtained on a well with limited entry are used to establish the presence or absence of skin (i.e., formation damage), and a correction is not made for this loss of productivity, the calculations would result in an erroneous skin value. They might indicate the presence of formation damage when in reality there is none, or they might indicate a value larger than the true value. This could lead to an incorrect basis for planning remedial measures. Muskat3 studied the problem of partially penetrating wells for the case of incompressible flow. He presented equations and figures which allow estimation of loss in productivity. Brons and Marting,4 using equations based on Nisle&apos;s work,5 studied the loss of productivity for three cases. The first was for a partially penetrating well; the second was for a well producing from only the central portion of a productive interval; and the third was for a well in which several intervals equally spaced were open to flow. Their work was for steady-state depletion-type reservoirs wherein the well radius of drainage is established and the fluid is considered to be slightly compressible. Considered in this paper is the problem of wells with limited entry in which the open intervals are located anywhere within the productive sand. The finite cosine transform is used to arrive at a

Jan 1, 1969

By D. E. Mikkola, G. E. Poquette

X-ray diffraction was used to study the growth of antiphase domains in quenched (or "disordered&apos;? Cu3Au annealed in the range 300" to 385°C. Measurements of the long-range order parameter indicate that a high degree of order is established rapidly at these annealing temperatures. Average domain sizes obtained by Fourier analysis of the superlattice peak profiles show that antiphase domain growth is analogous to classical metallurgical grain growth (i.e.,fol-lows a D2 US kt relation). The activation energy for the growth process, 44 kcal per mole, indicates diffusion control. The anisotropy in the observed effective domain sizes from seven different superlattice peaks can be best accounted for by a configuration involving antiphase domain boundaries on {100 } and (111 ) planes, where the (100) boundary is the low-energy type, {lOO} Type I. The disappearance of the (111) antiphase domain boundary during domain growth is dif-fusion-controlled with an activation energy of 48.5 kcal per mole. On the other hand, the behavior of the parameter representing the amount of (100) Type I boundary indicates that there may be a conversion of the higher-energy boundary types to (100) Type I boundary during the growth process. THE order-disorder transformation in the alloy Cu3Au has been the subject of numerous experimental investigations over the past 40 years, most of which have involved measurements of convenient physical properties such as resistivity and hardness as a function of heat treatment. The interpretation of these data is difficult because measurements of this type have the disadvantage that they yield total changes resulting from several different atomic processes which may be occurring simultaneously. The present study was undertaken to establish by means of X-ray diffraction the kinetic behavior of one of these atomic processes, namely antiphase domain growth. In the completely ordered state Cu3Au has an L12 structure which can be described as an fcc type arrangement of atoms in which the gold atoms occupy the corner sites and copper atoms the face-centered sites. Three other equivalent unit cells can be formed by allowing two gold atoms to occupy opposite face-centered sites and copper atoms to occupy the remaining corner and face-centered sites. These four different unit cells are crystallographically related by a shift of 1/2<110>. Quenching from above the critical temperature (392°C) to room temperature retains the "disordered" structure-a "random" arrangement of copper and gold atoms having the fcc structure. Annealing the disordered alloy below the critical temperature causes ordering to occur through the nucleation and growth of ordered regions at different points throughout the crystal. These small ordered regions, each based on one of the four types of unit cell, grow by consuming the disordered material until they impinge to form a domain structure in which the domains are antiphase by a shift of 4(110). The boundaries between domains are called antiphase domain boundaries (APDB) and they have been found to lie primarily on &apos; {100} planes in highly ordered Cu3Au. Two types of APDB can occur on ( 100) planes. An example of an (001)1/2[110] shear type APDB is shown in Fig. I. Because of the layer of copper atoms separating the domains in this case, there are no near-neighbor violations across the boundary and it has a low surface ener This type of APDB will be referred to as {lOO} Type I. Fig. 2 shows an (001): [011] climb type APDB, (100) Type 11. This type of APDB can be described as resulting from removal of a (200) plane followed by a shift of 1/2<110> to bring the separated regions together. Near-neighbor violations across (100) Type I1 APDB make it a high-energy boundary. There are numerous other possible APDB configurations; however, it is only worth noting that shear type APDB can be produced on the (111) plane by motion of a normal fcc dislocation with Burgers vector 1/2<110> through the ordered structure. A (111); [110] shear type APDB is shown in Fig. 3. Again, because of the near-neighbor violations this type of APDB has a higher energy than the (100) Type I APDB.

Jan 1, 1970

By A. Satter, J. M. Campbell

Reported herein are the results of a careful and detailed study of the non-ideal behavior of pure gases and their mixtures. Included are: (1) new data on five ternary systems composed of methane, ethane and H2 S; (2) a simple compressibility factor correlation that is inherently superior to present correlations, particularly for gases containing H2S and CO2; and(3) a detailed study of combination rules and the effect of system composition on the choice thereof. This study makes use of the rather large mass of data already available in the literature. A complete re-examination of the data and ideas presented in the last 25 years was considered desirable as a prelude to our basic concern — the effect of diluents on gas behavior. A consideration of both the macroscopic and microscopic properties of gases provides a better insight which, in turn, gives a firmer basis for improved correlation techniques. Such a study has shown that expressing the compressibility factor Z as a function of acentric factor w, as well as reduced temperature and pressure, yields a correlation that is broader in scope. The study of various combination rules has shown that better results are obtained by "tailoring" the rule used to the system composition. To do so improves the basic reality of results by overcoming some of the anomalies often found when using Kay&apos;s rule alone. Tentative recommendations are made regarding the most reliable combination rule for use with a given class of gas. The data presented are useful for estimating the direction and magnitude of the expected deviation when using a given rule. Although more work is needed, particularly around the critical region and with CO2 mixtures, the advantage of the classification scheme proposed is apparent. INTRODUCTION When one attempts to write a PVT equation to fit the data for actual gases, greater precision is obtained by the use of a multiple number of empirical constants. This has lead to multiple-constant equations such as Benedict-Webb-Rubin, Beattie-Bridgman, Keyes, etc., which are capable of yielding very precise results for pure gases in a range for which data to get the constants are available. As a matter of practicality, though, the use of such equations for gas mixtures is limited. Because of the infinite number of gas analyses available, any attempt to compile the constants needed requires a prohibitive amount of experimental data. This could be overcome by the use of a combination rule, but there is no real advantage in doing so because the end result offers no practical impovement over the Z factor correlation. The most widely used method of predicting the volumetric properties of pure gases is based upon the "theorem of corresponding states". According to this theorem, "all pure substances have corresponding molal volume at corresponding temperature and pressure if the reference point of correspondence is the critical point". Generalized compressibility charts for gases were prepared first by Cope and associates1 in 1931 and later by Brown and co-workers2 in 1932. However, the most commonly used charts are those of Dodge,3 Nelson and Obert,4 Hougen and atsson: and Standing and Katz.6 The work of Katz and co-workers has provided us with basic data for the hydrocarbons most widely used today. Their original chart6 was compared with a relatively large amount of multi-component data for gases consisting almost entirely of normal paraffin hydrocarbons. A deviation of only + 1.2 per cent was obtained.39 In the 20 years following publication of this work it has been found that the behavior of most mixtures of paraffin hydrocarbons could be predicted by this correlation within at least 5 per cent. Where difficulty has been encountered it has largely involved one or more of the following circumstances: pressures above 4,000 psig, mixtures containing large amounts of heavy ends and/or aromatics, systems in the critical region and mixtures containing polar compounds and/or CO2. The abnormal error sometimes found with such gases, not too unexpected for this method, is

By R. I. Jaffee, F. C. Holden, H. R. Ogden

Alpha solutes increase the strengths of Ti-Mn alloys through solid-solution strengthening. The substitutional a addition, aluminum, decreases, and the interstitial solutes, carbon and nitrogen, increase the rate of nucleation and growth of a from ß. The best combinations of properties of a-ß alloys are obtained when there is a sufficient quantity of a phase in the structure to dissolve the a solutes. OF the many different titanium-base alloy systems, the predominant alloy type is the a-ß alloy. The properties of the a-ß alloys are dependent on solid-solution strengthening and heat-treatment effects involving the a-ß ratio and transformation reactions. Another variable which influences the mechanical properties of a-ß alloys is the a-stabilizer content of the alloy. An a solute may be present as an intentional addition, such as aluminum, or as an impurity element, such as carbon, oxygen, or nitrogen. It is known that these a stabilizers, when added to titanium, form single-phase alloys which are not heat treatable but which obtain their strength from solid-solution strengthening. Thus, it would be expected that a additions to a-ß alloys would increase the strength of the alloys by solid-solution strengthening of the a phase. In addition, they would affect the transformation kinetics of the ß-to-a reactions and other processes based on the instability of the ß phase. The effects of heat treatment and structure on the mechanical properties of Ti-Mn alloys have been shown in a previous paper.6 This system offers a good base to demonstrate the effects of typical a solutes on the properties of a-ß alloys. The three a solutes described in this work are aluminum, representative of a substitutional a solute, nitrogen, representative of an interstitial a solute, and carbon, representative of an interstitial compound-forming element. The effects of heat treatment and microstructure on the properties of a alloys containing these three elements are described in concurrent publications. Some of these data are used for base-line points in several of the curves used for illustration herein. Experimental Procedures Iodide titanium was used as the base for all of the alloys studied in this work. The alloys were prepared as ½ lb ingots by double arc melting in an argon atmosphere. The ingots were forged to ¾ in. rounds, vacuum annealed for 6 hr at 900°C at a pressure of 10 &apos; to 10-5 mm of Hg to remove hydrogen, and hot swaged to 1/4 in. diam rod. After me- chanical descaling, test specimens were prepared for heat treatment. The alloys used in this study together with the fabrication temperatures are given in Table I. Heat treatments were done in argon. For the most part, the specimens were sealed in Vyeor capsules under a partial pressure of argon. Quenching was accomplished by breaking the capsule under water. Other cooling methods used included oil quench, argon cool (simulated air cool in an argon atmosphere), and furnace cool. The times for the various heat-treating temperatures are given in Table 11. The tests performed on the alloys consisted of tensile tests on ? in. diam specimens, hardness tests, and microimpact tests. Specimen sizes have been adequately described in a previous publication.&apos; The micrographs presented in this paper were taken from specimens cut from the shoulders of broken tensile specimens. Final polishing was done with Linde B on a slow-speed wheel, and the specimens were etched with a 1½ HF — 3½ HNO, solution. Ti-N-Mn Alloys The transformation diagram and microstructures of the Ti-0.1 pct N-Mn alloys used in this investigation are given in Fig. 1. The effect of small nitrogen additions on the binary Ti-Mn diagram is to raise the ß-transus temperature with little effect on the a solubility of manganese. Also, as has been noted previously,&apos; high manganese-content alloys containing nitrogen, when quenched from temperatures high in the ß field, contain a subgrain boundary phase which appears to be nitrogen-rich a. Marten-site is formed when alloys containing less than about

Jan 1, 1956

By Jonas Svensson

A new method is described for the production of cold-bonded pellets using a hydraulic binder, such as portland cement. Large-scale pilot-plant tests have proved that self-fluxing pellets of high reducibility and good handling strength can be made by the method. Blast-furnace trials have shown that the pellets are an acceptable burden material, comparable with self-fluxing sinter or heat-hardened pellets. Economic factors of commercial-scale production are discussed. The Grangcold Pellet Process—for which patents have been applied or already granted in a number of coun-tries—uses a hydraulic adhesive such as portland cement, slag cements, pozzolanic cements, etc., for the production of cold-bonded pellets. The idea of using a hydraulic binder for the agglomeration of iron-ore fines is not new. Portland cement was proposed as an adhesive for cold-bonded iron-ore briquettes in patents granted more than 50 years ago.&apos; In a report on the briquetting of iron-ore fines, published in Stahl und Eisen in 1959; it is stated that briquettes bonded with portland cement are used on a small scale at an ironwork in Germany. According to the report, the briquettes showed excellent strength in the blast furnace although their general use was made impossible because they required a long hardening time, during which they are sticky, soft, and difficult to store and handle. The Grangcold Pellet Process has overcome this particular disadvantage by mixing the balls with a suitable amount of the balling concentrate before storing them. The pellets are embedded in the concentrated during storing in such a way that they are isolated from each other and thus prevented from sticking together to form clusters. Thanks to the embedding concentrate, the pellets are subjected to a more or less uniform pressure from all sides which does not deform them. Thus, the mixture can be stored in a stockpile or in a bin until the pellets have hardened sufficiently. The concentrate is separated from the pellets by means of screening. The concentrate is returned to the balling operation and the pellets are either shipped to the blast furnace or stored for final hardening. The binder preferred for the Grangcold Pellett Process is portland-cement clinker, ground without the admixture of gypsum in order to avoid sulfur in the pellets as far as possible. Usually a 10% binder content is used. Two-thirds of the portland-cement clinker consist of lime and the rest is silica, alumina, and ferric oxide. Thus, self-fluxing or overbasic pellets are produced with this binder if the amount of silica in the concentrate used does not exceed 4%. The Grangcold Pellet Process was developed by the mineral Processing Laboratory of the Granges Co. Work started in 1963 with batch-scale tests. In 1966, a small pilot plant was put into operation in which 1800 tons of pellets were produced using 10% of rapid-hardening portland cement as a binder. Favorable results from a blast-furnace test with this batch led to the decision to erect a larger pilot plant which went into production in the summer of 1967. Since then, approximately 100,000 tons of cold-bonded pellets have been produced, mostly with 10% gypsum-free portland cement as a binder. Several full-scale blast-furnace trials have been performed with the pellets. The results of the trials indicate that the Grangcold pellets constitute a satisfactory blast-furnace feed. An industrial plant for the production of Grangcold pellets with a rated capacity of 1.5 million tpy is now under construction at the Granges Co.&apos;s mine at Grangesberg. The plant will come into operation in the summer of 1970. Results from Laboratory Work Pellets made from iron-ore concentrate bonded with portland cement harden slowly and their handling is very critical until they have hardened enough to loose their stickiness. It is therefore especially important to study the progress of the hardening action and the factors influencing it. This is best achieved by investigating the relationship between the compressive strength of the cement-bonded pellets and the curing time under varied conditions. The general course of this relation-

Jan 1, 1971