Search Documents

By E. P. Klier, V. Weiss

IN studies of the X-ray diffraction line geometry of iron with chromium radiation using techniques aimed at minimizing the background intensity, Kp and Ka emission satellites* were resolved with three techniques. These satellite lines are present with sufficient intensity to lead potentially to erroneous structure analysis, if not properly interpreted. The techniques used were: 1) film technique with un-filtered radiation and polycrystalline specimen, 2) film technique with unfiltered radiation and single crystal, and 3) counter technique with unfiltered radiation and single crystal. An example of results obtained with technique 1 is given in Fig. 1.

Jan 1, 1958

By E. G. Leonardon, C. Schlumberger, M. Schlumberger

Last year the authors presented a paper that discussed the various electrical measurements they perform in drill holes, which they name "electrical coring."' The object of the present paper is to give a brief account of the points of scientific interest that have been elucidated by further field work and laboratory research, as well as the economic results that have been attained recently. The practical examples given in this paper are drawn, for the most part, from the field work performed in Russian oil fields during the years 1931 and 1932. This is due to the fact that, thanks to the comprehensive cooperation of the Russian geologists and scientists, the authors are allowed to make public a large amount of recant information. In other countries in which the authors are engaged in similar work, the competition between private companies makes it imperative, for a considerable lapse of time, to avoid publication of the results obtained. The following points will be discussed successively, under separate headings: 1. Electrochemical phenomena in drill holes. 2. Stratigraphic correlations and tectonic studies. 3. Relations' between the productivity of oil horizons and their electrical resistivity. 4. Location of coal seams. 5. Summary and conclusions. Electrochemical Phenomena in Drill Holes Technical Publication 462l described the author's discovery concerning the existence of important differences of potential spontaneously gener-

Jan 1, 1934

Executive ARTHUR S DWIGHT, Chairman B THAYER CHARLES F RAND P MATHEWSON J V W REYNDERS Membership WILLIAM H BASSETT, Chairman W Y WESTERVELT Vice-chairman P MATHEWSON H G MOULTON F T RUBIDGE Finance WALTER H ALDRIDGE, Chairman GEORGE D BARRON GALEN H CLEVENGER

Jan 1, 1923

By J. B. Cheatham

The influence of friction on the force required for an idealized bit tooth to penetrate a "plastic" rock is analyzed. The rock is assumed to obey the Coulomb-Mobr yield criterion and the tooth is represented by a two-dimensional sharp wedge. At the tooth-rock interface the stress field not only satisfies the yield condition but also is such that the ratio of the shearing stress to the normal stress is equal to the coefficient of friction. The solution relates the force on the tooth to the depth of penetration, the tooth angle, the coefficient of friction between the rock and bit tooth and the angle of internal friction and compressive strength of the rock. INTRODUCTION Most rocks are brittle at atmospheric pressure but exhibit ductility and increased strength as the confining pressure is increased. In a previous analysisl the force required for a bit tooth to penetrate a rigid-plastic rock was computed for two limiting conditions: (1) a perfectly lubricated tooth-rock interface which should correspond to a lower limit for the penetrating force, and (2) a perfectly rough interface which should provide an upper limit. Experimental results2 for rock indentation under confining pressure have confirmed that the analysis generally predicts upper and lower limits for the penetrating force as a function of rock properties and tooth angle. The present analysis extends the previous work to account for the friction between the rock and the tooth. ANALYSIS The force required for incipient plastic flow of an idealized model of a rock under a bit tooth is computed subjected to the following assumptions. BIT TOOTH 1. sharp two-dimensional wedge (end effects neglected) 2. rigid tooth (elastic deformation of tooth neglected) 3. displacement of tooth is normal to rock surface 4. friction exists between tooth and rock ROCK 1. semi-infinite, isotropic and homogeneous 2. rigid-plastic (elastic deformation of rock neglected) 3. non-work hardening (horizontal stress-strain curve) 4. Coulomb yield condition* (linear Mohr envelope) 5. smooth, flat surface According to the Mohr theory of failure it is assumed that failure occurs when the state of stress is such that the Mohr stress circle becomes tangent to an experimentally determined envelope. The Mohr failure curve is frequent1y approximated by a straight line and referred to as the Coulomb-Mohr failure criterion. If the rock is under sufficient pressure to be ductile we can use the linear envelope as a yield condition. The Coulomb-Mohr yield criterion is illustrated by Fig. 1 and is expressed by the following equation:l

In 1934 the Southern Experiment Station of the U.S. Bureau of Mines in. cooperation with the University of Alabama began an investiga-tion of the availability of kyanite ores as a source of raw material for the manufacture of refractories. Under this program, gravity concentration and flotation tests have been made on two varieties of Georgia kyanite ore, mica schist and massive. Most of the attention has been directed to the mica schist ores, as they are more widely distributed and seem to offer greater economic possibilities than the massive ores. It is evident that the preparation of kyanite for use as a refractory material involves other considerations than the mere elimination of impurities. A concentration process that eliminates impurities satisfactorily may have to be followed by some additional treatment, since the final product must be of a coarse-ness and size ratio that will make it suitable for refractories manufacture. So far in the investigation at the Southern Experiment Station of the U.S. Bureau of Mines only the concentration problem has been considered, and this paper is intended as an interim report.

Jan 1, 1936

By H. M. Varner

Under sponsorship of the US Bureau of Mines and the Department of Energy, a new type of rotary rock drill was developed by The Bendix Corp. Originally developed for the production of holes for the installation of longer than seam height roof bolts, the flexible drill is a useful tool for many drilling applications. It allows hands-off or remote production of holes for increased drilling speed and greater operator safety in any strata suitable for rotary drilling. This paper discusses various applications and experience for the flexible drill system in coal, metal/nonmetal mining, and for civil engineering uses. Manual, remote control, and automatic roof bolter modules are also discussed.

Jan 1, 1984

By C. A. Schempp

STUDY of the adaptability of Tintic Standard ores to concentration dates back to somewhat before January, 1921, when the chloridizing mill at Harold, Utah, was put into operation. The operation of this mill has been fully covered in the TRANSACTIONS (Vol. 73). The process consisted essentially of a chloridizing roast followed by a percolating leach with a nearly saturated solution of common salt, acidified with sulfuric acid; precipitation of silver on sponge copper, and of copper and lead on tin-plate cuttings. This mill was built to treat the low grade siliceous ores having an average content of

Jan 1, 1933

By Frank S. Shuri

INTRODUCTION The Calumet Pumping Station, located on the south side of the Greater Chicago area, is part of the Tunnel and Reservoir Plan to accomodate the city's wastewater. The Station consists of two parallel rock caverns, each 18 m high, 20 m wide, and 62 m long, located in Silurian dolomite approximately 91 m below the ground surface. The caverns are oriented N-S with a 24-m-wide pillar between them. Prior to construction, rock mechanics studies were conducted in an L-shaped test adit at the location of the west cavern. The purpo3e of the rock mechanic studies was to characterize the site, particularly the in situ stress field and deformation characteristics of the rock. This information, together with other physical properties of the rock and geologic data, was used to evaluate the stability of the preliminary cavern design, with particular emphasis on cavern orientation, rock reinforcement, and pillar stability. GEOLOGY OF THE SITE Stratigraphy The Chicago area is located on the Kankakee Arch, a broad, gently sloping arch of Paleozoic sediments. Rocks in the project area consist of Silurian dolomites unconformably overlain by Pleistocene glacial deposits. The formations of interest to this study are: - Racine Formation, inter-reef facies. This dolomite is gray- brown, silty, and compact. It contains occasional prominent bedding surfaces. The Racine Formation in the project area varies from 73 to 74 m in thickness.

Jan 1, 1984

By Persifor Frazer

In his " Final Report," Vol. 11, part second, p. 763, Prof. Rogers sums up the metalliferous veins of the mesozoic sandstone by remarking that these are not associated with dykes or trap-rock, but are independent metalliferous injections. But singularly enough, in enumerating the different kinds of ores, no mention is made of

By M. J. Sinnot, J. C. Shyne

Low-frequency mechanical damping measurements were made to investigate internal friction in Fe-A1 alloys. The atomic ordering of the Fe-A1 system strongly influenced the stress-induced ordering internal friction. Magnetoelastic damping was also encounteyed and was shown to be reduced by the application of a static stress. THIS paper describes some damping experiments made on alloys of Fe and Al. Stress-induced ordering internal friction was measured with samples containing from 9.8 to 31.3 at. pct Al. Aluminum is soluble in a-Fe to about 50 at. pct and forms at least two long-range ordered structures, Fe3Al and Feu.' Stress-induced ordering internal friction is known to occur in many substitutional solid solutions, but few measurements of this damping effect have been made with alloy systems that have pronounced ordering tendencies. LeClair and Lomer developed expressions relating the relaxation strength of the damping process to the degree of atomic ordering and predicted that stress-induced ordering internal friction would be zero with complete ordering.' This concept was confirmed experimentally by Lulay and Wert using the system cd-Mg It is also consistent with the weak stress-induced ordering peaks observed in P -brass by Artman and in 16 wt pct Al Fe-Al by bert.' It was expected, therefore that the ordering characteristics of the system Fe-Al would strongly influence the stress-induced ordering internal friction exhibited by the experimental alloys. SAMPLE PREPARATION The alloys used in this investigation were induction melted under vacuum using high-purity melting stock. The iron was electrolytically refined Plastiron 101 which contained 99.85 wt pct Fe. The aluminum was a special 99.95 pct pure grade supplied by Alcoa. The only other raw material was spectrographically pure graphite which was used in small quantities as a deoxidant. The amount of carbon used was slightly in excess of the amount required to completely deoxidize the melt; this resulted in residual carbon contents of 0.01 to 0.02 pct in the finished alloys. The vacuum cast 2 1/2-in. diam ingots were hot rolled to 5/8-in. diam round bars. Portions of these bars were hot swaged and hot drawn to 0.050-in. diam wire. Straight pieces of the hot drawn wire were slowly heated to a temperature of 1300°C in a He atmosphere. After holding for 4 hr, the samples were allowed to cool in the furnace. This annealing treatment resulted in grain growth in the samples, the final grain size being about the same as the wire diameter. The grain boundaries were oriented perpendicularly to the wire axis, giving a bamboo grain structure. The existence of a preferred orientation could not be detected in these coarse grained samples. If the samples had a fiber structure, this probably would have been the same in all samples because of similar processing, thus the influence of crystal orientation on the relaxation strength would have been similar in all samples. The aluminum contents of the alloys are listed in Table I. EQUIPMENT The principle of the torsion pendulum was used for the internal friction measuring device. The

Jan 1, 1961

By T. E. Godson

AS this is the age of reform, a uniform mining law for North America is a moot subject for discussion at this meeting of the Institute. The question is one of peculiarly technical and, in many respects, local character. We all appreciate the value of the metal-producing industries and recognize the necessity and importance of a well-considered and evenly balanced mining law as a branch of our jurisprudence either for the Provinces or the Dominion as a whole. Mining has taken its place as a forempst industry and legislation that seeks to control and govern it is the concern of not only the active miner but the citizens of the state. A law that, through its charitable measures brings into being the prospector, the pathfinder and superstructure of all mining activity and industry! protects his interests, safeguards invested capital, and encourages and enforces development, possesses at least the salient requirements of a businesslike Act. The manner of doing so is, I think, one of local and internal concern. May I be permitted to say without presumption that of the five mining codes, or Acts, that we have in the Dominion of Canada born and bred within the Provinces of British Columbia, Ontario, Quebec, New Brunswick, and Nova Scotia, some of them could be materially improved. In many respects they do not measure up to the times; they were no -doubt creations of merit at the date of their .birth but they have not been clothed in seasonable raiment as the years passed by. It is a stern fundamental principle that all natural resources are the inalienable property of the crown. If it is mineral land, then it follows for the protection of the state and the direct advancement of the occupant that the land should be developed as such. The method or machincry by which this must be accomplished is a matter of detail, not of principle. If the right to possession as a licensee depends on discovery, it is not inconsistent with the duty the crown owes to the state that a grant in fee should pass to the discoverer if there is imposed, after patent issues, a requirement of continuous work or the alternative of an acreage tax sufficiently burdensome to make it unprofitable that the land should be held in an undeveloped state. If this requirement is recognized, the mental distinction between a grant and lease ceases to exist. A

Jan 1, 1920

By H. J. Ramey

Conventional calculation of total system isothermal compressibility for a system containing a free gas phase involves, among other things, evaluation of the change of oil and gas formation volume factors and the gas in solution with pressure. Preferably, this information should be obtained from laboratory measurements made with particular oils and gases. Often, experimental measurements are not available. In this case, it is necessary to obtain pressure-volume-temperature relationships from general correlations such as those of Standing' for California oils. In order to speed estimates of compressibility, generalized plots have been prepared of the change of both oil formation volume factors and gas in solution, with pressure from Standing's correlations. A generalized plot for estimating the change in the two-phase (oil and gas) formation volume factor with pressure is also presented. Usually, the effect of gas dissolved in reservoir water upon the total system compressibility is neglected for gas saturated systems, due to the low solubility of gas in water. Results of this study indicate that the increase in total system compressibility caused by solution of gas in water is often as large as the compressibility of wafer, and can be magnitudes larger for low pressure systems. Generalized results for estimating the change of gas in solution in water with pressure are presented in tabular and graphical form. INTRODUCTION During the past decade, pressure build-up and drawdown techniques have gained an important place in reservoir engineering. Build-up and drawdown analyses are only two special applications of the broad field of transient fluid-flow theory. All solutions of transient fluid-flow problems contain a parameter called the total system isothermal compressibility. This property of fluids and porous rock is a measure of the change in volume of the fluid content of porous rock with a change in pressure, and it may vary considerably with pressure. Evaluation of total system isothermal compressibility is not difficult, but it is tedious and time-consuming. Often compressibilities are estimated roughly, or transient flow methods are neglected completely. The benefits of using accurate system compressibility in properly-executed build-up or drawdown analyses are: 1. Better planning of pressure build-ups may be achieved to avoid unnecessary loss of revenue due to excessively long shut-in periods, or to shut-in periods too short to yield useable data. 2. Better and more reliable estimates of static formation pressures for reserves estimates and rate performance estimates. 3. Reliable information for evaluation of well completion effectiveness, and planning and interpretation of well stimulation efforts. The purpose of this paper is to clarify the nature of the total system isothermal compressibility, and to present useful methods for estimation of compressibility, particularly for systems containing a gas phase. DEVELOPMENT Numerous publications have presented solutions to transient single-phase flow of slightly compressible fluids, stressing pressure build-up applications. In transient flow, a compressibility* term arises to permit volume content of fluids in porous rock to change as pressure changes. The basic nature of the compressibility term is usually taken for granted. Problems arise in practical applications of transient fluid theory because most published works consider only one flowing fluid—in an ideal porous system containing only one fluid. In 1956, Perrine2 presented an intuitive extension of single-phase flow pressure build-up methods to multiphase flow conditions. Later, Martin- established conditions under which Perrine's multiphase build-up method had a theoretical foundation. Perrine has shown that improper use of single-phase build-up analysis in certain multiphase flow situations can lead to gross errors in estimated static formation pressure, permeability and well condition. It is likely that, much pressure build-up data for oil wells should be analyzed on the basis of multiphase flow. For both single-phase and multiphase build-up analysis, the isothermal compressibility term in dimensionless time groups often should be interpreted as the total system compressibility. All real reservoirs contain one or more compressible fluid phases. In addition, rock compressibility can contribute in an important way to the total system compressibility. The proper total system compressibility expression may contain terms for compressibility of oil, gas, water, reservoir rock and terms for the change of solubility of gas in liquid phases.

Jan 1, 1965

By A. E. Blakeslee

Morphological and electrical properties of GaAs epitaxial layers are influenced not only by changes in the nominal substrate orientation but also by small amounts of misorientation from the exact crystal planes. Deviations up to 5 deg from {11IA}, {11IB}, and (100) planes were investigated. Growth rates increase progressively with angle, approximately I u per hr per deg. Size and density of growth pyramids fall off with increasing angle, but other effects that are deleterious to the surface may occur which are heightened by increased misorientation. Carrier concentration decreases and electron mobility consequently increases as the angular offset increases, except in the case of strong compensation, where the mobility trend is reversed. It has long been known that changes in the crystallo-graphic orientation of the substrate may cause pronounced effects on the morphological properties of vapor grown semiconductor films. Reports of orienta-tion-dependent growth rates and surface characteristics are as old as the literature on epitaxy itself. shawl has recently published a comprehensive study of the dependence of growth rate on substrate temperature and orientation in epitaxial GaAs. It is also well-known that misorienting the substrate surface a few degrees away from the nominal low-index crystal-lographic plane often produces a much smoother epitaxial surface. This was reported by Tung2 for silicon, Reisman and Berkenblit3 for germanium, and by Kontrimas and Blakeslee4 for GaAs, and use is commonly made of this fact in the semiconductor industry to help guarantee smooth vapor deposits. The effects of substrate orientation on the carrier concentration and mobility of vapor grown GaAs were first documented by williams5 in 1964 and have been observed by several other authors since then,6,7 but no one has yet reported a careful study of how small changes influence these properties. We have made such a study and have found that sizable differences in growth rate, morphology, carrier concentration, and mobility can indeed be observed for epitaxial films grown on substrates that are oriented by progressive small increments away from the exact crystal plane. EXPERIMENTAL Early in the investigation an arsine synthesis system of conventional design8 was employed to produce growths on {111A}-oriented GaAs substrate crystals. In that early work, pronounced effects on carrier concentration and electron mobility were observed as a function of slight misorientation from this low index plane. That observation led to the more careful study that is reported here. An AsC13 system, differing in major aspect from those commonly in use today9 only in that the reactor is vertical rather than horizontal, was used for the detailed study. The gallium source was at 900°C and the substrates were at 750°C. The flow rate of pal-ladium-diffused H2 through the AsCl3 bubbler was 200 cu cm per min, and the flow rate of bypass H2 was also 200 cu cm per min. The substrates consisted of chro-mium-doped semiinsulating GaAs to facilitate elec-trical evaluation of the overgrowth by means of Hall and conductivity measurements on conventional eight-legged Hall bridges. They were misoriented by 0 to 5 deg from the {111A}, {111B}, and (100) planes, toward the (100) from the {111A} and {111B} and randomly toward the <111A> or <111B> from the {loo). The crystals were oriented for sawing by the Laue back-re-flection technique, which is good only to about ±1/2 deg; but after polishing or sometimes after epitaxial growth the wafers were checked by a diffractometer technique which is accurate to about * 0.1 deg. After lapping, the wafers were polished with NaOCl after the technique of Reisman and Rohr,10 and just before use they were cleaned in NaOC1, thoroughly rinsed with de-ionized water, and blown dry with nitrogen. Each run employed four wafers, each misoriented by differing amounts from one of the three major faces, and at least two runs were made for each orientation. The runs were continued long enough to provide at least a 15-µ or thicker layer. SURFACE MORPHOLOGY The appearance of all the films that were grown in a given run always changed from wafer to wafer as a function of increasing misorientation, but not always in the same regular fashion. At least three different trends were observed. These are more easily seen than described, and reference to the series of photo-

Jan 1, 1970

By A. H. Larson, T. P. McNulty

RECENTLY, an investigation of the absorption of sulfur dioxide gas in molten binary copper alloys was conducted. A Sieverts-type apparatus, consisting of a mercury-filled gas dispensing buret and a mercury manometer, was used initially for determining the volume of gas absorbed as a function of pressure. The equilibration behavior of the alloys studied indicated that the mercury in the gas measuring system was absorbing sulfur dioxide. Owing to the widespread use of mercury as a displacement medium in absorption studies, an investigation was made to determine the nature and magnitude of the mercury - sulfur dioxide absorption effect. The gas measuring system was modified by substituting a Worden Quartz Products Type PDHV fused-quartz-spiral pressure gage for the mercury-filled dispenser and manometer. The dispensed gas volume at known temperature and atmospheric pressure was measured by evacuating a Pyrex vessel of known volume and by admitting sulfur dioxide into the vessel until the attached quartz pressure gage registered atmospheric pressure. Atmospheric pressure was measured concurrently with a separate mercury barometer. The volume of the empty sample chamber and its attendant apparatus was determined by measuring the equilibrium pressure accompanying the addition of a measured volume of sulfur dioxide into the initially evacuated system. The volume of the mercury sample was calculated from the density of mercury at the temperature of the study (25°C). Measured volumes of sulfur dioxide were then dispensed into the system and the equilibrium pressure accompanying each gas addition was determined. From the difference between the system volume and the mercury volume, the number of moles of gaseous sulfur dioxide remaining in the system at each pressure was calculated. The difference between the number of moles of gas dispensed into the system, denoted Enso2: and the number of moles of gas remaining in the system after absorption equilibrium had been attained, denoted nso2(g), was equal to the number of moles of absorbed gas, denoted nSO2. The number of moles of absorbed gas was then converted to absorbed volume, denoted VSo2, in cu cm at stp conditions of (PC and 760 mm Hg. Table I contains calculated values of Snso2, nSo2(g), and VSo2 for different sulfur dioxide pressures. In the original system, denoted Run I, volume limitations of the gas dispensing system prevented absorption studies at equilibrium pressures near atmospheric pressure, so a different gas dispensing system, denoted Run 11, was used for determining the last pressure reading in Table I. The data in Table I are expressed in terms of the absorption of sulfur dioxide in 49.68 cu cm of mercury. In Fig. 1, these data are expressed in terms of the absorption of sulfur dioxide in 100 cu cm of mercury. Since the absorption data plotted in Fig. 1 show a linear relationship, the volume of sulfur dioxide absorbed in mercury is a function of the first power of pressure. The absorption reaction is So2(gas) = SO2 (in Hg) The first-power pressure dependence, coupled with the fact that the sulfur dioxide could be removed from the mercury by applying vacuum, indicated reversible

Jan 1, 1967

By ir. H. Eraly

The allocation of miners to teams, and of teams to production faces, is complicated by the high degree of absenteism of miners in Belgium. Therefore, the exact knowledge of who is actually present at the beginning of a shift and of the exact skills of those present, enables the foremen and mine captains to constitute their teams before all men go down into the mine in the most effective way possible. This paper describes the system of attendance recording and of displays which the foremen use to constitute their teams and/or to interrogate the personnel data base in order to do so. It shows how the foremen dialogue with the computer, to change the function of a miner within a team, to another team, or the function of a team as a whole. The implementation of the system, data bases, and data communication equipment and procedures, is described. The benefits obtained are presented for each level of the company: foremen and team supervisors, engineers, mine management.

Jan 1, 1977

Raymond Weir Smyth, born Nov. 3, 1888, was the son of Herbert Weir Smyth, professor of Greek Literature at Harvard University. He graduated (A. B.) from Harvard in 1909 and later pursued advanced studies there in chemistry and in metallurgy. He held the position of metallurgist for the American Steel and Wire Co. at Worcester, Mass., and also for the Steel and Tube Co. at Youngstomn, Ohio. For a time he was inspector of munitions for the British Government and stationed at the Railway Steel and Spring Co. at Latrobe, Pa. For a short time, in 1917, he was Inspector of Ordnance for the U. S. Government, and the following year, having entered the U. S. Naval Reserve Force, he was ordered in a similar capacity to the Midvale Steel Co. In September, he removed to the Navy Yard, League Island, Philadelphia, to train for the obligatory minimum of six months&apos; sea duty. There he contracted influenza, which was followed by pneumonia, from which he died, September 27, at the Navy Yard Hospital. Captain Braxton Bigelow* Captain Braxton Bigelow was the son of Major John B. Bigelow, U. S. A., retired, and grandson of the late John Bigelow, author, and Minister to France under President Grant. Captain Bigelow graduated

Jan 1, 1920

Raymond Weir Smyth, born Nov. 3, 1888, was the son of Herbert Weir Smyth, professor of Greek Literature at Harvard University. He graduated (A. B.) from Harvard in 1909 and later pursued advanced studies there in chemistry and in metallurgy. He held the position of metallurgist for the American Steel and Wire Co. at Worcester, Mass., and also for the Steel and Tube Co. at Youngstomn, Ohio. For a time he was inspector of munitions for the British Government and stationed at the Railway Steel and Spring Co. at Latrobe, Pa. For a short time, in 1917, he was Inspector of Ordnance for the U. S. Government, and the following year, having entered the U. S. Naval Reserve Force, he was ordered in a similar capacity to the Midvale Steel Co. In September, he removed to the Navy Yard, League Island, Philadelphia, to train for the obligatory minimum of six months&apos; sea duty. There he contracted influenza, which was followed by pneumonia, from which he died, September 27, at the Navy Yard Hospital. Captain Braxton Bigelow* Captain Braxton Bigelow was the son of Major John B. Bigelow, U. S. A., retired, and grandson of the late John Bigelow, author, and Minister to France under President Grant. Captain Bigelow graduated

Jan 1, 1920

By R. V. Mrazek, F. E. Block, S. B. Knapp

The mixed homogeneous and heterogeneous kinetics of the thermal decomposition of tungsten hexacarbonyl were studied by employing a batch reactor. The system was such that a sample of tungsten hexacarbonyl could be injected into the preheated reactor, and the progress of the reaction followed by a simple pressure measurement. Both the homogeneous and heterogeneous reactions were found to be first order, and approximate activation energies were determined for each reaction. It is shown that the dis-proportionation of carbon monoxide to give carbon and carbon dioxide cannot be the source of carbon in tungsten deposits prepared by this reaction. The kinetics of the thermal decomposition of tungsten hexacarbonyl have been investigated as part of a continuing study by the U.S. Bureau of Mines on the decomposition of organometallic compounds. Reactions involving the thermal decomposition of metal carbonyls have a potential application in the preparation of pure metals and fine metal powders. Indeed, it was these applications which provided the impetus for much of the early work involving the carbonyls of nickel1 and iron.&apos; The relative lack of study of other metal carbonyls can be traced to the comparative difficulty in synthesizing these compounds. The most common use for tungsten hexacarbonyl has been as an intermediate in vapor-phase plating.7&apos;8 However, attempts to obtain a carbon-free deposit of tungsten by this method have not been successful, and some investigators have taken advantage of the carbon contamination and used this process to form tungsten carbide deposits.lo Other investigators have studied the thermodynamic properties11"14 and molecular structure of tungsten hexacarbonyl. However, very little is known about the kinetics of this thermal decomposition, the mechanisms involved," or the source of carbon in the resulting plate. In contrast, studies have been made of the kinetics of the thermal decomposition of nickel tetracarbonyl, iron pentacarbonyl, and molybdenum hexacarbonyl.&apos;l It has been found that these thermal decompositions occur by a mechanism which is partially heterogeneous in nature. Information available on the equilibrium constants for the decomposition of tungsten hexacarbonyl was used to determine a temperature range, 500" to 560°K, in which the reaction could be expected to be essentially complete. APPARATUS The apparatus used allowed the injection of a sample of tungsten hexacarbonyl into a preheated batch reactor and the use of a simple pressure measurement to follow the progress of the reaction in the sealed reactor. The pressure was sensed by means of a pressure transducer (Consolidated Electrodynamics Corp., 0.3 pct)* capable of operating at the *Reference to specific products is made to facilitate understanding and does not imply endorsement of such brands by the Bureau of Mines._______ reaction temperature. This type of sensing element was chosen to avoid the problem of condensation of the sublimed carbonyl in the capillary tubing leading to any type of remote pressure-sensing device. stirring was provided by rotating the entire apparatus. Glass beads placed in the reactor provided a pulsating agitation. To minimize thermal gradients in the reactor walls, the reactor was constructed of aluminum. The support tube which held the reactor in the furnace was thin-walled stainless steel to minimize heat conduction out of the reactor. As a result of these measures, a nearly uniform temperature (°C) was maintained throughout the reactor. Fig. 1 is a schematic diagram of the apparatus. The small gear motor rotated the entire apparatus at about 200 rpm. The bearings shown at the ends of the air cylinder were perforated to allow air to be fed to the charging piston and to allow inert gas to be fed to the reactor during the preheating period. The sample was simultaneously injected and sealed inside the reactor by operation of the air piston. Fig. 2 shows a cross section of the air cylinder and the adjoining portion of the support tube leading to the reactor. The sample carrier is shown in place at the right-hand end of the injection rod extending from the air piston. The piston is shown in the retracted position, as it would be prior to the start of an experiment. The small Teflon gasket which encircled the sample carrier at the end of the injection rod sealed the reactor when the sample was injected. This seal was maintained throughout the test by maintaining air pressure on the piston. The sample carrier was a 2-in. section of thin-walled, -in.-diam nickel tubing with an internal blank about 1 in. from the base and with the base end sealed.

Jan 1, 1969

By J. L. LeBlanc, R. L. Lewis

This study presents an analysis of annular backpressure variations associated with controlled gas kicks and their pronounced effect on casing .strings and exposed under lying formations. A mathematical model describing the volumetric behavior of an extraneous gas as it is transported from reservoir to .surface conditions under changing temperatures and pressures has been programmed in a Kingston FORTRAN II language for digital computer analysis. The gases under investigation typify Gulf Coast reservoir gases within a 0.6 to 0.7 .specific gravity range. The program output has been substantiated by actual field cases. of gas kicks encountered in Gulf Coart we1l.s. The development of empirical equations for calculating suitable gamy deviation factors for unique temperatures and pressures was incorporated in the program to provide realistic solution.. An output listing of annular backpressures and corresponding equivalent fluid densities resulting at a predetermined critical depth (casing setting depth) and total depth for selected .stages of circulation is provided in a chronological .sequence. Additional information including reservoir pressure and temperature, kill rnrid density, produced gas or surface volume of the expanded gas intro vion, drill pipe and annular volumes can he obtained from the model. This paper illustrates that a precise knowledge of the volumetric behavior of extraneous gases in annular flow and its effect on equivalent fluid densities at a critical depth is significant and should receive .serious consideration in controlling threatened blowouts and in the design of drilling programs. Surface pressures in excess of formation limitations are a threat to zones of lost circula/ion and are potentially injurious to productive intervals. A knowledge of annular backpressure and equivalent fluid density profiles for probable gas kicks aids in a technological accomplishment of drilling programs and provides a .sale tolerance in the event a threatened blowout is encountered. Introduction Drilling operations are frequently interrupted when the drill bit penetrates permeable gas sands with reservoir CtfuJ manuscript was received in Society of Petroleum Engineers ofice Am. 1 1967. Revised manuscript received JuIy 7. 1968. Paper (SPE 1860) kae presented at SPE 42nd Annual Fall Meeting held in Houston. Tex., Oct 1-4, 1967. @ Copyright 1968 American Institute of Mining, Metallurgical, and Petroleum Engineem, Inc. pressures greater than that exerted by the drilling fluid. The differential pressures resulting permit an extraneous influx of gas into the wellbore. A suspension in drilling progress is necessary to restore fluid equilibrium throughout the system. Whether formation gas kicks originate unintentionally or by design, the prospect of a threatened or actual blowout exists and a method assuring a safe and effective well control procedure must be observed. A significant contribution to well control technology was advanced by Records et a1.l in 1962. Using the concept of transmitting a constant equivalent formation pressure at the point of intrusion, Records et al. introduced a calculation technique providing the annular backpressures encountered in a well control environment as a func tion of the volumetric behavior of a 0.6 specific gravity natural gas. In essence, the procedure outlined an annular backpressure schedule in terms of fluid volume circulated at different stages of a well control operation. A number of other publications2-&apos; proposing various techniques for controlling gas intrusions in a wellbore achieve pressure control essentially through maintenance of a constant bottom-hole pressure by surface choke adjustments. The subsequent pressure effects induced in the annulus unfortunately receive little emphasis. Due to the tedious and repetitive nature of annular backpressure computations, a theoretical solution by digital computer is introduced for predicting annular backpressure and equivalent fluid density profiles associated with controlled gas kicks. We point out the effects of volumetric behavior of extraneous gases in annular flow and related field phenomena on equivalent fluid densities at a critical depth. The investigation indicated that equivalent fluid densities at a critical depth are of significance and should receive consideration in the control of threatened blowouts and in the design of drilling programs. Theoretical Considerations The mechanism of vertical gas flow through an annulus is governed by the PVT properties of the fluid, the pressure distribution within the system, the fluid flow rates and the geometry of flow. Due to the numerous variables involved in this type of problem, certain assumptions were imposed in deriving the mathematical model and in establishing the solutions. Two gases, characterized by specific gravities of 0.6 and 0.7, were selected to typify Gulf Coast reservoir fluids. The gas intrustion entered the wellbore as an immiscible &apos;References given at end of paper. JOURNAL OF PETROLEUM TECHNOLOGY

Jan 1, 1969

By G. R. Belton, Y. K. Rao

A galvanic cell, using liquid MgCl2 or MgC12-CaC12 mixtures as the electrolyte, has been used to determine activities in Mg-A1 liquid alloys between 700&apos; and 880°C. The incovporation of a chlorine electrode in the cell also allowed measurements to be made of the standard free energy of formation of MgCl2(l). The results are shown to be in good agreement with thermo-chetrlical values from the literature, and this is taken as evidence that the small, known solubility of magnesium in iMgCl2 introduces no significant error in galcanic cell measurements. Within experimental error, the activity coefficients and relative partial molar enthalpies at 800°C are shown to be represented by the following "subregular" solution equations: logy~~ =-0.68(1 -xMgj3 log yAL =-1.02(1 - XMf + 0.68(1 - XMf H.M = -4400(1 - %)3 / cal Mg 7Ag&apos; HZ =-6600(1 - xA1)&apos; + 4400(1 - XMf cal SCHNEIDER and toll&apos; have used a transpiration technique to measure the vapor pressures of magnesium over Mg-A1 alloys between 544" and 594°C. amsstad,&apos; however, has since suggested that the extrapolation to zero flow rate, used by these authors in interpreting their apparent pressure vs flow rate data, gives unreliable results. Rogers, Tomlinson, and Richardson,3 in interpreting the results of solution equilibria between Mg-A1 alloys and liquid MgC12, also considered the measurements of Schneider and Stoll to be unreliable and preferred to derive activities for the alloys from the earlier boiling point determinations of ~eit~ebel~ and the partial molar heats recommended by Kubaschewski and ~atterall.~ These latter heats were based substantially on the early calorimetric work of Kawa-kami but, unfortunately, his work on other systems has sometimes been found to be inaccurate.7 Rogers et al., in the above-mentioned paper,3 tentatively concluded that the most likely species responsible for the limited solubility (0.3 mole pct at 800°C) of magnesium in MgC12 were Mg° (neutral) and Mg2++. Two more recent studies8,9 have supported Mg2++ as the soluble species. In the present study, activities in Mg-A1 alloys have been determined by means of a galvanic cell involving liquid MgCl2 or MgC12CaCl, mixtures as the electrolyte. Since the reactive nature of magnesium precluded simple Faraday yield experiments, a chlorine electrode was incorporated in the cell in order that the performance of the cell could be checked by measurements of the heat and free energy of formation of MgC12. This procedure was considered necessary since it has been suggested1&apos; that the solubility of a metal in a molten salt might introduce electronic conductivity; also, previous determinations of the standard electrode potential for MgC12 differed by as much as 70 mv11-13 EXPERIMENTAL Materials. Analyses of the materials used in preparing the alloys and the electrolyte mixtures are presented in Table I. The alloys were prepared by induction melting weighed amounts of the metals in a graphite crucible held under an argon atmosphere. Pure anhydrous magnesium chloride was prepared by heating the mixture MgCl, . 6H20 +NH4C1(1:1) to 650°C, followed by melting under dry argon. The melting point of the dry MgC12 was found by differential thermal analysis to be 714.8oC, which compares well with the accepted value of 714C.14 This agreement was taken to be an indication of the high purity of the dried salt. Table I. Compositions of Materials, wt pn Impurity Mg Al MgCI2 CaCI, Ba - - 0.005 Ca - - 0.010 Cu 0.02 0.02 Fe - 0.10 0.001 0.010 Pb 0.01 - 0.001 0.005 Mn 0.15 0.001 Si - 0.10 Sr - - 0.005 MBSO* - 0.040 ARGON TUNGSTEN CHLORINE LEAD—411 11 II ALUMINA &apos;A I / ave GRAPHITE on irA~_ ( ^"l ROD MAGNESIUM S>ILICA~^ /, OR ALLOY-. I /A] ___________ -«^- _ ELECTROLYTE I y FRITTED DISCS Fig. l—Arrangement of chlorine and metal electrodes in electrolytic cell.

Jan 1, 1970