Search Documents

By Alan M. Bateman

Before World War II we proudly considered that we were the nation of all the world most richly endowed in mineral resources. We knew it was no accident that those countries abundantly supplied with mineral resources became the great manufacturing nations, and the politically and militarily strong ones; and that our own great industrial cities sprang up where coal and iron met. We all reallized, especially we of the mining profession, that the energy of fuels and the solidity of metals spelled industrial growth and in turn industrial might and that other nations came to regard mineral self-sufficiency as one of the chief goalsof economic nationalism.

Jan 1, 1949

By B. G. Matson, M. A. Whitfield, G. R. Dysart

This paper describes the development of u computer program to calculate changes that occur in the length of tubular goods due to temperature and pressure changes during stimulation operations. Due to the numerous variables involved and the uncertainty of all static and dynamic conditions that could exist, it becomes a staggering task for individuals charged with completions to perform the necessary mathematical calculations. The computer program permits advance calculations for several sets of conditions. INTRODUCTION In the Delaware basin of West Texas alone, 50 wells were contracted or drilled to 15,000 ft or deeper in 1965. Deep well activity is continuing in this and other areas on an expanding scale. Many of these deep wells require extensive stimulation for successful commercial production, and during these operations, pressures and temperatures are encountered that have a pronounced effect on the length of tubular goods. This length change during a large-volume, high-pressure stimulation treatment utilizing fluids considerably cooler than bottom-hole temperature can be of such a magnitude that permanent damage to casing and tubing will result unless mechanical design, pressures and fluid temperatures are evaluated and controlled. These pressure and temperature effects can be calculated. However, the process lends itself well to computer solutions because of the mathematical nature of the problem and the calculating hours involved in arriving at an answer. The engineering-hour demand becomes more severe as tapered strings are involved. On initial treatments on a given well, surface pressure and injection rate conditions are unknown, and offset well conditions have not proven to be a reliable method for making predictions. For these reasons, it has become rather standard procedure for operators to compensate for these uncertainties by placing unnecessary pressure and fluid temperature restrictions on stimulation design. On a number of occasions treating fluids have been preheated to as much as 160F as a means of compensating for thermal contmction resulting from pumping cool fluids. The maintenance of packer seals has been treated by Lubinski, Althouse and Logan',' and the problem of therma1 effects on pipe has been explored by Ramey." These works were expanded and the results made applicable to everyday oilfield terminology before submitting them to computer programming. The pressure and temperature effects on tubing movement previously mentioned occur simultaneously as fluid moves through the pipe. The pressure changes, for purposes of explanation, are categorized here as to the various effects these pressures have on a tubing string. These divisions are (1) the piston-like results of forces acting on horizontal surfaces exposed to pressure, (2) swelling or ballooning of the tubing along its entire length due to the forces of pressure acting against the tubing walls, (3) the elongation of tubing due to frictional drag and (4) corkscrewing of the pipe due to internal pressure. Thermal changes are also of great importance, as their results may be more significant than any of the pressure effects. Steel is an excellent conductor of heat and the earth is a relatively poor conductor. It has been calculated that pipe temperatures at depths of more than 20,000 ft approach within as little as 25" the temperfature of the surface fluid after pumping for 2 hours, or a drop in temperature in some treatments of more than 220F. The equations presented in this paper were developed for computer programming and simplicity of input information; therefore, numerical constants such as Young's modulus for steel (28 X 10\ si), the coefficient of thermal expansion of steel (6.9 X 10."IF) and Poisson's ratio for steel (0.3) are included with unit conversion factors. The moment of inertia of tubing cross-sectional area with respect to its diameter was changed to a constant times (D' — d') where D is outer diameter and d is inner diameter. Units in the equations are length in feet, diameter in inches, density in pounds per gallon, pressure in psi, rate in barrels per minute and time in hours. PISTON-LIKE REACTIONS A change in tubing internal dimensions and the exposure of other horizontal surfaces to different pressures on the inside and outside of the tubing result in a reaction much like a piston under pressure. Such is the case when the internal diameter changes in a combination string of pipe, when seals of a slick joint assembly are subject to pressure and in the end effects of a tubing string. The change in tubing length due to the piston effects of a slick joint packer is affected by the various diameters involved, the tubing pressure Ap,, the casing pressure ,Ap,, length of pipe L, densities of fluid in the tubing before and during pump-

By H. M. Morse

Tinsley Oil Field.—Mississippi joined the oil-producing states when on Sept. 13, 1939, the Union Producing Company's G. C. Woodruff well No. 1, sec. 13, T. 10 N., R. 3 W., Yazoo County, was completed after drilling plug at 4540 ft. in the Woodruff sand of the Eutaw formation of Cretaceous, producing 300 bbl. per day of 34.4" gravity oil through a ¼-in. choke, with a gas-oil ratio of 80 to 1 and bottom-hole pressure of 2045 lb. This was the discovery well in the Tinsley oil field. The well was drilled to a total depth of 4567 ft. and no salt water was encountered. The sand underlies the Selma chalk formation. Nine producing oil wells and one dry hole were drilled and completed by the end of 1939. Two producing sands have been found in the Eutaw and a third sand in the top of the Tuscaloosa formation, called the Woodbine sand in Louisiana and Texas. Faulting is an important factor in the Tinsley field. Total oil production has been approximately 250,000 bbl. from the nine flowing wells. Total depth to top of productive zone was 4540 ft.; to bottoms of productive wells, 4580 ft. Net thickness of the producing formation is 20 to 40 ft., and its porosity is 24 per cent. The deepest zone tested was the Tuscaloosa, in which the depth of hole was 6112 feet. Six hundred and forty acres has been proved for oil production. Jackson Gas Field.—The Jackson gas field has shown a steady decline in the number of wells but the pressure has been maintained. This field is a perfect example of a water-driven field and the time of wells going to salt water is predictable. Five wells were drilled in the Jackson field, of which only one produced. Amory Gas Field.—Interest was renewed in the Amory gas field, where a new well was started in the fall of 1939. Geological Formations.—The deepest well drilled in 1939 was the Willmut Gas and Oil Company's Cleve Love S. F. Johnson No. 1, sec. 29, T. 6 N., R. 1 W., Hinds County. This well encountered the Lower Cretaceous, Trinity series from 3770 to 6422 ft.; Lower Mesozoic from 6422 to 6484 ft. The geological correlations and nomenclature of the formations in Mississippi are shown in the accompanying strati-graphic section.

Jan 1, 1940

By H. M. Morse

Tinsley Oil Field.—Mississippi joined the oil-producing states when on Sept. 13, 1939, the Union Producing Company's G. C. Woodruff well No. 1, sec. 13, T. 10 N., R. 3 W., Yazoo County, was completed after drilling plug at 4540 ft. in the Woodruff sand of the Eutaw formation of Cretaceous, producing 300 bbl. per day of 34.4" gravity oil through a ¼-in. choke, with a gas-oil ratio of 80 to 1 and bottom-hole pressure of 2045 lb. This was the discovery well in the Tinsley oil field. The well was drilled to a total depth of 4567 ft. and no salt water was encountered. The sand underlies the Selma chalk formation. Nine producing oil wells and one dry hole were drilled and completed by the end of 1939. Two producing sands have been found in the Eutaw and a third sand in the top of the Tuscaloosa formation, called the Woodbine sand in Louisiana and Texas. Faulting is an important factor in the Tinsley field. Total oil production has been approximately 250,000 bbl. from the nine flowing wells. Total depth to top of productive zone was 4540 ft.; to bottoms of productive wells, 4580 ft. Net thickness of the producing formation is 20 to 40 ft., and its porosity is 24 per cent. The deepest zone tested was the Tuscaloosa, in which the depth of hole was 6112 feet. Six hundred and forty acres has been proved for oil production. Jackson Gas Field.—The Jackson gas field has shown a steady decline in the number of wells but the pressure has been maintained. This field is a perfect example of a water-driven field and the time of wells going to salt water is predictable. Five wells were drilled in the Jackson field, of which only one produced. Amory Gas Field.—Interest was renewed in the Amory gas field, where a new well was started in the fall of 1939. Geological Formations.—The deepest well drilled in 1939 was the Willmut Gas and Oil Company's Cleve Love S. F. Johnson No. 1, sec. 29, T. 6 N., R. 1 W., Hinds County. This well encountered the Lower Cretaceous, Trinity series from 3770 to 6422 ft.; Lower Mesozoic from 6422 to 6484 ft. The geological correlations and nomenclature of the formations in Mississippi are shown in the accompanying strati-graphic section.

Jan 1, 1940

By A. Gatti, R. L. Fullman

A very fine dispersion of aluminum oxide is produced by internal oxidation of solid-solution alloy of 0.14 pet A1 in Ag. The particle size of the aluminum oxide is approximntely 50 to 100A in radius. The yield strength of the alloy is increased markedly by internal oxidation. A further increase in strength is produced by cold working the internally oxidized alloy. Recrystallization is retarded by the finely dispessed aluminum oxide particles, so that the strength increase resulting from cold work is retained on annealing at temperatures 14 to about 700°C. MANY workers'-3 in the past have studied various aspects of the internal oxidation of aluminum-silver alloys. This paper is an extension of these studies with emphasis placed on the effect of time and temperature of annealing on the strength of these alloys after oxidation and subsequent cold working. Two general conditions are necessary to internally oxidize an alloy. First, oxygen must diffuse through the base material more rapidly than does the addition; otherwise oxidation will take place as a surface layer. Secondly, the affinity of oxygen for the addition must be greater than for the base material. After internal oxidation of certain alloys takes place, a marked increase in hardness accompanied by higher yield stress and improved creep properties is noted, presumably as a result of the highly dispersed oxide within the base material. Meijering and Druyvesteyn1 also noted that the internally oxidized portion of a partly oxidized alloy failed to recrys-tallize under annealing conditions that led to coinplete recrystallization of the unoxidized part. EXPERIMENTAL-METHODS AND PROCEDURES Few alloys can be made to contain a second phase that is extremely stable at high temperatures. Silver plus aluminum in solid solution was chosen for these internal oxidation studies because of the high rate of oxygen diffusion through silver and the very stable nature of aluminum oxide. Two alloys were vacuum cast. The nominal compositions were: Alloy A—1 pct Al, balance Ag; Alloy B—0.1 pct Al, balance Ag. Chemical analysis, which does not distinguish between aluminum and aluminum oxide, showed the conlposition to be: Alloy A—1.6 pct Al, and Alloy B—0.14 pct Al. The ingots were machined for surface cleaning, swaged and drawn to 0.020-in. diam wire. A sample 20 ft long of the 0.020-in. dianl wire of each composition was annealed 24 hr at 800°C in pure dry hydrogen. Each wire was then cut into two equal pieces. Photomicrographs of the 0.14 pct A1 alloy are shown in Fig. 1, the annealed 0.020-in. wire at the left and the oxidized wire to the right. The oxidation treatment for the first set of data was 1000 hr at 800°C in air. After this treatment the 1 pct A1 proved to be brittle. It is assumed that high alunlinum oxide concentration at the grain boundaries was responsible. The 0.14 pct Al wire remained ductile and all further data were derived using this alloy. One-half of this wire, about 5 ft, plus 5 ft of as-homogenized wire, was then drawn cold to 0.005 in. diam. All tensile tests were conducted with an Instron Engineering Corp. tensile-testing machine, Model TT-B. Unless otherwise indicated, the tests were made at room temperature with a strain rate of 0.1 per min. All metallographic samples were etched with an aqueous solution of 2 pct each of CrO3 and H2SO4 . EXPERIMENTAL RESULTS AND DISCUSSION PARTICLE SIZE DETERMINATION A study was made of the particle size of the aluminum oxide produced in the samples of Ag + 0.14 pct Al, oxidized 1000 hr at 800°C. A cross section of the as-oxidized wire was mounted in bakelite, polished, and etched with an aqueous solution of 2 pct each of CrO3 and H2SO4. The specimen was then thoroughly cleaned by stripping successive coatings made by applying 10 pct nitrocellulose in amyl acetate. The final replica of the cross section was made by applying 2 pct nitrocellulose in amyl acetate. The replica was stripped, transferred to a copper screen, shadow cast with chromium at 10 deg and photographs taken using a Phillips Metallix electron microscope at an accelerating potential of 100 kv. A photograph of an etched sample of the as-oxidized material is shown in Fig. 2. We believe the pits in the photograph are places were A12O3 inclusions were sitting in the matrix. By inspection, it appears that the volume fraction ob-

Jan 1, 1960

By H. K. van Poollen, H. C. Bixel

A treatment is given of the transient pressure behavior of a well located at the center of a circular region surrounded by a radial discontinuity. On either side of the discontinuity, the values of permeability, viscosity, compressibility and porosity are uniform but may be different from those on the other side of the discontinuity. The results are obtained by solving a pair of finite difference equations. The numerical solution to these equations is obtained using a digital computer. The results are compared with previously published, approximated analytical solutions to the same problem. Solutions, presented graphically, show pressure decline for constant rate fluid production. The range of variables studied include dimensionless time from '0.001 to 100 and storage capacity ratio from 0.001 to 1,000. The well behaves as if it were in an infinite reservoir for dimensionless times less than 0.25. Reservoir properties near the well can be estimated in the usual manner. An overlay technique is used to match an experimental curve with one of the theoretical curves. It is possible to estimate the distance to a discontinuity by substituting the actual time t and the corresponding dimensionless time tD at which a match occurs into the equation a = (0.000264 tk1/tD , µ1 cI)I/2 where kI/ I µI cI is the diffusivity near the well, and may be estimated from data taken at early time. Several buildup curves are computed. These curves show that for early shut-in times, correct values for transmissibility are obtained from conventional analysis. However, erroneous values of static reservoir Pressure are obtained unless data at large shut-in times are taken. INTRODUCTION A mathematical treatment of the transient pressure response of a well located at the center of a region bounded by a circular discontinuity is given. Within a region (Fig. 20) the properties of both the rock and the fluid are considered to be constant on either side of the discontinuity. While these properties are considered constant, they may be different on opposite sides of the discontinuity. A discontinuity of this type could be a fluid-fluid contact or a sudden change in rock characteristics such as thickness, porosity or permeability. Analytical solutions to this problem are available. 1-3 However, they are so involved that they are of little practical use. An approximate solutionl is available but the range of times over which it is valid has not been specified. A numerical solution to a pair of finite difference equations is used to obtain the solution given in this paper. PREVIOUS WORK One of the first solutions to the problem was published by William Hurst.1 Hurst considered unsteady-state flow of fluids through two sands in series with different mobilities in each sand. He used Laplace transforms to obtain a solution for a single well located at the center of the circle enclosing the first of the two sands. In this case, the solution for the pressure change in Region I (Fig. 20) is2

By L. C. WYMAN

THIS paper discusses what mining reports should contain when presented to the California State Corporation Department, to accompany applications for the sale of stock to the general public, but the principles involved apply to mine financing everywhere. Such reports should 'be as clear and concise as possible, endeavoring to tell the truth in as few words as necessary. Should the engineer be aware that his report is to be used in connection with the sale of stock to the general public, he should consider the public as his client as well as the person who actually employs him. It is always required that the engineer be favorably known and of recognized standing. The following points should be given careful attention : 1. A legal description and location of the property. 2. Transportation conditions, and how they may be expected to affect the operating costs. 3. A brief history of the property, its production record as to tonnage, grade, and character of the ore should be given. Should the property have suspended operations for any reason, this should be given. Any details of former operating costs should be given, especially as to how any improvement could be made, due to better methods which might be employed.' 4. The main geological features and whether they are such as to lead the engineer to believe that the mine may possibly 'be exhausted or the ore of such grade as to be no longer profitable. If he considers them favorable, he should give his reasons for the belief that further development work may produce profitable results. A map showing these features should be submitted, and it is not necessary that such map be highly colored or contain any more than the essential matters. 5. Other mines in the district, or those with similar

Jan 1, 1929

By R. D. Nelson

The purpose of this technical note is to briefly present some data on a phenomenon—recrystallization with concurrent deformation—that has been found to occur in a plutonium. This phenomenon is unusual because a plutonium is considered brittle, not easily deformed, and not easily recrystallized; the a phase is simple monoclinic having 8 atoms per unit cell and it is stable below about 115°C. The properties of the recrystallized metal were different from the as-cast metal. Even though a plutonium is difficult to deform, Ianniello successfully rolled it' and he also observed some recrystallization at 120°C.2 Pavlick and Hanson3 detected some recovery at 109°C but they observed no recrystallization. Gardner4 and Bronisz5 studied the compression properties up to 100°C but they did not report having seen recrystallization. In the present deformation studies of electrorefined plutonium pronounced recrystallization took place concurrently with plastic deformation in compression between 24" and 115°C. The metal contained less than 300 ppm total impurities with the major impurities being 100 ppm Am, 30 ppm C, 40 ppm W, and 25 ppm U; all other impurities totaled less than 100 ppm. The compression specimens were machined to dimensions of 1.2 cm long and 0.8 cm diam from as-cast rods having a density of 19.65 g per cu cm. They were heated to the test temperature in a high-temperature silicone fluid that was evacuated to 10-4 Torr. With this procedure the specimens oxidized a negligible amount, and the temperature was maintained within ±0.2°C for times up to 3 weeks. Deformation and recrystallization

Jan 1, 1969

Some years ago it was my good fortune to inspect some coal properties in Germany, and the most striking impression I received on my trip was that in that country every one in the coal industry, miners and operators, was proud of the fact-not apologetic about it-and that industrially coal was looked upon as a King. The explanation, of course, was that at least 90 per cent of the entire mineral value produced in Germany was from coal, and that it was the very foundation of the nation's industrial life. The feeling was so different from that existing in the United States among those engaged in producing coal that it made a profound impression on me, and many times since then I have speculated about the reasons for the difference in opinion in the two countries. Here, of course, our units are much smaller and more numerous, there is not so large a proportion of technically trained men, and we have the American trait of depreciating the things we do at home; but among those not actively

Jan 1, 1939

By Jay A. Carpenter

FIRST of several sessions at the Annual Meeting devoted to mining methods was a joint program with the Coal Division devoted to the use of Diesels underground. Fred W. Stiefel, in the first paper, stressed the saving in original cost and in operation. Wm. B. Harris then presented the paper of which he was a joint author, and S. H. Ash stressed the poisonous nature of nitrous fumes from Diesel engines even in minute quantity. Determination is difficult but in exhaust gases they are present in amount two to five times that of carbon monoxide. Jay A. Carpenter, in the closing paper of the session, stated that state laws in general prohibit the use of Diesels underground, and that almost all mine inspectors are opposed.

Jan 1, 1942

By R. Scot Clark

The reactively sputtered silicon dioxide capacitor -was developed for use in the monolithic integrated circuit, thereby requiring the capacitor to be fabricated on an oxidized silicon slice. The silicon dioxide film is formed by reactively sputtering silicon in a 50 pct Ar-50 pct 0, atmosphere and the physical properties are indistinguishable from silica. A practical upper limit of capacitance per unit area of 0.25 pf per sq mil is reached with the capacitors fabricated from the Si0, film. Methods shown to enhance this value are double stacking the thin-film capacitors and addition of aluminum to the silicon cathode during sputtering to form an aluminosilicate dielectric. A major contribution to the field of diffused integrated circuits would be the addition of auxiliary passive devices for replacement of diffused passive devices which are currently being fabricated for many integrated circuits. This accomplishment would increase the flexibility of the diffusion process in order to concentrate more on transistor parameters rather than on fabricating diffused resistors and capacitors. To pursue this technique, a thin-film SiOz capacitor was developed which has _ proven applicable to many integrated circuits. Although the SiOl capacitor has an application, the major deterrent from extending the integrated circuit into many useful areas such as low-frequency linear application is the low dielectric constant of SiO, and the low usable capacitance in an integrated circuit. This paper will cover the sputtering techniques used for forming the SiO, film, the physical and electrical properties of sputtered SiO,, and yield information concerning the application of these capacitors to integrated circuits. REACTIVE SPUTTERING Reactive sputtering is simply the sputtering of a metal or semiconductor in glow discharge in the presence of a reactive gas. The material to be sputtered is seen in Fig. 1 as the cathode of the system and is bombarded with positively charged ions of the ambient gas. In this investigation, the ambient gas is composed of 50 pct Ar and 50 pct O2 at a pressure of approximately 2.5 X l0-' Torr. The ions are accelerated toward the cathode in the cathode dark space by the electric field and upon striking the cathode effect a momentum energy transfer to the surface atoms. The transferred energy is sufficient to dislodge a surface atom or atoms and these particles diffuse through the glow discharge to the collector or anode. Several mechanisms of oxidation in the reaction chamber can be considered during reactive sputtering. 1) The surface of the cathode is oxidized and the oxide is subsequently sputtered. 2) Oxidation and sputtering occur simultaneously. 3) Sputtering of the cathode material is followed

Jan 1, 1965

By E. P. Miesch, P. B. Crawford

A study was made of the effect of permeable and impermeable lenses in a reservoir on the production capacity of a well. Both steady-state and unsteady-state data were obtained. An electrical resistivity model was used to obtain the steady-state data and thermal models. were constructed to obtain the unsteady-state data. The productivity of a well is affected very greatly only when the lenses are close to the well. The effect of circular lenses on the productivity ratio can be correlated with the distance from the center of the lens to the center of the well divided by the radius of the lens. When this dimensionless distance is equal to six or greater, the effect of the lenses on production capacity will be negligible. The pseudo steady-state productivity of a heterogeneous reservoir can be predicted using steady-state data. INTRODUCTION Many analytical solutions of reservoir behavior assume that reservoir rock is uniform and homogeneous. Although this assumption is used, all of the data from core analyses and well logging indicate that the reservoirs are heterogeneous. Very little work has been done on the performance of heterogeneous reservoirs. The work of Landrum,l et al. showed that transient phenomena in oil reservoirs could be studied with thermal models. Pickering and Cotman2 used thermal models to study flow in stratified reservoirs and investigated the effect of inhomo-geneities in oil reservoirs on transient flow performance. Loucks3 made a mathematical study of the pressure build-up in a system composed of two concentric regions of different permeability. Root, Silberberg and Pirson4 studied the effect of the growth of the flooded region on water influx predictions using a thermal model consisting of three concentric cylindrical regions of different thermal properties which simulated the aquifer, the flooded region and the unflooded portion of the original hydrocarbon region. Tomme, et a1.5 made a mathematical study of vertical fractures. The object of this investigation was to study the effect of highly permeable and impermeable lenses in the vicinity of the wellbore on the pressure depletion history of the well. Steady-state data were obtained for both conductive and nonconductive lenses that completely penetrated the formation. The lenses were symmetrically located at various distances from the wellbore. The unsteady-state data were obtained on seven thermal models. EXPERIMENTAL EQUIPMENT AND PROCEDURE STEADY-STATE DATA The steady-state data were obtained from an electrical resistivity model 30 in. in diameter and approximately 11/2 in. deep. The outside of the model was lined with a 30-in. diameter copper strip, which served as the outer boundary of the reservoir. The bottom was covered with a sheet of plexiglass so that it would be nonconductive. The model was filled with a slightly saline solution. The well size was varied from an 0.064-in. diameter copper wire to a 10-in. diameter copper cylinder. Readings were taken with an impedance bridge using AC current to prevent polarization at the contacts. Copper and wax lenses were used to represent infinitely conductive and nonconductive lenses, respectively. The resistance was first measured for each well diameter with no lenses in the reservoir. Then the conductive and nonconductive lenses were spaced symmetrically at various distances from the well and the resistance read from each lens location. The diameters of the conductive lenses were 3, 1.022 and 0.624 in., and those of the nonconductive lenses were 3, 2.25 and 1.563 in. The ratio of each resistance reading to the resistance reading with no lenses in the reservoir

Jan 1, 1965

By E. T. Turkdogan, P. Grieveson

It is shown experimentally that, by making use of the coupled S-O reaction in ionic melts, it is possible to transfer slclJur or oxygen from a lozv to a high chemical potential through an ionic nzenzbrane. This uphill transfer of sulfur is accompanied by a counter downhill transfer of oxygen and vice versa. The Materials balance shows that the amoulits of sul -fur and oxygen lost or gained by one system are the same as those gained or lost by the other systenz — the two systejns being separated by an iofzic membmne. The systems used in these experi?nents were solid Mn-MnS-Mno and liquid Fe-S-0. Sufficient results were obtained Lo study the kinetics of the transfer and the indications are that the counter diffusion of sulfide and oxide iojzs in the membrane is the rate controlling process. WHEN an ionic oxide-melt reacts with an atmosphere containing sulfur and oxygen-bear ing gases the following reaction occurs: 1/2 S2 (gas) +O2- (melt) = S2- (melt) + 1/2 0, (gas) [1] Under the restrictions that i) electric conductance in the melt is purely ionic and ii) each constituent element in the melt does not change valence, the solution of an atom of sulfur in the melt will result in the evolution of an atom of oxygen, so that the electric neutrality is maintained. For a given temperature and melt composition, the equilibrium concentration of sulfur in the melt is determined by the ratio, po2 /ps2 , in the gas phase and not by the individual partial pressures of oxygen and sulfur. This has been demonstrated by a number of investigators, for example by Richardson and withers', Fincham and Richardson,la by St Pierre and Chipman,' and by Turkdogan and Darken.3 In his Howe Memorial Lecture for 1961, Darken discussed the possibility of uphill pumping of sulfur through an ionic membrane at the expense of oxygen. TO test the validity of this concept associated with coupled reactions, experiments were carried out in the following manner. A presintered mixture of Mn-MnS-MnO and prefused mixture of Fe-S-0, contained in platinum and iridium crucibles, respectively, and separated by a thin layer of soda-glass (to act as an ionic membrane), were placed side by side in an evacuated silica capsule and sealed. This was then kept at 1400°K for a required time to allow Reaction [11 to occur via the ionic membrane. When partial equilibrium is reached, the ratios Po2 /pS2, for systems on either side of the membrane, are equal and the flux of sulfur and oxygen through the membrane becomes zero, although the individual partial pressures po2 andp,, in these two systems may differ considerably.

Jan 1, 1962

By Harold B. Goldman, Don Reining

The sand and gravel industry is the largest nonfuel mineral industry in the nation (Drake, 1972), Table 1. In 1970, the production of sand and gravel totaled 944 million tons valued at $1.1 billion. California, which leads the nation with more than 140 million tons, together with Michigan, Ohio, Minnesota, Illinois, Wisconsin, and New York, account for 43 % of the total production in the nation. In commercial usage, "sand" applies to rock or mineral fragments ranging in size from particles retained on a No. 200 sieve (0.074 mm openings) to those passing a No, 4 sieve (4.76 mm openings). "Gravel" consists of rock or mineral fragments larger than 4.76 mm, ranging up to 3%-in. maximum size. The construction industry consumes 96% of the sand and gravel produced; the remainder is sand used for specialized products such as glass (see the chapter on "Silica and Silicon"). Utilization The building industry uses sand and gravel chiefly as aggregate in portland cement concrete, mortar, and plaster; the paving industry uses sand and gravel in both asphaltic mixtures and portland cement concrete. Aggregate is commonly designated as the inert fragmental material which is bound into a conglomerate mass by a cementing material such as portland cement, asphalt, or gypsum plaster.

Jan 1, 1975

By H. N. Kalia, J. B. Gresham

Several attempts have been made in the past 60 years to commercialize the vast oil shale deposits of the US. However, the industry has yet to become economically viable. To date, it has not been possible to produce oil from oil shales at a competitive price compared with oil produced by conventional methods. The development work, nevertheless, has been fruitful in furthering the art of thick bed mining and technology of in situ retorting. The in situ method has the potential of recovering oil from thick beds, and the resource recovery potential is much greater than that from underground mining and surface retorting. In situ methods require that the shales/marlstones be fragmented in place to induce adequate porosity and permeability to allow in situ heating of the fragmented shales. This can be accomplished by using explosives. However, it has been found that the existing blasting systems, though very efficient, have some drawbacks. The explosives become insensitive when shot in multiplevertical decks. They can also become insensitive when spaced horizontally at close proximity to other charges. Also, since the blasting is done in a very limited free face, the delay time that can be allowed between charges is also quite limited. Consequently, it is not always possible to routinely predict the performance of the blasting system. Furthermore, since it is not possible to undertake secondary blasting, it is imperative that the blast design function properly. Recent successful retorting by Occidental Petroleum Co. Of Retorts 7 and 8 suggests that some of these problems may have been overcome. This paper addresses some aspects of in situ retorting and problems that have impeded the development of a viable oil shale industry in the US.

Jan 1, 1986

By J. V. Gluck, Ping-Wang Chiang

The tellurium-rich region of the Sb-TI-Te ternary system was investigated by means of DTA, metallo-graphic, X-ray, and electron beam microprobe techniques on the sections Sb2Te3-T12Te3, SbTlTe2-Te, SbT1Te2-Sb2Te3, and SbTlTe2-T12Te3. The phase behavior of this region is summarized in terms of four ternary invariant reactions and a schematic reaction diagram is suggested. Isopleths for the sections SbT1Te2-Sb2Te3, Sb2Te,-T12Te3, and SbTlTe2-Te were constructed, and a schematic diagram of the projections of the liquidus lines and invariant planes is presented. No evidence was found to support the existence of the ternary compound "SbTlTe3", or pseudo-binary behavior of the section T12Te3-Sb2Te3, as reported by Borisova and Efremova. Electrical conductivity, Seebeck coefficient, and thermal conductivity measurements were made at room temperature on fully annealed samples. 1 HE phase relationships in chalcogenides are often complex and difficult to resolve, particularly since the approach to equilibrium is a rather slow process. For example, the phase diagram of the T1-Te binary system was in doubt until clarified by Rabenau et al.,1 the phase fields at compositions near Bi2Te3 in the Bi-Te binary system have only recently been satisfactorily elucidated by Glatz,2 and there may still be some question as to the extent of the Sb2Te3 field in the Sb-Te system.3-5 In ternary systems, the existence of the compound "AgFeTe2" was the subject of a number of conflicting reports6-8 and the stoichiometry of the composition "AgSbTe2" was in doubt for a period of time.9 Recently, questions have arisen regarding the existence of certain compounds in the ternary systems Bi-Tl-Te10-14 and Sb-Tl-Te.15 The impetus for studies of these latter systems stemmed from the report of Borisova et a1.10 of a congruently melting ternary compound, "BiTlTe3", which apparently had extremely favorable thermoelectric properties for room-temperature cooling applications. Attempts by other investigators to produce the compound or confirm the transport properties proved to be unsuccessful.12-14 Recently, Chiang and Gluck14 reported studies of the phase relations in the tellurium-rich region of the Bi-T1-Te system which indicated that the section T12Te3-Bi2Te3 was not pseudobinary as suggested by Borisova et a1.10 The contention of Spitzer and sykes12 was supported that the composition "BiT1Te3" was multiphase, with the primary constituent actually being BiTlTe2, a compound whose existence has been well demonstrated.16,17 The investigation reported in the present paper was prompted by a later report of Borisova and Efremova15 on a similar study of the section T12Te3-Sb2Te3 from the Sb-T1-Te system. They also claimed this section to be pseudobinary, and that a ternary compound "SbTlTe," was formed peritectically. Some "preliminary" crystallographic data were given for the compound and thermoelectric transport properties were presented. In view of the questions concerning the behavior of the Bi-T1-Te system and the existence of the compound "BiT1Te3" it was suspected that the Sb-T1-Te system might behave in a similar fashion, particularly in light of the known existence of a compound SbT1Te2, iso-structural with BiT1Te2.17 Consequently, an investigation was undertaken to clarify the phase relationships in the tellurium-rich region of the Sb-T1-Te system. It is the purpose of this paper to present the results of this study, including a representation of the phase relations, isopleths for various composition sections, and the determination of some phase compositions and transport properties. EXPERIMENTAL PROCEDURES Commercially available high-purity (99.999+ pct) elements, purchased from the American Smelting and Refining Co., were used for the sample preparation. All samples were made from thoroughly mixed powders of previously prepared master alloys: SbTlTe2, Te, Sb2Te3, and T12Te3. Stoichiometric quantities of the constituents for each 10-g sample were weighed into a specially cleaned fused silica tube and sealed under a vacuum of better than 5 x 10-5 torr. The sealed constituents were fused and reacted at 650° to 750°C for at least 4 hr under continuous agitation in a "rocking" furnace, and the resulting product was air-cooled. The tube was opened and the sample was ground to a powder. A portion of the powder was rebottled in a DTA tube under vacuum, and the rest of the material was similarly resealed in a separate tube, re-fused in the rocking furnace, and again cooled to make the ingots for electrical and microstructural studies. All samples were subjected to further heat treatments as discussed in the section on experimental results. Each DTA tube was made of 7-mm-OD fused silica tubing with a concentric 2-mm-ID depression about 4 mm long formed in the bottom to accommodate a thermocouple. The size of a DTA sample was 0.5 to 1.0 g. An Aminco Thermoanalyzer whose accuracy was within 2°C18 was used for the DTA measurements. The metallographic samples were prepared by conventional techniques. A solution of FeCL dissolved in a methanol-HC1 mixture was found to be the most satisfactory etchant. Electron beam microprobe scanning and point-count examinations were made on polished and unetched samples using an ARL Electron Microprobe at an electron beam voltage of 20 kv. The detectors were set to receive characteristic La1 radiation. Calibration standards of the pure elements were incorporated in each sample mount; quantitative point counts were calibrated by a method similar to Ziebold

Jan 1, 1969

By Charles Austin

IN an earlier series of studies on 18-8 stainless steel at 600°, 700°, and 800°C.1 one pretreatment was used throughout; viz., 15 min. in hydrogen at 950°C., followed by an air quench. Several manufacturers of this alloy since have expressed doubt as to the suitability of the temperature employed, recommending instead the more customary Strauss treatment as promising superior results. In this subsequent investigation on the effects of the temperature of pretreatment several interesting points have arisen, which are described in this paper. Previous work on our equipment had shown a marked difference between alloys of "similar chemical composition" that had been manu-factured by different companies. Accordingly, one mill-bar length was selected from which to prepare all specimens. It could then be assumed that any marked differences in creep characteristics would be due to effects resulting from variations in the pretreatment of the alloy. The material was furnished by the Allegheny-Ludlum Steel Co. in the form of 5/16-in, dia. rod, finished by air cooling from a mill anneal at 1950°F. (1066°C.). It was analyzed only for the elements shown: carbon, 0,07 per cent; chromium, 18.73; nickel, 9.46; manganese, 0.40. Three pretreating temperatures were chosen, the specimens being held for 15 min. in hydrogen at either: (1) 1150°C., to conform to the recom-mended Strauss treatment; (2) 950°C., to compare with the results of previous tests; or (3) 750°C., to initiate precipitation of carbides in the material before testing. As the test cross sections were only 1/8 -in. dia., air cooling followed the annealing treatment. These treatments per-mitted two direct comparisons: (1) between the 1150° and 950°C. treat-ments to indicate the effect of grain size when all carbides were probably in solution at the start of the test; and (2) between the 950° and 750°C. treatments to indicate the effect of carbide "nucleation" for similar grain sizes.

Jan 1, 1940

By L. D. Mullins, H. B. Bradley

Numerous articles have appeared in the literature citing the application of the potentiometric analyzer to cycling operations. Specific information obtainable by a potentiometric analysis, as noted by various investigators, includes: 1. Pattern sweep efficiency for various injection and production rate programs. 2. Injected fluid breakthrough time at production wells. 3. Optimum production and injection rates. 4. Prediction of injection and/or production well locations. 5. History of advance of the in-jected-produced fluid interface. 6. Ultimate life of the reservoir. 7. Ultimate reservoir production. This note describes a procedure for predicting pressure distribution in a gas-condensate reservoir by using the potentiometric analyzer to obtain potential distribution data on an analog model of the reservoir and then applying Muskat's' equations. The method relates the volumetric weighted average datum pressure to the mean potential in the model.

Jan 1, 1958

By J. J. Gilman

The data presented indicate that the critical shear stress and strain-hardening Thedatapresentedrate of a zinc monocrystal depend on the orientation of its slip direction with respect to its external boundaries. The tendency of a crystal to form deformation bands also depends on its shape. THE plastic behavior of pairs of zinc monocrystals in which both members of the respective pairs had the same orientation with respect to the longitudinal axis, but each had different orientations with respect to their rectangular external shapes, were compared in this investigation. The purpose of the investigation was to see what influence the shape or surface of a zinc crystal has on its mechanical properties. In a previous investigation of triangular zinc monocrystals,1 anomalous axial twisting was observed which seemed to be related to the triangular shape of the crystals. Wolff,' in 400°C tensile tests of rectangular rock-salt crystals bounded by cubic cleavage planes, found that, of the four equivalent slip systems, the two with the "shorter" slip directions yielded and produced slip lines at lower stresses than the other two. This observation and the work of Dommerich³ as formulated by Smekal4 as a "new slip condition" for rock-salt: "among two or more slip systems permitted by the shear stress law, with reference to the formation of visible slip lines by large individual glides, that slip system is preferred which has the shortest effective slip direction." More recently, Wu and Smoluchowski5 reported essentially the same effect for ribbon-like (20x2x0.2 mm) aluminum crystals at room temperature. Experimental Chemically pure zinc (99.999 pct Zn), purchased from the New Jersey Zinc Co., was the raw material. Glass envelopes, containing graphite molds and zinc, were evacuated while hot enough to outgas the graphite but not melt the zinc. At a vacuum of about 0.2 micron the envelopes were sealed off and then lowered through a furnace at 1 in. per hr so as to melt and resolidify the zinc and produce mono-crystals. One-half of one of the molds is shown in Fig. la. Each mold consisted of four pieces from a cylindrical graphite rod that was split longitudinally and transversely at its midpoints. Rectangular milled grooves 0.050 in. deep and % in. wide formed the mold cavity when the split halves were assembled with twisted wires. Fig. lb shows the specimen shape obtained when the top and bottom mold-halves were rotated 90" with respect to each other. Good fits prevented leakage and excess zinc was necessary to provide enough liquid head to fill the mold completely. In removing soft crystals from the molds it was impossible to avoid small amounts of bending. However, manipulations were carried out whenever possible with the crystals protected by grooved brass blocks. All specimens were annealed prior to testing. From the top and bottom sections of each crystal, X-ray specimens and tensile specimens 7 to 8 cm long were sawed. The tensile specimens were annealed inside evacuated tubes for 1 hr at 375°C. Next the crystals were cleaned and polished by 2-min dips in a solution of 22 pct chromic acid, 74 pct water, 2.5 pct sulphuric acid, and 1.5 pct glacial acetic acid.' Cleaning was followed by a 10-sec dip in a 10 pct caustic solution, then washed in water and alcohol, and dried. This treatment results in a bright surface covered by an invisible oxide film. The testing grips were a slotted type with set screws and were supported in a V-block during the mounting operations in order to avoid bending the crystals. A schematic diagram of the recording tensile-testing machine is shown in Fig. 2. The machine has been described elsewhere.' The head speed was 0.3 mm per sec for all tests. The crystal orientations were determined by the Greninger X-ray back-reflection method with an estimated accuracy of 1. Description of Crystal Geometry A schematic picture of a rectangular zinc mono-crystal is shown in Fig. 3. ABD designates the front edge of a basal plane (0001) of the crystal, the only active slip plane for zinc at room temperature. Of the three possible (2110) slip directions, the active one is indicated by an arrow. Cartesian coordinates are taken parallel to the specimen edges. The normal, n, to the basal plane (n is parallel to the hexagonal axis) has the direction cosines a, ß and ?. X0 = 90 — y is the angle between the longitudinal axis and

Jan 1, 1954

By H. C. Rogers, B. W. Roberts

Vanadium foils and wires, either cold-worked or recrystallized, show a ductile-brittle-ductile fracture sequence with temperature. At about 150°C the hydrogenated vanadium wires are found to be ductile. At room temperature the wires show brittle fracture, and at liquid nitrogen temperature the wires are again ductile, although to a lesser extent than found at 150°C. Hydrogenated cold-rolled vanadium foils have been found to fracture in unusually straight lines along the [100] texture directions. The hydrogen content required to show this [loo] texture fracture is limited to a few atomic percent in range. Hydrogen content above this range causes fracture to occur in random directions. PRELIMINARY experiments with hydrogenated vanadium foils indicated that the embrittling effect of the hydrogen on the vanadium, which was severe at room temperature, was reduced at both lower and higher temperatures. In order to investigate more quantitatively the ductility changes with temperature, vanadium wires were tested in tension at three temperatures. The reduction of area was measured and the fractures examined. Specimen Preparation—The material used was kindly supplied by A. U. Seyboltl in the form of M-in. rod. The nominal analysis was: 99.2 pct V assay, 0.2 pct C, 0.01 pct Si, 0.01 pct Fe, 0.015 pct Ca, 0.02 pct O,, 0.01 pct N2, and 0.003 pct H,. The specimens were 0.035-in. diam wires. These were prepared by cold-swaging the supplied rod to the final diameter without intermediate anneal. They were finished with long-bearing dies. The surface was then given a light polishing with 0 emery paper and degreased in trichlorethylene. An X-ray check indicated that the cold-swaged wire had a fairly strong [110] fiber texture. The wires were then recrystallized in vacuum in continuously pumped quartz tubes at two temperatures to give two different grain sizes. One group of wires was given 45 min at 800°C; another, 60 min at 1000°C. The microstructures in Fig. 1 show the wires after they have been electropolished and elec-troetched in 10 pct HCI. After the 800°C anneal, the vanadium grains had a diameter of 1 to 2p and there appeared to be a tendency to elongation in the longitudinal direction. However, the latter may be an etching effect. After the 1000°C anneal, the grains appeared to be equi-axed, but there was a very large spread in grain size, probably due to some impurity segregation in the wire, Fig. 1, right. The grain diameters varied between the limits of 1 to 150p. The small particles shown particularly clearly in Fig. 1, left, are also visible on the polished surface of all samples before etching and are undoubtedly carbides and nitrides of vanadium. An X-ray check indicated these annealed wires had a strong [110} recrystallization fiber texture. The hydrogenation was carried out in an iron retort with dry hydrogen flowing through it, the retort and contents being heated in a tube furnace with a hydrogen atmosphere. The hydrogenation temperature was approximately 500°C. The hydro-genation times chosen were approximately those which would be just enough to cause the vanadium to be brittle at room temperature and thus allow the greatest chance for ductility to occur at the other two temperatures. Part of the fine grained specimens were hydrogenated for 21/2 min at 490°C. Part of the coarse grained specimens were hydro-genated for 11/2 min at 515°C.

Jan 1, 1957