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By H. Groeneveld, C. A. Connally, P. J. Hoenmans, J. J. Justen, W. L. Mason

A miscible displacement pilot using a slug of LPG driven by separator gas was conducted in the Cardiurn reservoir of the Pembina field. The injection pattern was a 10-acre, inverted, isolated five-spot. Upon completion of the LPG-gar phase, an experiment was conducted using a slug of water followed by gas. Calculated performance of the pilot is compared with actual performance. Equations are developed to calculate the distribution of LPG into zones of varying permeability, to estimate the progress of the flood at different times in the various zones and to estimate gas rates after breakthrough. The analysis indicates that permeability stratification was a dominant factor in controlling oil recovery and that oil was completely displaced from the swept pore volume. The results of the pilot indicated that miscible flooding is a practical means of pressure maintenance in this reservoir. The total recovery from the pilot area was good in spite of the early breakthrough of LPG. The effects of stratification were reduced by injecting a slug of water into the partially swept reservoir. INTRODUCTION The Pembina field,' located in Alberta, is the largest oil field in Canada and one of the largest in the North American continent. The reservoir is a stratigraphic trap producing from the Cardium sand. Neither bottom water nor free gas has been found. The recovery of oil by the natural depletion mechanism has been estimated at 12.5 per cent. Pressure maintenance studies of various areas have indicated that the recovery can be increased 21/2 times by water flooding, and a large area of the field is presently under water flood. However, reservoir studies of the North Pembina area indicated that miscible flooding might be competitive with water flooding. A pilot test was conducted to evaluate the performance of a miscible flood. A 10-acre, inverted, isolated, five-spot pattern was selected for the pilot. The pattern area was large enough to minimize wellbore fracturing effects and contained sufficient oil to provide significant working numbers. The performance of each of the four producers could be evaluated individually and compared. In the event of breakthrough in one direction, the effect would be isolated from the other producers. The use of a single injector minimized the volume of LPG required, and, because of the high mobility of gas, one well was sufficient to inject the necessary daily volume to replace the high rate of production. With four producers, the test could be completed in time for results to be evaluated, additional engineering studies to be made and a unit to be formed before the reservoir pressure in the North Pembina area declined below the bubble point. The pilot was located in an area developed on staggered, 80-acre spacing. The injection well was drilled at a regular location, while the four producers were drilled 467-ft north, east, south and west of the injector. Each quadrant and its associated producer were identified according to their direction from the injector— that is, north, east, south or west. The eight surrounding producers on 80-acre spacing were shut in to isolate the pilot area and provide for reservoir pressure observation. The pilot wells were completed using permanent-type completion techniques. After coring, casing was run through the pay section and cemented. Inside 51/2-in. casing, 2 1/2-in. tubing was hung. The wells were perforated opposite the Upper Cardium sand and lightly fractured. Fracturing volumes, rates and pressures were low to minimize the extent of the fractures. The fracturing treatments average 1,000 lb of 20-40 mesh sand in 700 gal of a low fluid-loss sand-carrying agent. Feed rates and wellhead fracturing pressures averaged 5.5 bbl/min at 2,535 psig, respectively. After fracturing, the productivity index was measured in each of the five pilot wells. The average PI of the four producers was 0.41 BOPD/psig drawdown. The measured PI'S were approximately the same as PI'S calculated from core analysis data, indicating that the fracturing treatments were just sufficient to overcome

By Wm. Reuben Webster

THE greatly enlarged demand for small sizes of seamless copper tube which has recently occurred, due particularly to the rapid growth of the electric household-refrigerator industry, has emphasized the superiority of phosphorized to tough pitch copper for the purpose of producing this commodity. In the manufacture of this material exceedingly heavy reductions by cold drawing are employed, customary practice involving as much as 90 per cent. reduction of cross-sectional area in four runs without intermediate annealing. Although this superiority has long been recognized by tube makers, no quantitative expression of it has heretofore been published. It is believed that the data herewith presented will serve this purpose. Recent investigators are not in agreement as to the relative mechanical properties of copper containing small amounts of oxygen as compared with copper containing sufficient oxygen to produce that condition known as tough pitch. Hanson, Marryat and Ford' found that "oxygen has a relatively small effect on the properties of copper." Johnson,2 on the contrary, states "it cannot be denied that it (tough pitch copper) is inferior, to deoxidized copper where severe mechanical manipulation is concerned." These authorities in the reports of their investigations, as might be expected from their conclusions, do not present data of a character requisite to a conclusive determination of the question.

Jan 1, 1927

By Vernon A. Mrak

The Powder River Basin of northeast Wyoming was the first area in the state to receive attention during the early days of uranium exploration. Although the uranium occurrences are many and widespread, most of the known ore deposits are quite small and difficult to mine. As a result of this, detailed regional exploration in the Powder River Basin has been neglected. The uranium ore deposits occur in that part of the Wasatch Formation that is of earliest Eocene age, and they are scattered over an area of about 400 square miles. All uranium ore deposits are associated with red beds or altered sandstones within the Wasatch Formation. Uranium ore was first shipped from the region in 1953. Total production through June of 1965 is 506,257 tons of uranium ore containing 1,922,527 pounds of U3O8. The average grade of ore is about 0.19 per cent U3O8. The major producing area of the Powder River Basin is the Monument Hill district where about 91 per cent of the basin's total uranium ore has been mined. The source of uranium is presumed to have been the Oligocene, Miocene, and perhaps Pliocene tuffaceous rocks that once overlay the area. Joints, fractures, and permeable beds or zones were the passageways for the migration of uraniferous waters from the overlying beds to the Eocene host rocks.

Jan 1, 1968

By Turno De Michelis

The Porto Marghera plant was erected in 1936 for the production of 10,000 tons of electrolytic zinc annually. Since then it has been continuously enlarged until annual production of the metal reached 40,000 tons in 1969. At the same time the processing cycle was modified bringing it up to date with modern techniques, and was completed by installations for the recovery of by-products in the minerals treated and subsequent processing of the base metal. 90% of the zinc produced is of 99.993% purity . At present the plant comprises, first of all, the zinc blende desulphuration department which has a single modern fluid bed furnace capable of processing 220 - 250 tons of dry crude mineral daily; it is connected to the sulphuric acid plant with its three catalysis sections each capable of producing 60-70 tons of sul9huri.c acid monohydrate daily. The roasted blende is conveyed pneumatically to plants for leaching of the zinc and purification of the resulting solution. During recent years this department has been completely transformed from the discontinuous cycle, for which it was built, to the continuous cycle, paying great attention to

Jan 1, 1970

By Gerhard Derge

THE extension of metallurgical control of steelmaking processes has always made it desirable to have some quick method for determining the oxygen content of molten steel. To meet the practical demands of the steel industry, this method must also be simple enough so that the sampling can be done by the regular furnace crew. This requirement was kept in mind continually in the work to be described. An oxygen value is required for proper control, whether it be of a rimming steel or of a fully killed steel. However, two factors have discouraged the development of such direct methods: I. The reaction C + FeO -+ Fe + CO is rapid enough to make the correct sampling of the bath a difficult problem. The most generally accepted means of circumventing this difficulty have been the aluminum-killed bomb test of McCutcheon and Rautio1 and the aluminum-killed spoon test of Herty.2 The theory of these tests is that all of the oxygen in the iron is converted to A1203, which can then be determined by chemical methods. Even when simplified so that the analysis is made by a measurement of turbidity, this method is too slow to be used in routine control. Furthermore, the results obtained have never been entirely satisfactory, and some of the reasons for this will be discussed later in this paper. 2. The ordinary chemical methods of analysis for oxygen in steel are not reliable. The only analysis that seems to possess sufficient dependability to be of value is vacuum fusion,3 and the apparatus and technique developed for this have been too complex and slow for routine work. INDIRECT METHODS Indirect methods of estimating the oxygen have been resorted to in mill practice. Generally these depend upon the chemical equilibria involved. The oxygen in the bath is related to other components in the slag or metal that can be analyzed more readily. These methods have many difficulties in common. Steelmaking processes involve a complicated set of interrelated reactions, all of which tend to approach equilibrium at varying rates. The degree to which any particular equilibrium is approached, is not , well established. Moreover, a proper use of theoretical equilibrium constants requires a more extensive knowledge of the activities of the reactants than we now have. This is well illustrated by the irregularities observed when trying to determine the oxygen in the metal by its ratio to the iron oxide in the slag. Equilibrium relations may be used more readily if they are evaluated by plant experience, but the extent of approach to equilibrium remains an undetermined variable and lack of an entirely satisfactory means of determining oxygen for the calibration is felt keenly. For example, the statistical analysis of the relation between carbon and oxygen4 5 illustrates that even in a single plant wide variations exist under normal conditions of operation. Nevertheless, this is one of the best methods now

Jan 1, 1943

By Sidney Powers

CONTENTS PAGE Distribution of fields 4 History of development 6 Origin of oil 7 Structure, accumulation and migration 8 Reservoir rocks 9 Methods of drilling and exploration 10 Oil-field statistics : 12 Description by regions: United States: Appalachian region ; 12 East-central states 17 Kansas 18 Oklahoma : 19 Texas : 24 Arkansas : 32 Louisiana 33 Mississippi ....... 34 Rocky Mountain region : 34 California 37 Canada 41 Mexico 43 Cuba 46 Bibliography 46 THE purpose of this brief account- of the occurrence of petroleum in North America is to make available to those who have a knowledge of geology, but who are not engaged in the petroleum industry, a few salient facts about the location of oil and gas fields, their productivity, the important structural types of accumulation and the age of the rocks containing petroleum. A few useful data and statistics are furnished, yet not complete statistics that are available elsewhere. Geology has been treated in simple terms because the reader is presumed to have little interest in the names of formations and of oil sands. Mineral deposits are more or less analogous. Whether oil or metals, minerals are found in rocks, largely in sedimentary rocks which carry water or have at one time carried it. A genetic or accumula-

Jan 1, 1931

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

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

Jan 1, 1967

By Stuart E. Buckley, C. R. Hocott

The viscosity of the oil in the reservoir is one of the properties that influence its movement through the sand to producing wells. Measurements of viscosity, therefore, are pertinent to problems associated with well behavior and with the estimation of recoveries, and afford an indirect means for partial evaluation of various methods of controlling reservoir behavior. The effect of dissolved gases on the viscosity of crude oil has been determined,ls2 but no data have been published on the viscosity of representative samples of reservoir oils. This paper describes a simple instrument that has been used to determine the viscosities of a number of subsurface oil samples at the temperatures and pressures existing in the reservoirs, and presents the results of the determinations for typical fields. Construction oF the Apparatus The principal requirements of any instrument used for the examination of subsurface samples are that it be strong and simple both in design and in method of operation. Accuracy beyond that of the degree of reproducibility of subsurface Sam-~les from various wells in a reservoir or exceeding that of the common measure-merits of reservoir temperatures and Pressures is not required. Because of the expense of procuring subsurface samples, it is necessary also that the instrument operate on a relatively small fraction of a sample, leaving the remainder for other tests, and that there be few or no failures of the equipment to cause undue delay or loss of a sample. After preliminary experiments with a falling bullet, the results of which were not satisfactory, a simple viscosimeter was built of the rolling ball type first proposed by Flowers3 and later used by several investiga-tor. 5.8 The apparatus consists essentially of a removable, accurately bored cylindrical barrel of 1/4-in. nominal internal diameter, 8 in. long, in which a closely fitting steel ball rolls through the oil with the barrel inclined at a definite angle. The ball makes contact at one end of the barrel with ail insulated electrode, closing an electrical circuit, which actuates a buzzer. The meas-urements consist essentially in determining the time required for the ball to travel the length of the barrel. The details of the construction are shown in Fig. I. The barrel in which the ball rolls was made from a section of 25-caliber blank rifle barrel, specially bored to an exact uniform diameter and polished. The barrel slides snugly into a hole bored in a solid stainless-steel cylinder, an upper external shoulder of the barrel compressing a small spring, and is held in place by a hollow nut. The spring prevents the barrel from seating against the bottom of the bored hole in the cylinder, while narrow external longitudinal slots in the barrel permit fluid to flow around it and through the bottom. The upper part of the recess in the steel cylinder is enlarged to form a tapered chamber, which acts as a reservoir for the oil and affords space for agitation to ensure

Jan 1, 1941

By C. R. Hocott, Stuart E. Buckley

The viscosity of the oil in the reservoir is one of the properties that influence its movement through the sand to producing wells. Measurements of viscosity, therefore, are pertinent to problems associated with well behavior and with the estimation of recoveries, and afford an indirect means for partial evaluation of various methods of controlling reservoir behavior. The effect of dissolved gases on the viscosity of crude oil has been determined,ls2 but no data have been published on the viscosity of representative samples of reservoir oils. This paper describes a simple instrument that has been used to determine the viscosities of a number of subsurface oil samples at the temperatures and pressures existing in the reservoirs, and presents the results of the determinations for typical fields. Construction oF the Apparatus The principal requirements of any instrument used for the examination of subsurface samples are that it be strong and simple both in design and in method of operation. Accuracy beyond that of the degree of reproducibility of subsurface Sam-~les from various wells in a reservoir or exceeding that of the common measure-merits of reservoir temperatures and Pressures is not required. Because of the expense of procuring subsurface samples, it is necessary also that the instrument operate on a relatively small fraction of a sample, leaving the remainder for other tests, and that there be few or no failures of the equipment to cause undue delay or loss of a sample. After preliminary experiments with a falling bullet, the results of which were not satisfactory, a simple viscosimeter was built of the rolling ball type first proposed by Flowers3 and later used by several investiga-tor. 5.8 The apparatus consists essentially of a removable, accurately bored cylindrical barrel of 1/4-in. nominal internal diameter, 8 in. long, in which a closely fitting steel ball rolls through the oil with the barrel inclined at a definite angle. The ball makes contact at one end of the barrel with ail insulated electrode, closing an electrical circuit, which actuates a buzzer. The meas-urements consist essentially in determining the time required for the ball to travel the length of the barrel. The details of the construction are shown in Fig. I. The barrel in which the ball rolls was made from a section of 25-caliber blank rifle barrel, specially bored to an exact uniform diameter and polished. The barrel slides snugly into a hole bored in a solid stainless-steel cylinder, an upper external shoulder of the barrel compressing a small spring, and is held in place by a hollow nut. The spring prevents the barrel from seating against the bottom of the bored hole in the cylinder, while narrow external longitudinal slots in the barrel permit fluid to flow around it and through the bottom. The upper part of the recess in the steel cylinder is enlarged to form a tapered chamber, which acts as a reservoir for the oil and affords space for agitation to ensure

Jan 1, 1941

By D. P. Harris

The construction of a model to associate probability of occurrence of some measure of mineral wealth with the geology for each subdivision (cell) of the area is postulated. The questions (1) are the observations made in reconnaissance geology sufficiently related to mineral wealth to distinguish the cells of high value from those of low value, and (2) can this geology be related mathematically to mineral wealth and probability are answered in a case study of 97,000 square miles in Arizona and New Mexico. Measurements on mineral wealth and geologic variables of 243 cells were made. The geologic variables, valued in counts, percentages and lengths, quantified the theoretical concepts of the model. It was found that multiple discriminant analysis and classification analysis by Bayesian statistics and multivariate normal probability function constitute a two-phase probability model that associates probabilities with geologic information and mineral wealth. The cells of explored area must be allotted the value class indicated by their cumulative production and estimate reserves (given well-defined geological relationships in a mineral wealth area), and a discriminant and classification analysis must be performed in which probabilities of the cell belonging to each of the value groups are generated as a function of the geologic variables. This determines whether high value cells can be distinguished from low value cells by their geology as well as indicating those cells misclassified by the model into a higher value group than warranted by their known mineral wealth. The second use of the model is for extrapolation. It is demonstrated how geologic information on an explored area can be utilized in guiding exploration in an unexplored area. Exploration decisions can be predicted on explicitly determined measures of uncertainty (the probabilities). SUMMARY This study postulates the construction of a model to associate probability of occurrence of some measure of mineral wealth with the geology for each subdivision (cell) of the area. Such a model will distinguish those cells deserving further exploration on the basis of their geology: The basic postulates of this study are as follows: v = Q(R,S,F,A) P(V) = G(R,S,F,A,V), where V = a measure of mineral wealth P(V) = the probability of occurrence of V R = age and type of rock F = rock fracturing A =age of igneous activity and contact relationships. There are really two questions to be answered: 1) are the observations made in reconnaissance geology sufficiently related to mineral wealth to distinguish the cells of high value from those of low value, and 2) can this geology be related mathematically to mineral wealth and probability? In order to answer these questions, an area of about 97,000 square miles situated chiefly in Arizona and New Mexico was selected as a case study. This case study area was divided into 243 cells, each 20 miles square, and measurements were made on mineral wealth and geologic variables. Crude geologic variables valued in counts, percentages and lengths are constructed to reflect the above postulated variables. These measurement variables thus provide quantified values defining the theoretical concepts of the model. It was found that multiple discriminant analysis and classification analysis by Bayesian statistics and the multivariate normal probability function constitute a two-phase probability model that associates probabilities with geologic information and mineral wealth. Given the availability of an area that is well explored and upon which the relationships of mineral wealth to geology can be adequately defined, there are two ways in which the analysis outlined in this paper can prove beneficial. First, the cells of the explored area must be allotted the value class indicated by their cumulative production and estimated reserves, and a discriminant and classification analysis must be performed in which probabilities of the cell belonging to each of the value groups are generated as a function of the geologic variables. Such an analysis determines whether cells of high

Jan 1, 1967

By J. C. Trantham, J. W. Marx

From 1955 to 1958 the Phillips Petroleum Co. conducted a series of small scale counterflow combustion field tests in a tar sand about 60-ft deep and 6 to 12-ft thick near Bellamy, Mo. A total of seven different well patterns, including conventional five-spots and seven-spots plus a 15-well line drive pattern and a 10-well radial pattern, were employed. Electric heaters, gas burners and wellbore fuel packs were tested as counterflow ignition devices. Direct drive ignition followed by reversal to counterflow operation was not possible in this case because of formation plugging by the semi-solid tar during the direct drive phase. Sustained counterflow burning was achieved with wellbore fuel packs under conirolled conditions which permitted close correlation of fire front velocity, air velocity, air-oil ratios and yields for a wide variation in process parameters. The tar in place was about 10' APl with a reservoir viscosity greater than 500,000 cp. The composite oil prodlcct was 26' API with a viscosity in the range of 5 to 15 cp. Vertical sweep efficiency in the line drive pattern was essentially 100 per cent, with no evidence of gravity segregation. Original tar in place ranged between 800 and 1,000 bbllacre-ft, specific rock permeability averaged about 800 md before burning and effective air pemeability with residual oil and water in place (at the time of ignition) averaged 250 md. The volume of oil recovered during stabilized line drive counterflow burning represented about 67 per cent of the volume of tar originally in place in the burned out zones. A minimum was found when air-oil ratios were plotted against formation air velocities, and a limiting air velocity existed below which the counterflow fire front reversed and burned back over its own trajectory, using the residual coke left behind. INTRODUCTION Early in 1955 the Phillips Petroleum Co. began preparations to field test counterflow underground combustion as a method for producing oil from high viscosity hydrocarbon deposits, such as bituminous (tar) sands. At that time all published information on the use of underground burning io increase oil recovery was based on the direct drive process, in which the fire front moved through the formatim in the same direction as the injected air stream. Such direct burning is not applicable to many heavy oil sands or to most tar sands because the heat-thinned native hydrocarbon congeals in the cold rock ahead of the fire front forming a gas permeability block which smothers the combustion. Laboratory experiments first demonstrated that this permeability blocking would not occur if the fire front and the air stream moved in opposite directions. In this counterflow (reverse) burning process the heated heavy oil or tar is driven back through the combustion zone. Here thermal cracking produces relatively light hydrocarbon products which pass through the heated rock behind the fire front (largely in the vapor phase) and are incapable of causing a gas permeability block.' Exploratory wring revealed that consolidated bituminous sandstones with a combination of tar saturation, permeability, thickness and depth favorable for experimental field testing existed at several points in western Missouri. By the fall of 1955, a test site for determining technical feasibility of the counterflow process under field conditions had been selected near Bellamy, Vernon County, Mo. — about fifty miles north of Joplin. The pay zone was too thin and too shallow to constitute a commercial prospect, but these same factors permitted controlled experimental operation with a small compressor installation and with a large number of monitor wells. These were needed for adequate observation of the underground phenomena at reasonable cost. RESERVOIR CHARACTERISTICS The reservoir chosen for the experimental field tests was a 124 thick section of tar sand extending from 49 to 61 ft subsurface, with shale and siltstone laminations sealing the top and bottom. This section was part of a larger 30-ft thick tar sand deposit which extended both above and below the test zone. Core analyses showed that the 12-ft sand was effectively subdivided into two approximately equal sections, with the lower zone being consistently more permeable than the upper zone. The most significant laboratory core data are summarized in Table 1. The line drive test which is the principal subject of this report utilized only the lower 6-ft thick zone, with the upper zone regarded as part of the 55-ft overburden. WELL PATTERNS The over-all field test program involved a total of seven different well patterns, including conventional five-spots and seven-spots plus a 15-well line drive pattern and a 10-well radial pattern. In some of the tests the full 12-ft zone was employed; in other cases only the more perme-

Jan 1, 1967

By I. J. Hegyi, J. J. Tietjen, H. Nelson, J. I. Pankove

The fabrication of p-n junctions in GaAsl-,P, alloys by a vapor-phase gowth technique has for the first tirne resulted in room-temperature injection lasers capable of operating over a broad range of wavelengths extending into the visible region of the spectrum. The shortest wavelength achieved to date is 6750A at room tetnperature. In addition, at 78°K the threshold current density values for these lasers are generally the lo~vest reported, and the emitted radiation extends to the lozc,est wavelength ever attained (6350A). With lasers fabricated from material containing 14 pct Gap, quanticm efficiencies of 26 pct and peak power outputs of 25 zu were obtained at room temperature. ALTHOUGH room-temperature operation of GaAs injection lasers has been well-documented,&apos;-5 the operation of GaAsl-,P, (x > 0) laser diodes has been restricted to relatively low temperatures.8-&apos;0 This has been previously attributed5, 7, 10-12 partially to the difficulty of preparing single-crystalline GaAsl-& alloys having a high degree of chemical homogeneity and purity. Also, with these materials it has been difficult to prepare high-quality, abrupt p-12 junctions by diffusion techniques; and, in turn, this has made it difficult to obtain optimum electrical properties for room-temperature operationL3 in the resulting laser diodes. As a result, GaAsl-,P, laser diodes have not been efficient enough to permit operation at room temperature. For example, using diffused structures, only a few diodes were obtained which could be operated even close to room temperature (255K)." Recently, a vapor-phase growth method of preparing epitaxial deposits of GaAsl - .P, alloys has been described,14 and the high-purity and homogeneity of these materials has been previously demonstrated. Of special significance, with this technique, n- or p -type doping can be initiated or discontinued at any time and at almost any rate during the crystal growth so that the donor and the acceptor concentrations can be easily controlled to obtain desired impurity profiles. This permits high-quality, abrupt p-TZ junctions to be vapor-phase grown entirely during the crystal growth process, so that diffusion or other p-n junction fabrication processes are unnecessary. After growth, the device does not have to be heated to elevated temperatures, which avoids the possible unwanted introduction and motion of both impurities and lattice defects. Using the vapor-phase growth method cited above, over 300 room-temperature injection lasers have been prepared from GaAsl-,P, alloys having compositions in the range of 0 5 x 5 0.41. These lasers have emitted cohe~ent radiation in the spectral range of 8350 to 6350A at 78°K or from 9000 to 6750A at room temperature. The threshold current densities of the best lasers are independent of the alloy composition over the range 0 < x < 0.2 and compare favorably with values for good GaAs lasers.&apos; MATERIAL PREPARATION Multilayer, epitaxial deposits of GaAsl-,P, alloys are prepared by a vapor-growth technique described elsewhere.14 With this technique, the individual layers which comprise the multilayer structure are prepared sequentially in the deposition apparatus without interrupting the crystal growth. The epitaxial layers are deposited on GaAs substrate surfaces oriented normal to the ( 100) direction. The substrate wafers employed in this study were usually doped with tellurium to an electron concentration of approximately 2 x 10" per cu cm. To avoid strains, the first 10 to 15 p of the deposited material is uniformly graded from pure GaAs to the specific GaAsl- ,P, alloy composition of interest. The GaAsl - ,P, alloy growth is then continued to form a layer of constant composition having a thickness in the range of 25 to 75 p. Both the graded region and the layer of constant composition are doped with selenium to an electron concentration of about 2 x 10" per cu cm. The p region of the diode is then incorporated in the crystal by abruptly changing the dopant concentrations in the vapor phase to facilitate doping with zinc. This layer has a hole concentration of approximately 3 X 1019 per cu cm and typically is 50 p thick. DEVICE FABRICATION In general, the GaAs substrate and the region of graded composition are removed. Ohmic contacts are made to the n-type side by tin evaporation and to the p-type side by an electrodeless nickel deposition. This is followed by an electrodeless deposition of gold on both sides. The crystal wafer is then cleaved along (110) planes and sawed into rectangular parallelepipeds. Typical dimensions are 100 by 300 for the junction area and 100 µ for the diode height. The diodes are either soldered to a copper stud or pressure-mounted in a copper clip. RESULTS AND DISCUSSION Approximately 400 laser diodes having compositions in the range of 0.41 have been prepared by the method described above. Each laser was routinely tested at liquid-nitrogen temperature. The lasers were operated with l-psec current pulses at a repetition rate of 60 pulses per sec. The parameters of greatest practical interest are the photon energy or wavelength of the laser output and the threshold current density. Fig. 1 shows the variation of photon energy with alloy composition at 78°K. The composition was determined from the lattice constant of the material obtained by X-ray back-reflection measurements. Although there

Jan 1, 1968

By Raymond Ward

IN the past few years several papers have appeared dealing with different aspects of the oxidation of dilute alloys, especially with respect to the formation of internal oxides or subscales. Subscale has been defined1 as that layer or zone of oxide particles precipitated in a matrix of metallic metal in which the oxide particles are dispersed uniformly and occur by diffusion of the oxygen inward from the metal surface. Alloys composed of a solvent metal more noble than the alloying elements are subject to subscaling or internal oxidation. In these alloys the solute must be present in such quantities that if the alloy is exposed to an oxidizing atmosphere at elevated temperatures, the rate of diffusion of the oxygen into the metal will be greater than the rate of diffusion of the solute outward. There is a composition range of the iron-silicon system that falls into this classification. Knowledge of the nature and rates of oxidation of iron-silicon alloys is of great commercial importance, but very little information of this nature is available. Darken2 recently has made calculations to show the limits of concentration of silicon for which subscales are produced in iron-silicon alloys; however, the main thesis of his paper was to analyze and to explain the already existing data. The purpose of this paper is to present the effect of com position, temperature, time, and atmosphere on the type of scale-metal layer obtained and to give some qualitative indication of the effect of these variables on the rates of oxidation. Since this paper is a study of silicon steels that are available commercially, extremely low-silicon and high-silicon alloys are not included. EXPERIMENTAL PROCEDURE The alloys used in the experiment were taken from heats of silicon steel that ranged in analysis from 0.70 to 5.8 per cent silicon. This composition range takes in most of the commercial silicon steels. In Table I are listed the compositions of alloys used. Other than iron and silicon, the alloys normally contained approximately the following impurities: carbon, 0.03 per cent; manganese, 0.07; phosphorus, 0.008; sulphur, 0.02; copper, 0.07; tin, 0.01, and from nil to a trace of chromium, nickel and copper. All of the alloys used were melted in open-hearth furnaces, except where otherwise noted, and were hot-rolled to 0.100-in. plate. Samples approximately 1/2 in. square were then cut from these materials. So that the surface conditions of the samples used for oxidation would be standardized, each sample was ground through 000 emery paper immediately before oxidation. Two different techniques were employed in carrying out the oxidizing treatments. One consisted simply of heating the samples with free access to air. In this treatment the samples were set on edge on a refrac-

Jan 1, 1945

By K. A. Gschneidner, O. D. McMasters, T. J. O’Keefe

X-ray diffraction, differential thermal, ad rnetallo-graphic methods were used to establish the Dy-Pb Phase diagram. Lead additions lower the 1377°C transformation temperature of dysprosium to 1360°C leading to an inverted peritectic reaction. The 327°C melting point of lead is lowered by dysprosium additions to about 326°C yielding a eutectic reaction. A second eutectic reaction occurs at 13.3 at. pct Pb and 1200°C. The dysprosium-richest intermetallic compound DysPb3 melts congruently at 1695°C and crystallizes in the hexagonal Mn5Si3 (D8,) type structure. The peritectic decomposition temperatures for the remaining compounds are Dy5Pb, at 1555C, DyPb2 at 955C, and DyPb3 at 880°C. A fifth compound near the DyPb stoichiometry exists over a 310°C temperature range decomposing at 1130°C by means of an inverted peritectic reaction and melting incongruently at 1440°C. The crystal structures of the compounds are discussed. A systematic study of the rare earth-lead alloy systems is underway in an effort to supply information concerning the alloying behavior of the rare earth metals. The Dy-Pb phase diagram is the fourth system to be investigated in this study. The Yb-Pb,1 Y-Pb,2 and Eu-Pb 3 diagrams have been published recently. Utilization of the rare earth series of metals as a research tool in this manner should yield a better understanding of alloy formation. EXPERIMENTAL PROCEDURE Materials. The lead used in this investigation was obtained from Cominco Products, Inc., and was specified to be 99.99 pct pure. The dysprosium was prepared in this Laboratory by the calcium reduction of the fluoride followed by distillation of the dysprosium. The major impurities in the dysprosium in ppm are: A1 (<40), Ca (400), Er (<50), Gd (<200), Ho (<200), Mg (<50), Si (30), Ta (400), Tb (<100), Y (<50), 0 (651, H (15), N (not detected), F (430), C (35). Alloy Preparation. Most of the alloys were prepared by melting weighed amounts of dysprosium and lead in sealed tantalum crucibles. The tantalum crucibles were sealed by are-welding in a He-Ar atmosphere welding chamber. Thus the alloys are in contact with He-Ar at about 1 atm pressure. Homogenization was achieved by holding them in the liquid state for about 1 hr, cooling, inverting the crucibles, remelting, and repeating the process at least twice. Since these alloys were prepared in sealed tantalum crucibles, chemical analysis for final composition was thought to be unnecessary. No detectable reaction of these alloys with the tantalum crucible was observed by metallographic examination. Metallographic evidence was also used to confirm the homogeneity of some of the alloys prepared in this manner. The compositions of a few alloys, which were prepared by nonconsum-able are-melting, were corrected for the small weight losses involved by assuming that the weight loss is due to vaporization of lead. The specimens obtained from the alloy samples were prepared under a dry-argon atmosphere because they were rapidly attacked by air and moisture. Thermal Analysis. Differential thermal analysis methods were used to determine the liquidus curves and reaction horizontals of the system. Both Pt vs Pt + 13 pct Rh and W + 5 pct Re vs W + 26 pct Re thermocouples were used to measure the temperature. An X- Y recorder was used to record the specimen temperature and differential electromotive force between the specimen and molybdenum standard. The arrest temperatures were measured potentiometri-cally. The accuracy limits (* values) associated with the reaction temperatures obtained by this method were estimated on the basis of both the reproducibility of the particular temperature value and the accuracy of the thermocouple at a given temperature. Liquidus temperatures were obtained from cooling arrest data while both heating and cooling arrest data were used to establish the horizontals of the diagram. Heat treatments during the thermal analyses of the alloys between 40 and 70 at. pct Pb were necessary in order to approach equilibrium conditions. The samples were held at temperatures between the various peritectic horizontals for l to 2 hr before the thermal analyses were continued. The entire range of compositions was investigated at the expense of a minimum amount of materials by adding appropriate amounts of lead to master alloys. More than sixty alloys were analyzed by this differential thermal method and for each alloy the results given herein are taken from two or three heating and cooling cycles. X-Ray and Metallographic Methods. Slice specimens for metallography and powder specimens for X-ray diffraction were prepared from rod-shaped samples which had been melted in sealed 0.62 5-cm-diam tantalum crucibles. The specimens were heat-treated in sealed tantalum crucibles which were protected by sealing them in argon-filled quartz ampules. Quenching was accomplished by breaking the ampules in ice water after heat treatment. X-ray powder specimens were sealed in 0.3-mm-diam glass capillaries under a dry-argon atmosphere. Copper, iron, and chromium radiation were used to obtain the powder patterns for these alloys. More than 150 powder patterns were obtained for specimens of various compositions and heat treatments. Included in these were several patterns for specimens which had purposely been oxidized. Patterns from specimens which had been accidentally exposed

Jan 1, 1969

By M. Metzger, T. A. Read

The strengthening effects of hydroxide and synthetic plastic films in the creep of cadmium crystals were studied. The results were broadly consistent with the naive mechanical model. The dislocation-film reactions and the significance of the macroscopic stresses associated with certain films are discussed in the paper. ALTHOUGH a number of studies have been made of the strengthening of metal single crystals produced by surface films usually less than Ir in thickness, the mechanisms underlying this phenomenon are still not well established. Roscoe&apos; first noted the critical shear stress and the stress-strain curve of cadmium-crystal wires to be raised markedly by the presence of oxide films. Subsequent investigators2-&apos; have confirmed the effect for several metals and films including a number of plated poly-crystalline metal films. Harper and Cottrel1" with a thin film on zinc presumed to have formed as a result of etching and washing treatments) did not detect a strengthening at a rate of extension of 10 &apos; sec-&apos; although at lo-&apos; sec-&apos; the film raised the flow stress by 7 pct at 0.0005 extension and by 22 pct at 0.01. The marked strengthening at moderate strains thus appeared to be the result of a dynamical effect dependent on the rate and amount of plastic flow. Other observations&apos;. " are consistent with this view. The large effects of films on the tensile creep rate of single crystals were demonstrated when the observation of Andrade and Randall," that the creep rate of cadmium crystals increased on immersion in aaueous solutions of certain cadmium salts. was shown&apos; * to hold only when a film was present initially and was explained by the attack of the solution on the film and the removal of its strengthening effect. Changes in the creep rate interpretable in terms of the removal or formation of various films have been observed by other investigators.3,8,10,31 Certain other experiments have been reported in which surface films or liquid environments have affected the plastic behavior of metals, but these are not within the scope of the present work which deals with the effect of solid films on single-crystal slip. Possible Mechanisms—The film does not significantly reduce the load on the crystal in the elastic range (the elastic moduli of film and crystal are not too greatly different and the area of the film is so small that its share of the load is negligible) so that the initial operation of internal Frank-Read sources is not affected. However, as Fisher" has pointed out, a source terminating on the crystal surface requires only half the critical stress for activation as an internal source of the same length and a relatively strong film (even a very thin one) would pin the free ends of the surface sources so that, if surface sources are responsible for plastic flow in a clean crystal. such a film would increase by roughly a factor of 2 the stress necessary for generation of dislocation loops at a given rate. The other general possibility is that the film resists the passage to the crystal surface of internally generated dislocations. If the film is adherent and if the specimen is to exhibit slip of the same general character as a film-free specimen, the film must deform or fail in shear at the active slip planes. The naive mechanical model, where shear-stress relaxation across the active slip plane in the metal transfers load to the film until it deforms and slip can

Jan 1, 1959

By Thomas W. Yardley

In many years&apos; experience as a maker and purchaser of cast-iron coated pipe, I have never met with any standard form of specifications for such. Each water-works company, employing a hydraulic engineer, has, under his direction, prepared complete specifications for the particular conditions required; but I cannot find that any two are alike; and each foundry, in bidding for the supply of such pipe, makes the price to cover the conditions&apos; required. I, therefore, have the honor of offering to the Institute a form of specifications for cast-iron coated water-pipe, that may be found useful to water-works companies and others requiring pipe of this kind. The conditions are all reasonable, and can be carried out by makers without additional cost, and with advantage to the purchaser. Section 1 gives the kind of pipe, with its general characteristics. Section 2 specifies that neutral pig-iron shall be used, since such iron possesses the strength required, and is uniform in its shrinkage. Section 5, requiring makers to give the brands of pig-iron used

Jan 1, 1890

By G. F. LOUCHLIN

A FEATURE of the International Geological Congress to be held at Pretoria, South Africa, in the summer of 1929,. will be a symposium on the gold resources of the world. In this connection the U. S. Geological Survey and Bureau of Mines have been asked to prepare a report, showing production in the United States, describing the geology of its principal gold- producing districts, and estimating reserves (a) assuming a continuation of presen6economic conditions, and (b) assuming lower costs. This report will not be completed before April 1, but data thus far assembled are here presented with the hope of profiting by discussion and by information from those well informed on any of the important gold-producing districts. Gold production in the United States rose to a maximum exceeding $100,000,000 in 1915 and then rapidly declined to about $52,000,000 in 1920. Since then it has fluctuated, but on the whole slightly declined. Reviews of the eight leading states afford the following tentative conclusions :

Jan 1, 1929

By E. M. Wise

THE properties required of gold alloys for jewelry are not well standardized, due in part to problems peculiar to certain branches of the jewelry industry, in part to the individual preference of the fabricator and to his willingness to cope with certain difficulties in manufacture, which arise with the use of certain alloys. GENERAL REQUIREMENTS In general, the properties desired may be classed as follows: 1. Color should conform to the dictates of good taste and smart style. 2. Corrosion resistance and tarnish resistance should be good. This is to a considerable extent determined by the carat. Resistance to such corrosive agents as mercuric chloride as well as certain depilatories is unreasonable to expect and difficult to meet. 3. Strength and hardness must be adequate to maintain the delicate contours of finely modeled jewelry. 4. Wear resistance must be great enough to resist abnormal wear, such as is encountered by a wedding ring in a lifetime of wear. 5. Ductility must be sufficient to permit the fabrication of drawn shells, tubes and difficult shapes. Material having a yield point of not less than 60,000 lb. per sq. in., an ultimate strength of 100,000 lb. per sq. in., and an elongation of 40 per cent. is desirable. 6. Melting point should be between 800° and 1200° C.

Jan 1, 1928

By Philip Davidson, Wm. B. Price

The object of this paper is to present, a survey of some of the physical properties of sheet nickel silver when subjected to cold rolling and when annealed at temperatures extending from 350" C. throughout the coininercial annealing range.. A number of alloys were taken from stock and analyzed. Four of these, representing low nickel and high nickel both with and without lead, were chosen for the tests. The analyses were as follows: Alloy Copper, Lead. Iron. Nickel, ManGanese, Zinc, PeR Cent. Per Cent. Per Cent. Per Cent. Per Cent. PEr Cent. A................ 64.68 Trace 0.194 6.73 0.06 remainder B................ 65.82 1.27 0.227 6.17 0.06 remainder C................ 65.44 Trace 0.345 17.83 0.08 remainder D................ 65.60 1.08 0.238 17.77 0.06 remainder These alloys were lolled in accordance with regular mill practice to approximately No. 6 R. & 6. gage. The bars (which were then coiled) were annealed together in a mill muffle and afterwards pickled in a 10 per cent. sulfuric-acid solution and cold rolled in stages of approximately one number (B. & S.) at a time to No. 18 B. & S. gage. After each stage, suitable samples were set aside for physical tests. Additional samples were chosen for tests after the bars were rolled to Nos. 8, 10, 12, and 14 gage. These samples were annealed together in the mill muffle and, after pickling, were finished on 0.050-in. gage, yielding a series of specimens 2, 4, 6, and 8 numbers hard for the subsequent annealing tests. Tensile test pieces 9 by 1 in. (22.9 by 2.5 cm.) were cut from both lots and the central portion was milled to give a test section 2 1/2 in. long by 1/2 in. wide. A distance of 2 in. was marked off on the edge of each specimen with light punch marks. In the case of the annealed alloys, Erichsen test pieces 4 by 235 in. were also taken.

Jan 1, 1921

By Albert Sauveur

My first paper dealing with the theories of the hardening of steel by rapid cooling was published in the Transactions of this Institute in 1896— 30 years ago-under the title "The Microstructure of Steel and the Current Theories of Hardening," hence, also, the title of the present paper. It was extensively discussed and was, I believe, one of the starting points of many subsequent papers and discussions of the same subject, dis-cusssions which at times became almost violent and which led to the formation of different schools such as the "Carbonists" and the "Allo-tropists." Some of the older members of the Institute, who took part in the debate or who were interested observers, will, I am sure, have kept a vivid remembrance of it. The controversy gradually quieted down, apparently for lack of ammunition, without any side acknowledging defeat. Recently, however, interest in it ha been revived through the claims of some that these vexed questions had at last been solved. In an effort to ascertain if possible the prevailing view of those best qualified to express an opinion a questionnaire was submitted to the following gentlemen: J. 0. Arnold Sir Robert Hadfield Edgar C. Bain W. H. Hatfield Carl Benedicks Samuel L. Hoyt N. Belaiew Kotaro Honda H. M. Boylston Zay Jeffries Harry Brearley H. Le Chatelier G. K. Burgess H. H. Lester William Campbell Francis F. Lucas H. C. H. Carpenter John A. Mathews Pierre Chevenard A. McCance P. Dejean Albert Portevin C. A. Edwards Walter Rosenhain F. Giolliti Bradley Stoughton G. Grenet F. C. Thompson Leon Guillet

Jan 1, 1926