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By Donald C. Barton

The elastic earth waves produced naturally by earthquakes have been used for a long time as evidence from which to draw conclusions in ; regard to the constitution of the interior and crust of the earth. The I elastic earth waves produced artificially by occasional explosions and ' recorded by seismological observatories were used to draw conclusions regarding the geology of the intervening area. Intentionally produced elastic earth waves in the past five years have come to be used extensively in the investigation of very local geologic structure. The scismic method of working geologic structure, which makes use of artificially controlled explosions and the resulting earth waves, has developed almost clairvoyant power in handling certain geologic situations; and, in the discovery of salt domes in the Gulf Coastal Plain region of Texas and Louisiana, it has scored the most brilliant success. The first proposal for the use of artificial earthquakes in the study of velocity of elastic earth waves in the surface formations of the earth's crust were made before 1888, by the English seismologists mallet and Abbot. Partly on the basis of their work, A. Schmidt in 1888 proposed the use of time-(Iistnncc graphs of artificial earthquakes to study the variation of vellocity with depth. Belar in 1902 proposed the practical 'application of such investigation in connection with boring tunnels. Galitzcn repeated1y (1912. I9IX) proposed the use of explosions to study the velocity of the longitudinal and transverse waves in the uppermost formations and pointed out that the velocity depended in a high degree on the physical character of the beds and that from changes in the velocity, conclusions could be drawn in regard to the composition of the beds. Somewhat the same thought was proposed by von dem Borne (1908), by Benndorf, Udden and others.' First Use of Artificially Excited Earth waves to Determine Local structure The first application of the use of artificially excited elastic earth waves to thc determination of local geologic structure was worked out,

Jan 1, 1929

By J. E. Pavlick, W. W. Mullins, H. W. Paxton

The growth of nitrogen-austenite during nitriding of large-gvained ferrite between 650" and 800°C has been studied as a functimz oJ time and nitrogen potential of the atmosphere for a variety of alloying elements dissolved in the ferrite. Whereas no preferential grain boundary penetration by aistenite takes place in zone-refined iron, the addition of aboit I zot pct oj' V, Ti, Cr. Si, or A1 produces significant protrusion of austenite down former 0-0 boundaries. This group of elernents also produces ragged y-0 interfaces in the a grains which advance more slozuly than those in zone-refined iron. 1 zut pct of Ni, Co, Mn, or Mo dissolved in ferrite leads to essentially smooth 7-a interfaces, which advance at rates very sinzilar to those in zone-refined iron. The reasons for this effect are not clear. Two possible limiting hypotheses, not necessarily exclusive, are discussed. One involves p.referentia1 grain bozindary diffusion of nitrogen. the other the production of a zone of ferrite, stpersatcirated with respect to nitrogen, from which austenite precipitates helerogeneozisly on the a-a gyain boundaries. In many phase transformations which occur by nu-cleation and diffusion-controlled growth, information on the parameters which control the rates of nuclea-tion and of growth is frequently not quantititative. The present work describes a continuation of efforts to obtain quantitative data on growth rates in systems where thermodynamic and kinetic factors are known independently, and thus where comparison with models of the growth process is possible. The work has been conducted on iron-base systems for two reasons. Firstly, there are several interesting transformations in this system, many of which are of practical importance. Secondly, the information on phase diagrams, activities, and diffusion coefficients is more complete in this system than in any other. These data are still inadequate to check all the effects of alloying elements, but at worst it is possible to make estimates and thus examine order-of-magni-tude agreement with proposed models. It will be necessary to do this in the present work. The problem studied was the growth of nitrogen-austenite in from the surface of large-grained columnar crystals of alloyed ferrite exposed to an NHs/Hz atmosphere. Earlier work by Grozier et al.' had suggested that growth of austenite may occur preferentially along grain boundaries of alloyed ferrite, whereas zone-refined (ZR) iron shows no such effect, Fig. 1. Growth of nitrogen-austenite into single crystals of zone-refined ferrite is planar provided sufficient nu-cleation sites for austenite are present, and is controlled by volume diffusion of nitrogen through the

Jan 1, 1967

By S. R. B. Cooke, S. W. Clark

Adsorption of calcium and magnesium by quartz was determined over a wide pH range using flame photometry for solution analysis. A parallelism was noted between calcium adsorption at alkaline pH and flotation of activated quartz by means of various fatty acid collectors. Abstraction of calcium from 100 ppm solutions increased above pH 10.5 until all of the calcium was removed at pH values between 12 and 12.5. Calcium was desorbed from the quartz over the pH range 12.5 to 13.0 and returned to the solution. Precipitation of magnesium hydroxide prevented measurement of magnesium adsorption above a pH of 9.9. A calcium adsorption isotherm determined at pH 9 matched measurements of barium adsorption by other investigators over the range where adsorption corresponded to the equation of a Freundlich adsorption isotherm. In accordance with the Gouy-Chapman theory for adsorption in the diffuse layer, adsorption of the divalent cations under these conditions was four times the adsorption of monovalent sodium. Activation of quartz by multivalent metal cations in flotation using anionic collectors has been studied by many investigators. The occurrence of activator cations in the water of flotation mills makes depression of silaceous gangue very difficult. Alternatively, in some flotation systems it is practical to cause activation of quartz so that it is floated from the desirable mineral values. The present study was initiated to investigate the activation of quartz by measuring adsorption of calcium and magnesium ions as a function of solution pH. Early empirical tests showed that quartz would be activated to flotation using anionic collectors if any of a number of divalent or trivalent metallic cations were present in the pulp.1*2 Subsequent studies by Clemmer,3 Cooke and Digre,4 Cooke,5 Schuhmann and Prakash,6 and Cooke, Iwasaki, and Choi,7-8 showed that flotation depended strongly upon the alkalinity of the flotation pulp, the concentration of the activating cations, and the chain length and structure of the organic collectors used. The concept of the electrical double layer has been applied to the case of the quartz-aqueous solution interface by Gaudin and Fuerstenau,9-10 and by de Bruyn 11 to explain the activation of quartz by multivalent metal cations. Studies of the surface of quartz by Gaudin and Fuerstenau9,10,12 and by Li " using the streaming potential technique contributed much information on the electro kinetic condition of the surface of quartz in the presence of various organic and inorganic ions. Measurement of adsorption of ac-

Jan 1, 1969

By Ernest F. Burchard

The Pao deposits of iron ore are in the State of Bolivar, Venezuela, near Upata, about 30 miles south of the Orinoco River and 90 miles east of Ciudad Bolivar. They were discovered 4 or 5 years ago and have not yet been developed to the stage of mining. In March-April, 1929, the writer devoted a week to the examination of these deposits. The maps, drill records and chemical analyses presented herewith were derived from original sources, and the field photographs were made by the writer. The petrographic and metallographic data are from notes by C. S. Ross and M. N. Short, of the U. S. Geological Survey, who have kindly collaborated in these special phases of the study. The Iron Obebodies Topography and Accessibility The deposits are in a region of low mountains representing northern outliers of the Guayanan Highlands. These mountains reach altitudes of 1800 to more than 2000 ft. above sea level, as determined by aneroid barometer. The iron ore is found on mountain crests that reach altitudes of 1915 to 1930 ft., and may be followed down precipitous slopes for 200 • to 300 ft. or more. The greatest vertical range in outcrop is nearly 400 ft., and drilling has indicated that the ore extends to this depth below the surface in one place, at least. The superior hardness of the iron ore accounts for the preservation of the local mountain crests with the intermediate valleys eroded in softer granitic rock. The deposits of iron ore are reached by a private road for automobiles branching northeast from the Ciudad Bolivar-Upata road, a distance of about 12 miles. This road was used in 1928-29 by trucks for transportation of food and camp supplies, gasoline, drilling equipment, etc., but was not suitable for the transportation of iron ore. Between Ciudad Bolivar and the iron-ore area the western two-thirds of the automobile road passes through nearly level, open country known as the savanna, largely used for grazing cattle. About 96 km. (60 miles) east of Ciudad Bolivar at

Jan 1, 1931

By Albert F. J. Bordeaux

Alluvial gold was first discovered in Guiana in 1852, in the sands of the Arataye river, by Paulino, a Braziliaii convict. During the following years, gold was found also in the rivers Orapu, CirubQ, etc. In 1873 the famous placers of the Sinnamary system were opened: Saint-Elie, Dieu-Merci, Adieu-Vat, and Couriege. This group of mines has produced nearly $10,000,000, according to official records, not including the gold that escaped the taxes. The discoverer was a mulatto named Vitalo. Except in a few rich spots, the gold was rather evenly distributed along the creeks. In one instance, gold was found in the red dirt from the slope of a hill, which, after transport to the creek, gave an amount of 150 kilograms. The placers of the Mana system, Enfin, Elysee, Pas-Trop-Tot, date from 1878, and their production has been about %g5,000,000. In 1888, the Awa placers, along the boundary bet.ween the French and Dutch Guianas, on the Maroni and its tributaries, were discovered. They have yielded $12,000,000. The only industrial company, the Dutch Guiana Freiich Minillg Co., produced in 15 years about 2,500 kg. of gold, worth $1,500,000. From 1893 dates the famous Carsewene discovery, in territory then in dispute between France and Brazil. A settlement was made recently in favor of Brazil, by arbitration of the Switzerland State Council. Carsewene is said to have produced about $18,000,000 in six years (1894-1900), but not even one-fourth of tho production went through French Quiana and

Jan 1, 1911

By Wayne E. Glenn

The San Miguelito Field of Ventura County, California, lies along the coast approximately five miles northwest of the city of Ventura. The structure is one of several in the Ventura anticline, a series of anticlinal folds trending northwest-southeast through the San Miguelito Field. The Ventura Avenue Field lies to the southeast along the anticline, and Padre Canyon and Rin-con Fields lie to the northwest; the series then extends beneath the Pacific Ocean. Production is obtained from the Lower Pico and Repetto formations of Pliocene age, and oil accumulation is controlled by faulting, lithology and structure. The first well in the First Grubb Pool was completed in November, 1931, and to date 48 producing wells have been drilled on the 276 productive acres. Approximately 685 ft of net pay are contained in the eight sand bodies grossing 1,220 ft of section. Production of oil to date has been 15,-600,000 bbl. A gas injection project was instigated in April, 1940, but was discontinued in September, 1949. This paper is confined to a discussion of the development and performance history of the First Grubb Pool of the San Miguelito Field. LOCATION AND GEOLOGY The San Miguelito Oil Field is located in Ventura County about five miles northwest of the city of Ventura along the coastal highway to Santa Barbara. It is located within sections 23, 24, 25, and 30 of Township 3 North, Range 24 West, San Bernardino Base and Meridian. Surface elevation in the field ranges from sea level to plus 1,200 ft, and the terrain is extremely rugged. The structure is well defined on the surface and on the wall of the Amphitheatre Canyon where appears a so-called "text book" anticlinal section. The San Miguelito structure is an asymmetrical, elongated anticline about two miles long and three-fourths of a mile wide. The trend of the axis of the anticline is northwest-southeast. Fig. 9 illustrates the contours and major faults of this structure. Dips on the southwesterly flank average about 40 degrees, whereas the northeasterly flank ranges from 60 to 75 degrees. There are several faults striking generally east and west. These faults do not appear to affect materially the area of accumulation or performance behavior. It is believed that accumulation was affected by steeply dipping beds and extremely low permeability of the northeast flank of the structure. As shown by the typical log, Fig. 1. the San Miguelito Field is divided into two stratigraphic producing intervals. The First Grubb Pool comprises the interval from the "G" to "L" markers; the Second Grubb Pool from the "L" to "M" markers. The First Grubb Pool, ranging in thickness from 1,105 to 1,680 ft, with an average of 1,220 ft, includes approximately 685 ft of oil-bearing sands. The First Grubb zone consists of eight sand intervals separated by shales. The shale bodies separating the eight sand intervals within the First Grubb Pool are continuous throughout the major part of the structure and serve as an effective barrier. Many of the thin, irregular shale or siltstone streaks within these sand bodies are discontinuous and do not affect well performance appreciably. The productive horizons in the First Grubb Pool are siltstones and sandstones of the Lower Pico and Repetto formations of Pliocene age. It is apparent from inspection of the typical log that the "G" to "L" interval might have been separated into at least six producing zones and selectively pro. duced. Unfortunately the electric log and some of our modern tools were not available or were in their infancy dur. ing the period 1931 through 1937. Not until 1937 when eight wells had been completed were there sufficient geological data to permit definition of the sand bodies. Then the problem of reservoir control in this multiple-sand field, where all sands are open to a common

Jan 1, 1950

By Charles S. Barrett, Herman F. Kaiser, Robert F. Mehl

The copper-silver system presents several points of special interest in the study of segregate structures. The system is simple eutectic, with limited solid solutions terminal with the pure component metals. The extent of solid solubility decreases with decreasing temperature for both the copper-rich and the silver-rich alloys, thus offering a possibility for the formation of Widmanstätten figures and also a possibility for aging after quenching. In contrast to the structures studied previously the structures in this system are unique in their origin, for one terminal solid solution will precipitate the other, and vice versa. In most of the other systems for which crystallographic data on the precipitation (or transformation) process arc available, either intermetallic compounds or intermediate phases partake in the decomposition process; the absence of such phases thus distinguishes this system. The lattice structures of the two solid solutions are identical in type, differing in lattice spacing by approximately 10 per cent; because of this it seems difficult if not impossible to predict on the basis of present theory either the outward form of the precipitate or the lattice orientation relationships between matrix and precipitate. The eutectic temperature in the copper-silver system' is 779" C. At this temperature copper dissolves 4.3 atomic per cent (7.0 weight per cent) of silver in solid solution; this solid solubility decreases to zero at room temperature.² Silver at the eutectic temperature rctains 14.0

Jan 1, 1935

OF the many categories into which scientific knowledge has been arbitrarily 'divided, the one that has proved most. applicable in our attempts to gain an insight into the details of steelmaking processes is physical chemistry. To the young metallurgist who has only recently survived a college course in this subject, the application of its principles to reactions in liquid steel should not be difficult. The many excellent textbooks of physical chemistry provide ample material on the principles of this subject for the student of steelmaking processes. It is the purpose of this chapter to provide a concise review of the principles of physical chemistry that have proved useful in studies of steelmaking and at the same time to present some of the data that are essential to the application of physical chemistry to reactions at high temperatures. Certain parts of physical chemistry require rather formidable mathematics for their complete development, but in the main those applications in which we are here interested can be expressed in fairly simple terms. Many of the equations are logarithmic, and we shall use the symbols In X and log X to represent, respectively the natural and the common logarithm of X. The two are related-by In X = 2.303 log X. Logarithms may, be read from a good slide rule with sufficient accuracy for our purposes. In a few spots a knowledge of the calculus will be helpful. MATTER Innumerable forms of matter may, be recognized, and these may be converted by chemical processes into others, as ore, coke, and air are converted into iron, slag, and gas.. Whenever such a change occurs there is a corresponding change in the amount of energy associated with the matter. The process may require an input of energy, as in the electrolytic production of aluminum, or it may result in an output of energy, as in the combustion of fuel. The basic laws of the conservation of matter and of energy tell us that we cannot change the total amount of matter or the total amour t of energy.. When the fuel pile is used up, we realize that it has simply been converted into other forms of matter; .i.e., ash

Jan 1, 1964

By W. D. Keller

THE high-alumina clays of Missouri are interesting for several reasons. They are the only sedimentary deposits in North America of first grade (over 70 pct A1,0,) diaspore and boehmite sufficiently large to be mined commercially. Mineralogically, they are composed of diaspore and boehmite in intimate coexistence, but gibbsite, the common hydrated alumina mineral in bauxite and laterite, is absent, or is exceedingly scanty if present.* Therefore, the Missouri high-alumina clays do not represent typical laterization. The physical chemistry leading to their mineral genesis, and the geolbgical setting for their formation, present important problems for scientific study. The origin of the Missouri high-alumina clays has been discussed in earlier reports by Allen1 (1935) and McQueen 8, 9 (1929, 1943). These investigations were made under difficult conditions, however, because no diaspore deposit had been opened where a Paleozoic (Pennsylvanian) rock cover lay undisturbed over the high-alumina clay. The relationship of the clay to only the underlying rocks could actually be observed. Lacking the guidance of critical postdepositional geologic evidence, undue and erroneous emphasis was placed on the postdepositional leaching of the deposits in the theories on the origin of diaspore and boehmite from clay (hydrous aluminosilicates) . With new geologic evidence at hand, a clearer picture can be made for the origin of the Missouri high-alumina deposits. In this paper the geology of a diaspore deposit whose original Paleozoic cover had not been eroded will be described and interpreted genetically. The close relationship of boehmite and diaspore (also with kaolinite and a chloritic mineral), will be established. A theory of origin for the high-alumina clays, consistent with the new data, will be postulated.

Jan 1, 1952

By M. C. Miller, M. R. Tek, D. L. Katz

Previous studies have shown the influence of geometric variations on the drawdown and buildup behavior of a well completed in a homogeneous, porous medium containing a single-phase fluid. Other papers have shown the influence of leakage across caprocks on drawdown tests on water wells and aquifers. This paper presents two additional cases: the influence of an adjacent, expansible source of fluid, and the effect of caprock leakage on the measured in situ permeability and compressibility. Methods are developed for evaluating the influence of these two deviations from a uniform aquifer upon the in situ permeability and compre.ssibility indicated by pump tests. INTRODUCTION In relatively uniform porous media, saturated with a single-phase fluid, the effective reservoir permeability and compressibility of the water porous bed system may be obtained from drawdown and build-up data on wells, such as the initial wells drilled in aquifer storage reservoirs (Homers and Katz et al.7). In considering the drawdown and build-up behavior of wells adjacent to storage reservoirs, or of wells in an aquifer adjacent to an unknown gas field, questions arise as to the quantitative effect of the presence of compressible fluid on the measured permeability and compressibility of the formation. The solution to this problem is presented, using a constant pressure line source at some distance from two wells, one of which is pumped and the other used as the pressure observation well. The solution is presented in terms of the geometry of the wells and their relationship to the constant pressure line. It is known that caprock leakage can interfere with the determination of an aquifer in situ permeability and compressibility (Mantush4, Hantush and Jacob3 and Witherspoon and Muellerll). This paper presents an added case of the effect of leakage through a caprock of known thickness and permeability on well tests starting with a reservoir of constant pressure above the caprock and contributing to the aquifer as a result of the pump test. Again, both a pumping well and an observation well are postulated. These two cases are presented together since both a compressible fluid nearby and. caprock leakage show similar deviations from expected in situ permeability and compressibility results, and the solutions are similar in form. EFFECT OF A NEIGHBORING CONSTANT PRESSURE SOURCE ON IN SITU MEASUREMENTS Bixel, Larkin and van Poollenl presented a paper showing the influence of a discontinuity of the properties of a fluid formation system on drawdown and build-up performance. Their case is related to the present study but may be distinguished from it in that their numerical work and resulting graphs relate only to the performance of the pumping well itself. Incorrect values for in situ reservoir properties may be obtained from pump test data if the skin effect of the well and after-flow are not considered. Analysis of this problem by the authors indicated that the more reliable method of evaluating the influence of an adjacent gas field or expansible source was to use one well for pumping and another well at some distance from it for observing the aquifer pressure performance. An expansible source of hydrocarbon near a pumping well may be approximated by a line of constant pressure for a pump test. Fig. 1 illustrates a pumping well and an observation well near a line of constant pressure. Pressure behavior of an observation well during a drawdown pump test near a line of constant pressure is given by the diffusivity equation:

Jan 1, 1967

By C. A. Stout, S. W. Nicksic

The materials that stubilize emulsions of some Southern California crude oils were isolated from the produced crude. These substances were separated into acidic and nonionic fractions by ion exchange chromatography. Each fraction was further broken into groups of homogeneous molecular weight composition by gel permeation chromatography. Both ionic character and molecular weight of the individual fractions are reflected in the properties of the original crude oil emulsion. Specifically, the more acidic and the higher molecular weight fractions appear to be the most effective stabilizers. INTRODUCTION The treatment of oilfield emulsions is a continuing problem for the oil industry. In almost all cases, these are water-in-oil emulsions. Much more is known about the formation and stabilization of oil-in-water (O/W) emulsions than of the water-in-oil (W/O) type. To understand W/O emulsions, more information is needed on the materials responsible for their formation and stabilization. This is especially true in the case of oilfield emulsions where the stabilizing materials are complex mixtures of large asphaltene-like molecules. To study the chemical and physical properties of these emulsion stabilizers, it is necessary first to separate them from crude oil. This separation was achieved in the case of two Southern California crude oils. The materials that were isolated appear at first to be little different from an asphaltene mixture. However, if a mixture of distilled water and mineral oil containing about 1 percent of the natural emulsion stabilizers is passed through a colloid mill, the W/O emulsion formed may be stored in the laboratory for many months without any sign of breaking. This could not be done using undifferentiated asphaltenes from the same wells, indicating that there is a real difference between these materials and ordinary asphaltenes. The colloid mill used to generate the emulsion was required because tile natural emulsion stabilizers had very little effect on oil-water interfacial tension. The one characteristic — complexity of composition — that emulsion stabilizers share with asphaltenes makes virtually impossible the exact structure determination of the components of the mixture. For this reason, it was decided to investigate first the influence of molecular weight on the ability of these materials to stabilize emulsions. The emulsion stabilizers were first separated into acidic and neutral fractions according to whether or not the material was retained on a weakly basic ion exchange column. The extraction procedure was not designed to remove basic components from tile oils, and no attempt to isolate such a fraction was made. Following this separation, selected fractions were analyzed by gel permeation chromatography. Gel permeation separates according to molecular size, largely independently of chemical or polar characteristics. A heterogeneous mixture is separated into a number of fractions having much more homogeneous molecular weight distribution. A number average molecular weight of each fraction is therefore close to the true molecular weight of the principal component of that fraction. The fraction weights, expressed as weight percent of the sample, and the number average molecular weight of a representative selection of the fractions, will be referred to in this paper as the molecular weight profile of the original sample. DESCRIPTION OF GEL PERMEATION ANALYSIS The first reported gel permeation analyses were for separating partially hydrolyzed protein molecules in an aqueous system using expanded starch granules. Most of the theoretical work on gel permeation has been done by biochemists.1 This theoretical treatment is still incomplete, but the

Jan 1, 1969

By Scott Howard

MANGANESE being perhaps the least expensive of the metallic alloying elements that can be advantageously added to iron in considerable quantities, the basic characteristics of its alloys with iron are properly receiving much attention at present. In the course of a dilatometric investigation of this system several years ago, the writer observed certain transformation phenomena not found in other iron-base alloys. The interpretation of those effects was not evident from the information then available, but recent X-ray studies clear up at least one anomaly and permit a more satisfactory description of the results than would have been possible otherwise. Aside from the new phenomena observed, the effect of manganese on the Ar3 transformation is of timely interest because of its bearing on the critical compositions of austenitic alloys, the applications of which are now being greatly extended. It is known that the properties of these alloys are unstable unless the Ar3 transformation occurs at a temperature considerably below atmospheric and that manganese is very effective in depressing the temperature of this transformation. The writer aims to establish a simple general relation which expresses the location of Ar3 quantitatively in terms of the content of the common alloying elements used in steel. A step in that direction is taken here. Early dilatometric investigations1 indicated that only one transformation other than the eutectoid A1 occurs in the high-iron alloys of the iron-manganese system. Dejean represents the Ar3 point as falling to 0° C. with a manganese content of 11 per cent and carbon content of between 0.30 and 0.40 per cent. Esser and Oberhoffer,2 using alloys low in carbon (under 0.03 per cent), arrived by extrapolation at 14 percent for the manganese content at which Ar3 is depressed to 0° C. Not until both low carbon contents and alloys having a manganese content

Jan 1, 1931

By R. Kerby, T. R. lngraham

The rates of cadmiuln cementation from buffered solutions were studied on both the cylindrical and circular faces of a rotating zinc disk. The activation energies are equivalent on both surfaces, but the rate is more rapid on the cylindrical face. At higher temperatures and at pH values above 6.4, the rate of deposition increases because of an increase in the cathodic area of the deposit. The rate may also be increased by decreasing the thickness of the diffusion layer by rapid stirring. The presence of small amounts of copper, cadmium, lead, iron, or aluminum in the zinc does not affect the cementation rate, but when srnall amounts of copper, cobalt, and arsenic were present in the solution cadmium deposition ceased shortly after it started. Small amounts of copper in solution become cemented with the cadmium to form a coarse deposit of Cd3Cu. When zinc ores containing cadmium are processed for electrolysis, the cadmium appears with the zinc in the leach liquors. Because of the discharge potential of the cadmium ion and the hydrogen overvoltage on metallic cadmium, the cadmium ion must be removed prior to zinc electrolysis to prevent its codeposition. Cadmium is usually removed from acidic zinc sulfate solutions by cementation on zinc. When zinc sheets are used with the appropriate conditions of pH and temperature, a finely divided, high-purity cadmium powder is obtained; it floats to the surface with attached hydrogen bubbles and, after careful washing, may be processed directly to a marketable product.' The reaction on zinc sheets is relatively slow because of the limited amount of exposed cathodic area on the sheets. A much more rapid reaction is obtained when zinc powders are stirred into the solution, but this procedure does have a potential disadvantage: some unreacted zinc may be trapped in the cemented cadmium and thus lower its grade.1 The equilibrium constant at 25°C for the displacement of cadmium by zinc is of the order of lo", which indicates that at equilibrium the displacement would be essentially quantitative and no back reaction need be considered. This indication is not entirely true, however, because in the presence of oxygen any loose cadmium which is out of contact with metallic zinc tends to redissolve after cementation.' The overall effect is much the same as that to be expected if the equilibrium constant were much smaller. Previous experimental work on cementation reac- tions3 is in general agreement that the rates of cementation usually follow first-order kinetics. The metal on which cementation occurs is considered to consist of anodic areas from which metal dissolves and cathodic areas onto which the reactive metal is cemented. For the reaction to continue, the cemented deposit must remain open and porous for the removal of ions. Usually, the deposited metal influences the rate of cementation; when it blocks the pores in the deposit, the rate of cementation will be decreased. Alternatively, when the cemented metal grows as den-drites or as coarse powder the cathodic area is correspondingly increased and the rate of cementation increases,3 Thus, it is only during the initial stages of cementation, prior to the development of deposit effects, that the kinetic behavior of the reaction may be studied without ambiguity. In this paper, experiments will be described for cementation of cadmium from dilute solutions onto the surface of a rapidly spinning zinc cylinder. The effects of ionic concentration, disk rotation speed, temperature, and impurities will be described. APPARATUS AND PROCEDURE The apparatus used for the experiments was described in a previous paper.4 It consisted of a 2-liter vessel in which the contents were protected, against oxidation, by a stream of prepurified nitrogen. The vessel was immersed in a water bath which controlled

Jan 1, 1970

By Charles C. Fatino, Joel S. Hirschhorn

Loose compacts of strained and annealed stainless-steel powders were sintered at various temperatures and times to determine the effect of residual strains on the sintering behavior. The atomized powders were prepared by annealing, ball milling, and rean-nealing. The residual strains and domain size were determined by a Fourier analysis of X-ray diffvaction dala. The specimens were prepared by siwzultaneously sintering cylinders of both strained and unstrained powder. The evaluation of the sintered compacts included density measurements, metallographic examinations, and analyses of X- ray diffraction data. The results of these studies reveal a definite increase in sintered density and sintering rate for the strained powders. THE pressure compacting of metal powders causes deformation of the particles, mechanical interlocking, and increased contact area. After the deformation, severe residual strains remain in these particles. The subsequent contributions of these strains to the sintering process have been considered to be negligible, since the recovery and recrystallization temperatures usually occur prior to the temperature required for the sintering process. Sintering is con-sidered to be the process by which the powders are transformed into solid compacts at temperatures below their melting points. The sintering operation for stainless steel usually takes place in the range of 2050" to 2400°F (0.84 to 0.95 T,, where T, is the absolute melting point or liquidus temperature) while the temperature required for recovery is approximately 1800°F (0.75 T,). However, it has been shown for several metal powders that densification becomes significant in the range of 0.35 to 0.45 T,.' It is the purpose of this study to determine what effect residual strains have upon the sintering behavior of stainless-steel compacts. Loose compacts were selected for study in order to isolate the strain contributions and eliminate the variables inherent in sintering of pressure-formed compacts. Additional variables were minimized by using only one mesh size, one composition, one particle shape, and also by simultaneously sintering both types of powder. Very little work has been carried out previous to the present study to delineate the effect of strains on sintering behavior. Lenel et 01.2 observed that residual stresses in copper compacts caused shrinkage at comparatively low temperatures. Delisle3 loose-sintered ball-milled electrolytic iron and observed that bonding among particles began at a lower temperature as compared to the behavior of annealed powder. Increased densification of ball-milled oxide powders has also been noted.4'5 EXPERIMENTAL PROCEDURES Powder Preparation. The powder used for this study was a commercial-type 316L stainless steel made by the atomization process. A typical chemical analysis is: C- 0.025 pct Mo- 2.2 pct Cr-18.6 pct Ni-12.5 pct Fe—Balance The atomizing process is essentially the rapid freezing of liquid droplets. This nonequilibrium cooling causes coring to occur and two distinct phases are present within the solid particle, the austenitic phase and the ferritic phase. Due to the presence of this ferritic phase, the particles tended to fracture as well as become cold-worked during the subsequent ball-milling operation. (It was also found that this type of cooling produced a broadened and shifted

Jan 1, 1968

By Russell W. Dayton

THE metallurgical polarization microscope has been utilized in several researches in the last few years, thus attaining a fair degree of prominence, but little has been written in a manner suitable to a metallurgist concerning the theory of this instrument. In this investigation the theory was carefully studied, and the results are presented here in a detailed manner, yet as simply as possible. The theory - is discussed with particular reference to the three chief functions of the instrument: (1) determination of anisotropy; (2) effect of strain; and (3) identification of inclusions. Each of these is investigated experimentally, with especial attention to the mechanism of producing any effect. Where possible, the discussion is supplemented by photomicrographs. The instrument used had numerous defects as a polarization microscope; these and their remedies are discussed. In the microscopic study of transparent mineral sections (chalcography) the use of polarized light has aided tremendously in the identification of a mineral. The determination of strain in transparent substances (photoelasticity) by the use of polarized light has lately become a commercial process, used in testing finished glass articles. The success of the use of polarized light with opaque materials has not been so great. The magnitude of the effects obtained is much less than that of the corresponding effects with transparent materials, and the mechanical difficulties are much greater. Königsberger, (1)‡ in 1909, was the first to apply polarized light to the microscopic study of

Jan 1, 1935

By H. D. Williams, R. A. Scriven

The distribution of elevation angle of finite plane facets distributed symmetrically about a given axis is derived in terms of the angular distribution of lines which these facets produce in a plane section parallel to the axis. It is assumed that the facets are not markedly elongated in preferential directions. The theory is intended for application to the angular distribution in polycrystalline metals of slip planes and of particular grain boundaries on which certain phenomena such as cavitation can occuv. Illustrative examples are given in closed form and simple numerical techniques are de-ueloped for practical application. The results are applied to the distribution of cavitated boundaries in a copper specimen after fatigue at 400°C and it is found that voids form on the boundaries that exper~enced maximum shear stress. When investigating the distribution of elevation angle between a given axis and planes symmetrically distributed about this axis the angular distribution observed in a plane section parallel to the axis is not necessarily the same as the required distribution. Consequently a technique for processing the results obtained by sectioning methods is required. An example where such a technique would find application is in the problem of intercrystalline void formation during uniaxial tensile creep. Two theories have been proposed to explain this cavitation in terms of the normal and the shear components of stress, respectively. Hull and Rimmer (1959) postulate that the growth of intercrystalline voids is controlled by the rate of supply of vacancies from the grain boundary, the local vacancy concentration being proportional to the normal stress on the boundary. Gifkins (1956) considers that slip arising within a grain causes a ledge to be formed at the grain boundary which is subsequently opened up into a cavity by grain boundary sliding. It might be possible to differentiate between these mechanisms by determining the angular distribution of grain boundaries containing cavities since the former theory predicts a predominance of cavitated facets normal to the stress direction whereas the latter should favor an angle of 45 deg to this direction. In a similar manner an indication may be obtained of the type of mechanism responsible for intercrystalline cavitation during high-temperature fatigue. Davies and Wilshire (1962) have analyzed the slip-plane distribution in a nickel specimen but the problem was not treated in any detail nor was any account taken of the finite extent of the planes being sectioned. Hilliard (1962) has given a very general account of how anisotropy in the microstruciure can be related to measurements taken in one or more plane sections by expressing both the measured and the true angular distributions as expansions in spherical harmonics.* The present analysis is con-

Jan 1, 1965

By N. J. Grant, A. W. Mullendore, Y. Ishida

Creep tests were performed at 500°F on polished specimens of A1-3 pct Cu at stresses of 2000, 4000, and 6000 psi. The effects of the size and distnbution of the second phase were studied in connection with the mechanisms of deformation, especially grain boundary sliding. Although the amount of grain boundary sliding varied considerably for the different heat treatments, yestriction of grain boundary sliding is not due primarily to precipitate on the grain boundary. NUMEROUS prior investigations of grain boundary sliding, notably those of McLean, 1 Rachinger, 2 Rhines, Bond, and Kissel, 3 and Brunner and Grant,4 have established the importance of this phenomenon in the deformation of pure aluminum and its solid-solution alloys at elevated temperatures. An extension of this kind of study to the case of a simple two-phase structure is an important step towards understanding the deformation behavior of more complex alloys. A two-phase A1-3 pct Cu alloy was selected for this study. The creep behavior of alloys in this system has been studied by Sully and Hardy,5 by Underwood, Marsh, and Manning,' and by Pelloux, Chaudhuri, and Grant.7 In these studies, the prior heat treatments were such that some precipitation took place during the tests in most cases. Pelloux, Chaudhuri, and Grant7 studied the creep of A1-2 and 3 pct Cu alloys in the overaged condition. Their results indicated that the structure most effective in promoting high-temperature strength consisted of a fine, closely spaced grain precipitate and large, widely spaced particles on the grain boundary. The present work consists of quantitative meas- urements of grain boundary sliding during creep of an A1-3 pct CU alloy with four different precipitate distributions. The aims were to quantitatively define the role of the second phase on grain boundary sliding, and to obtain information regarding the mechanism of grain boundary sliding. MATERIALS AND PROCEDURE A high-purity A1-3 pct Cu alloy, kindly supplied by Alcoa, was used in this investigation. The composition of the alloy in weight percent was as shown in Table I. This composition is such that A12Cu exists as a second phase at temperatures below 850°F. A homogeneous grain size of 0.6 to 0.8 mm was obtained by annealing the machined test bars for 5 min at 1000°F, furnace cooling to 930°F, and homogenizing for 5 hr. Following the recrystalli-zation and homogenizing anneal, four different heat treatments shown in Fig. 1 were utilized. The F7 and F5 treatments utilize a furnace cool to the aging temperature while Q7 and Q5 have a water quench from the homogenization temperature before aging. Figs. 2 to 5, and Table 11, show the size and shape of precipitate dispersions obtained with the above heat treatments. The heat treatments produce variations in the dispersion both in the grains and along the grain boundaries. Precipitate particles along the grain boundaries are rounded and large (about 1.5 p diameter) in the F5 and F7 structures (Figs. 3 and 5). The grain boundary precipitate was somewhat smaller (0.9 p diameter) in the Q7 structure and no grain boundary precipitate was detected in the Q5 structure using light microscopy. The pre-

Jan 1, 1964

By G. Krauss, J. M. Thompson, H. Y. Kumagai

Boron-doped p-type and arsenic-doped n-type source materials were used to deposit thin silicon films on amorphous fused quartz substrates by cathodic sputtering in argon atmospheres. All as-sputtered films were found to have high electrical resistivities of about 104 ohm-cm, despite controlled variation of the substrate temperature from 50O to 400°C. The high resistivity of the n-type films persisted even after postdeposition heat treatments as high as 1000°C, while p-type films showed a sharp decrease in re-sistivity to values on the order of 1 ohm-cm or lower after heat treatments above 650°C. X-ray and electron diffraction, together with transmission electron microscopy of the p-type films, revealed that the improved electrical properties resulted from two distinct processes. A primary crystallization or recovery within the pains, which were approximately 200Å diam in the as-sputtered films, accompanied the initial sharp drop in resistivity at 650°C. Following this process, a secondary recrystallization or discontinuous grain growth was nucleated in films heated at 1000°C. The resulting significantly increased size of certain grains and the corresponding decrease in grain boundary area accompanied an additional decrease in resistivity after heat treatment at 1000°C. The properties of thin silicon films are of interest because of their possible application in device technology. Although evaporated silicon films on amorphous substrates1-3 and both sputtered and evaporated germanium films4-' have been studied in some detail, sputtered silicon films have not been widely investigated. It has been observed that evaporated silicon films deposited at substrate temperatures below approximately 600°C are amorphous.1,3,9,10 At substrate temperatures higher than this, the films are polycrys-talline, sometimes exhibiting a fiber texture with the fiber axis normal to the substrate surface.' Similar results have been obtained with germanium films, although in this case the substrate temperature for the amorphous to crystalline transformation is reported to be as low as 150OC.5 The mechanism of film deposition by cathodic sputtering differs markedly from that of thermal evaporation. It might be expected, therefore, that the properties of sputtered and evaporated silicon films would also differ. The purpose of our study was to determine the effects of deposition conditions and heat treatments on the electrical resistivity, structure, and composition of thin silicon films sputtered on fused quartz substrates. EXPERIMENTAL DETAILS Apparatus. A schematic diagram of the sputtering apparatus is shown in Fig. 1. The vacuum chamber was enclosed by an 18-in.-diam by 12-in.-high Pyrex bell jar mounted on a stainless-steel base plate. Access holes in the base plate were used to supply argon gas to the chamber, to allow for various electrical feedthroughs, and to provide mechanical motion to the shutter between the source material and substrate. The chamber was evacuated by a pumping system consisting of a 720 liter per sec oil diffusion pump backed by a 13 cu ft per min mechanical pump. Ultimate pressures of less than 1 x 10-6 torr could be achieved. The substrates were securely mounted on the stainless-steel substrate holder by quartz tabs held in place by stainless-steel screws. Temperatures of the substrate holder were measured by a thermocouple inserted within the holder. A quartz lamp was used to heat the holder and temperatures as high as 420°C could be maintained. Deposition Conditions and Procedure. The substrates used were polished fused quartz slides 116 by 1-12 by 3 in. and were outgassed at 200°C for 1 hr at a pressure less than 1 x 10-5 torr before film deposition. This was followed by a presputtering period of 2 hr during which the movable stainless-steel shutter was so positioned that deposition on the substrate was prevented. At a sputtering voltage of 5000 v dc and an argon pressure of 0.03 torr, the cathode cur-

Jan 1, 1967

By W. A. Alexander, L. M. Pidgeon

Metallic magnesium and similar meta!s near the top of the electromotive series have been commercially produced by the electrolysis of a suitable molten salt. Despite the success of electrolysis, sufficient inherent objections exist to justify the search for a direct reduction method. Such a method would widen the choice of raw materials, relax the rigid electrolytic requirements of raw-material purity, and, by obviating direct current, over simplicity of plant equipment. This paper describes the pilot-plant development of one such method, which has subsequently formed the basis of operation of six commercial plants-—one in Canada and five in the United States. Unlike aluminum, magnesium is volatile at relatively low temperatures. This physical property, which produces its greater inflammability, also offers possibilities of direct reduction that are not available with aluminum. In the basic reaction MgO + X = XO + Mg if X is nonvolatile, the reaction may be forced to the right at high temperatures by the evolution of magnesium vapor, despite the large negative value of the heat of reaction which is almost bound to follow the use of any available commercial reducing agent. The cheapest X, of course, is carbon, but this notable advantage is modified by the production of a volatile oxide CO, so that both Mg and CO are evolved simultaneously. Elaborate devices are required to shock-cool the equilibrium mixture in order to prevent back reaction. At best, a pyrophoric powder is produced, requiring redistillation to provide marketable metal. The practical development of this process, is due to F. Hansgirg, and his methods have recently been given a trial on a grand scale in the plant at Permanente, California, and smaller plants were previously built in Austria, England and Japan. A second class of reducing agents is available, those which produce nonvolatile oxides. When XO and X are relatively nonvolatile, magnesium is the only volatile member of the system. It may be evolved in a simple distillation step and condensed without the formation of powder. Two basic requirements must bc fulfilled in order that such a reaction may proceed: I. The reducing agent when heated to a reasonable temperature in presence of MgO must cause the production of an appreciable equilibrium vapor pressure of magnesium. This magnesium must be removed continuously. z. A supply of heat must be maintained. In order to fulfill the first requirement, operations must be conducted in vacuo or in a stream of Hz. Owing to its greater efficacy and relative safety, vacuum has been employed in the work to be described. The choice of a suitable reducing agent formed the subject of an extensive series

Jan 1, 1944

By B. A. Rogers

THE etching effect which is produced on a piece of polished iron or steel when it is heated in hydrogen or in a vacuum seems to have been observed first by Osmond,1 who believed that he could distinguish four systems of grain boundaries on a piece of steel which had been heated in hydrogen. In a number of other investigations, samples of pure iron were found, after heating, to have complex networks in which two or three systems of grain boundaries could be detected. It was further noticed that samples that had been polished plane before being placed in the furnace were, after treatment, roughened and undulating over their entire surfaces. From a comparison of the temperature of heat treatment with that of the A 3 transformation, it was concluded that the changed appearance of the samples was definitely related to the latter phenomenon. Certain other deductions were made but these are not of importance here and only observations on the appearance of the samples will be reviewed. Ewen2 heated a strip of polished iron in a vacuum in such a way that one end was maintained at a temperature of 1000° C. and the other at 580° C. On the cooler end there was outlined a simple polyhedral network, and at the hotter there appeared the complex system of lines and the undulating surface characteristic of iron which has passed through the A3 transformation. He found that in going from the cooler toward the hotter end the sample maintained much the same character of surface up to the beginning of the transformed area, but that near this region double grain boundaries were of frequent occurrence. Rawdon and Scott' concluded that the simple type of network brought out by heating a sample of pure iron in a vacuum was of the same type as that developed by ordinary etching methods. They also confirmed the observations of

Jan 1, 1929