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By S. E. Maddigan

MANY experimental and theoretical investigations have been made on the processes involved in annealing and recrystallization of metals. Most of these, however, have treated the time element as constant and heat-treatments used have been for relatively short times. Aside from the early work by Carpenter and Elam,1 the few that have investigated the effect of time on the processes have usually done so for fairly short time periods. During recent years the growing interest in long-time creep properties of metals and alloys under stress has made increasingly important a better knowledge of the recrystallization during prolonged heating. The recrystallization temperature of 70-30 brass given by Clark and White2 in 1932 was somewhat above 400°F. (204°C.) but under 500° (260°C.), whereas in our laboratory recrystallization has been observed in creep specimens at 204°C, the lowest temperature of Clark and White's range. Since the creep properties are quite different above and below the recrystallization temperature, erroneous conclusions can readily be drawn by the application of short-time recrystallization data to creep problems. It was thus considered of both practical and theoretical value to make long-time annealing studies near the minimum recrystallization temperature. In this way useful additions could be made to data on recrystallization temperatures and, since the reactions in this range are relatively slow, additional insight could be obtained into the factors involved in annealing. Several comprehensive reviews of recrystallization processes have been written,3-5 therefore only a brief review of the generally accepted facts will be given here.

Jan 1, 1940

By C. J. Bier, J. F. O?Keefe

THIS study was carried out with copper because it represents the simplest form of sintering, in that but one metal is involved and all reactions occur in the solid state. [ ] The present work will cover three variables affecting the sintering process; namely, briquetting pressure, sintering temperature and time in hot zone. Although strength and dimensional changes were observed, this is primarily a metallographic study of the sintering process in copper. The term "sintering" should be understood to mean the process by which the metal powder particles of the compact become united into one body. MATERIAL USED The copper powder used was made from reduced copper oxide, and is typical of a grade used for the mass production of parts formed of metal powders. The screen analysis of the powder was as follows: [ ] The minus 325-mesh analysis was made by using a Roller Air Analyzer.1,2 The apparent density is here defined as the weight per cubic centimeter of the [ ] loose, unpacked powder as measured with the Hall flowmeter. The value for the powder used was 2.57 grams per cubic centimeter.

Jan 1, 1944

Jan 1, 1953

By Reinhardt Thiessen

During the last few years a type of coal called "splint coal" has been brought to the attention of the United States Bureau of Mines, through numerous inquiries concerning its nature. Until recent years it appears to have escaped general notice. The term "splint coal" is of long standing, but was thought to be merely another expression applied by the miner to coal having certain minor characteristics. When closely examined, however, these coals were found to form a marked and distinct type, with distinctive characteristics that cannot be mistaken. Because splint coals produce a hot cheerful flame, possess a clean blocklike nature, and have a high volatile content, they have lately become much valued for domestic, gas-producer and steaming purposes, and have attracted considerable attention. Mattkohle For many years we have heard from the Germans about Mattkohle and Streifenkohle, in contradistinction to Glanzkohle, but have not realized that they were of a different type from the coals with which we were most familiar. This type of coal was first brought to general notice by Muck, in 1881, who gave a good description of it.' Because this coal is often intercalated with thin sheets of brightly shining cod, Schondorff, who was more familiar with the Saar coals, called it Streifernkohle. This term was later used by Muck also. Still later Potoné² used this term exclusively for the whole group in contradistinction to a class called Glanzkohle, and considered these coals to be composed alternately of Humuskohle and Faulkohle or Mattkohle (Pig. 20). Not knowing the nature of the German coals and not realizing that the term Streifenkohle was applied to a distinct class of coal, the terms of its components as used by Potonié and others were translated to "bright Coal" and "dull coal" and applied to the components of our

Jan 1, 1930

By V. N. Krivobok

THE study and use of low-carbon manganese steels have been curiously neglected in the general history of developments in alloy steels. Hadfield1 made an extensive study of manganese-iron-carbon alloys about 1886, which culminated in the wide application and use of Hadfield austenitic manganese steel. His alloys were nearly all high in carbon, as compared with the steels discussed in this paper, and he found a marked tendency towards brittleness in the alloys of medium and low manganese content, that is, below 7 per cent. manganese. As a result, there has been a widespread prejudice against the use of manganese steels containing between 1.0 to 3.5 per cent. manganese with comparatively low carbon. Steels of this composition have never been studied adequately in comparison with other alloy steels, and have had little use in practice. In a very recent paper by Sir Robert Hadfield2 the following statement appears: ?. . . manganese-iron alloys with little or no carbon do not seem to offer any practical employment; they only become valuable in the presence of quite high percentages of carbon, 0.90 to 1.50 per cent." The results of the present investigation are so contrary to the findings of Hadfield that the writers feel fully justified in presenting the preliminary report incorporated in this paper.

Jan 1, 1927

By D. L. Martin, E. R. Parker

IN a previous paper, one of the authors observed that the rate of cooling from the anneal prior to testing greatly influenced the life of copper under sustained load at 200°C. Furnace-cooled bars of oxygen-free copper (with, and without silver) had a life four to twenty-five times that of the water-quenched specimens. The addition of 0.054 per cent silver to the oxygen-free copper increased the life at a stress of 20,000 lb. per sq. in. from about 2 hr. to 50 hr. Fractures in these bars were intercrystalline. An explanation was advanced to account for the profound influence of cooling rate on the rupture properties at 200°C. The suggestion offered was that at the high annealing temperature the minor constituents are distributed at random. By water quenching, this condition is maintained at room temperature, whereas furnace cooling permits some segregation at the grain boundaries. The higher concentration of the minor constituents in the grain boundaries results in a strengthening, so that a longer life at a given stress and temperature results. Small amounts of cadmium or manganese have also been found to increase the life of copper at 200°C., and to a much greater extent than silver .2 The increase in the long-time strength of copper resulting from small additions of cadmium or silver appears to be related, indirectly at least, to the higher softening temperatures of such alloys. The elements, such as silver or cadmium, which greatly increase the rupture life of copper also cause large increases in the softening temperature. As little as 0.05 per cent of cadmium or silver is sufficient to raise the softening temperature more than 100°.3,4 The effects of cooling rate and of minor constituents on the rupture properties are of considerable fundamental as well as practical interest; therefore a more detailed study of their nature was conducted and is reported in this paper. EXPERIMENTAL PROCEDURE Materials The materials studied in this investigation may conveniently be classified in two groups: one consisting of a wide variety of commercial coppers, and the other composed of special high-purity, laboratory-prepared coppers. The commercial materials were tested to determine whether or not the effect of cooling rate occurred with all coppers, whereas the high-purity coppers were investigated in order to establish a basis for evaluating the effect of minor constituents on the rupture properties. In Table I are given the analyses of the coppers tested. The samples I to 6 are commercial materials and were obtained for the most part from stock supplies.*

Jan 1, 1943

By G. A. Parks, C. Kovacs

The xanthate flotation of chrysocolla can be improved by preheating the ore to 500° to 600°C. Addition of water vapor reduces the preheating temperature required. The temperature range of flotation improvement correlates well with the range over which dehydroxylation occurs. This observation is consistent with changes in the structure and properties of the mineral as detected by measurement of solubility, D.T.A., T.G.A., X-ray diffraction, and infrared absorption and with recently proposed explanations of chrysocolla flotation. A brief experiment by one of the authors several years ago showed that exposure of chrysocolla to high temperature water vapor resulted in increased recovery by subsequent xanthate flotation. Recently renewed interest in flotation and thermal properties of chrysocolla1-5 prompted further study of this effect and more detailed reporting.6 This paper explores the response of pure chrysocolla recovery in Hallimond tube flotation tests to the time and temperature of exposure and to changes in the water vapor pressure. Brief attention is paid to the effects of such treatment on accessory minerals. A single experiment with flotation of chrysocolla from an ore is reported. MATERIALS Chysocolla from Inspiration, Gila County, Ariz. was crushed in a porcelain mortar, cleaned of visible and magnetic impurities, and screened to obtain -48 +65 mesh (Tyler) material for flotation test work. The clean material contained 28.5% Cu and was identified as chrysocolla by comparison of X-ray diffraction, D.T.A., and infrared absorption data with that reported for similar materials by others.4,5,7 Samples of malachite and chalcopyrite, prepared in a similar way, were also identified by X-ray diffraction. The sources of these materials are unknown. A sample of chysocolla-bearing oxidized copper ore from Pima, Ariz. was crushed and dry ground for thermal activation and subsequent flotation. PROCEDURES Activation: The apparatus used for exposure of materials to high temperature water vapor is illustrated in Fig. 1. The furnace temperature was controlled to ±5°C Water vapor pressure was controlled by pre-saturating a nitrogen carrier stream with water in an adjustable thermostatted saturator (multiple bubbler). A water manometer and capillary orifice flow meter were used to measure nitrogen flow rates for activation and for subsequent Hallimond tube tests. Gas flow rate and temperature were adjusted prior to introduction of samples. Exposure time was measured from the moment of introduction of the sample to the furnace, hence includes an initial drop below the control temperature. After heating, the samples were removed from the furnace and stored at room temperature in air. Representative samples of activated materials were examined by X-ray diffraction and infrared absorption.

Jan 1, 1967

By F. Keller, A. H. Geisler

ALTHOUGH the subject of precipitation from solid solution appears to be one of the more profitable fields in metallurgy for study with the electron microscope, few comprehensive studies have yet been made. Occasionally electron micrographs have been published that illustrated alleged precipitation in various alloys, but frequently the apparent size, shape and distribution of the particles do not fully agree with those expected from theory or from observations of the precipitate when the particles have grown to a size resolvable with the light microscope. The presence of a Widmanstätten pattern for submicroscopic precipitate particles has been demonstrated for only a few aged alloys.1 The initial problem has been the development of suitable techniques for applying the transmission-type instrument to a field that has been inherently associated with reflection-type microscopes. The various techniques have been the subjects of numerous publications, and instead of describing them individually here it will suffice to say that the oxide film method has proved to be the most satisfactory method yet found for studying the microstructure of aluminum alloys with the electron microscope. This method has the definite characteristic advantage that the actual surface layer of the specimen is examined and not a plastic or silica replica. Doubtless suitable methods for forming and removing the oxide film could be developed for alloys of other metals. The purpose of this report is to point out the characteristics of the oxide film method that have been observed during the studies of numerous aged aluminum alloys and to present the results of these studies. PREPARATION OF SPECIMENS The oxide film method for preparing specimens of aluminum alloys for examination in the electron microscope has been described in detail previously.1,2 Briefly, the procedure consists of preparing the metallographic specimen, forming the film by anodic oxidation and removing the film from the prepared surface of the oxidized specimen. The specimen is polished according to the usual procedure for microscopic examination.3 The specimen may then be etched to remove flowed metal but etching to attack the alloy constituents or to leave them in relief as in the replica processes is not necessary. Electrolytic polishing is not generally recommended. Deep-etched specimens are used frequently, however, since they provide information that is not revealed by polished specimens and frequently present the same information more clearly than do the polished specimens. The surface preparation of specimens to be deep-etched is not important, since specimens that have been subjected to the first wet polishing operation are generally used, but frequently the as-rolled surface is suitable. These specimens are then etched using a suitable macroetching reagent.

Jan 1, 1946

By C. G. Fink, E. P. Polushkin

A PART of the material incorporated in this paper was derived from the studies of ancient metal objects examined by the authors from time to time for museums and art collectors, in order to verify the age of the metal. The data thus accumulated during several years were systematically surveyed and supplemented by new material obtained in examination of a set of specimens that had been generously donated by museums for this study. Altogether over 50 pieces were investigated, of which 39 are described in this paper. Every specimen is at least 1500 years old; the majority are considerably older. Exact conditions to which these bronze and copper objects were exposed in the ground are unknown, unfortunately. It is safe to say that exposure conditions did not remain constant during the long period of burial. Although the collection of specimens studied represents a wide variation in location and age of the objects, as well as in the nature and composition of the metals, it was found that fundamental changes in the metal structure were limited to a few typical cases which, therefore, may be considered as more or less general. The authors' chief aim was to study the effect of extremely long periods of corrosion on the structure of bronze and copper. Specimens Studied As the majority of specimens were very small and sometimes had a heavy coat of patina, or crust, which further reduced the amount of metal available for analysis, quantitative chemical analyses were not made. Small detached specimens were not always obtainable and studies had to be made on the statue, or other object, itself. In the description of specimens (Table I), their approximate compositions determined under the microscopc are given. The proportion of tin in bronze containing eutectoid was found by visual estimation of the area occupied by the eutectoid. It was based on the assumption that maximum solubility of tin in copper on moderately slow cooling is 7 to 8 per cent in thin castings and 9 to 10 per cent in heavy castings. When the metal was all

Jan 1, 1936

By D. R. Packard, J. D. Verhoeven

The resistivity us atom fraction relationships for dilute solutions of cadmium, mercury, and tin in molten sodium have been determined. With these data and the resistivity capillary-reservoir technique, the electro-transport mobilities, effective valences, and the diflusion coefficients of the three solutes have been determined. The mobilities are found to be higher than in other molten alloys by a factor of around 20. The results are compared to the Mmgelsdorf model for electrotrmtsport. The high values found for the mobility to diffusion coefficient ratio indicate that small quantities of the alkali metals should be susceptible to purification from many solutes by means of electrotransport. PASSAGE of a direct electric current through a liquid metal containing a solute will usually cause a relative motion between the solute and solvent atoms of the alloy. This electrotransport phenomenon may be described experimentally in terms of the mobility of the solute atoms, i.e., the drift velocity of the solute relative to the solvent per unit electric field. In dilute solutions of liquid alloys this relative mobility becomes a measure of the velocity of the solute with respect to the observer since the motion of the solvent is negligible. The mobility is a significant parameter in evaluating the potential usefulness of electrotransport for such things as purification or solute control upon solidification. Prior to around 1958, quantitative data for the mobility of solutes in liquid metals were restricted to some solutes in liquid mercury. Since that time ad- ditional data have been reported for the mobility of solutes in liquid mercury, bismuth, tin, and lead, as shown in Table I. In 1963 Drakin et al.11 reported some values of a transport number for mercury and thallium in molten sodium and potassium. When these values were converted to mobilities, it was found that the mobilities were higher than any of the previously reported values by a factor of around 20, as shown in Table I. Drakin's experimental technique did not eliminate the presence of back-diffusion and consequently his data were expected to be lower than the true values. The purpose of the present investigation was to determine the mobility of a number of solutes in molten sodium with an experimental technique which eliminates back-diffusion errors. EXPERIMENTAL The technique used to determine the mobility was a resistivity capillary-reservoir technique which had previously been used with a high degree of precision on Sn-Bi alloys.4 This technique consists of dipping the vertical Pyrex capillary cell shown in Fig. 1 into a molten bath of alloy while the bath and capillary are under vacuum. The capillary is then filled by intro-

Jan 1, 1969

By E. F. Raffo

THE design of the Chuquicamata concentrator offered an unusual combination of problems, all of which had, in one way or another, a definite effect upon the final arrangement of all the equipment and necessary facilities. First of all, a remotely located project of this magnitude required careful selection of equipment with an adequate supply of replacement parts and in some cases necessitated stand-by spare equipment ready for immediate use. Fortunately, in the course of determining the proper flowsheet, in itself a prime factor in the concentrator design, it was possible to conduct numerous grinding and flotation tests at the Anaconda and Andes concentrators. As a result of these tests made under actual operating conditions, most of the major equipment best suited for treating the Chuquicamata ore efficiently was decided upon while preliminary design layouts were still being made. The design has been based primarily on the treatment of sulphide ore crushed to about 3/4 or 1 in. However, until the new sulphide crushing plant is completed it will be necessary to handle ore crushed to 3/8 in. in the existing oxide crushing plants and to some extent a mixed ore which has had its oxide copper content removed by leaching. This mixed ore, known as leached residue, will contain a certain amount of sulphuric acid from the leaching process which necessarily requires special protective measures. Several factors influenced the final location of the Concentrator. The only established fact known during preliminary design layout was the elevation of the dumping floor over the fine ore bin. This was predetermined by the desired level railroad grade across part of the existing tailing and leached residue dumps from the oxide plant to the bin. Next it was necessary that a site be chosen that would not require an excessively long haul from either the present oxide plant or the mine and in addition provide a fairly constant natural ground slope sufficiently wide to accommodate the length of the ultimate concentrator. The site as finally chosen to meet the foregoing restrictions provided a natural ground slope of 6 to 7 pct. This was excellent, especially in a region subject to earthquakes, as it assured that foundations of heavy equipment and footings for building and crane columns would rest on cut or undisturbed ground. However, this shallow slope, although having some definite advantages in the overall consideration of plant layout, resulted in the need for extensive studies in the general arrangement of equipment. Wasteful and excessive vertical drops had to be eliminated in the

Jan 1, 1952

By Michael B. Bever, Carl F. Floe

he possibility that carbon may be soluble in copper to a limited extent has bten recognized for over a century. The quantitative investigation of this problem, however, requires more sensitive techniques than have formerly been available. Three recent developments have made possible more accurate determinations: the vacuum-fusion method of analysis, the production of copper of high purity and the availability of high-purity refractories, particularly graphite. In addition to its obvious theoretical interest, the problem of carbon solubility in copper is of practical importance. In the production of copper and of high-copper alloys, carbonaceous covers are freauerltlv used. If even minute amounts of carbon are dissolved, insoluble carbon oxide gases will be formed when such metals are poured under oxidizing conditions. A mechanism of this kind could well be one of the principal causes of gas porosity in casting copper-base products. Review of Literature In 1823 Vivian1 raised the question as to whether copper by overpoling becomes "combined with a minute portion of carbon." Karsten2 asserted, in 1832, that carbon reduces the high-temperature strength of pure copper, so that when the carbon content has reached 0.2 per cent the metal will be brittle at a dark red heat. According to Karsten, carbon contents of 0.05 per cent make it difficult to hot-work copper. He also reported that the specific gravity of copper is 8.8969 and that it increases to 8.9258 if the copper is cemented with carbon and then melted. He emphasized the difficulty of determining analytically the small amounts of carbon present in copper. The metal was removed by wet methods and the residue considered as carbon. At Percy's request, Dick,3 in 1856, carried out various working tests on copper that had been ill prolonged contact with carbon, and found that the working properties of the metal had not been affected. He also attempted to determine the presence of carbon analytically. In one experiment the copper was dissolved and the residue was fused with litharge, and in another essentially a combustion analysis was made on a copper sample. In a final experiment, a sample was dissolved and the residue subsequently subjected to a combustion analysis. Indications of as much as 0.005 per cent carbon were found, but Dick considered his work inconclusive largely because of the possible interference of sulphur. Percy4 concluded, from Dick's experiments and from some experimental work of his own, that the solubility of carbon in copper had not been established with

Jan 1, 1946

By Carl F. Floe, Michael B. Bever

he possibility that carbon may be soluble in copper to a limited extent has bten recognized for over a century. The quantitative investigation of this problem, however, requires more sensitive techniques than have formerly been available. Three recent developments have made possible more accurate determinations: the vacuum-fusion method of analysis, the production of copper of high purity and the availability of high-purity refractories, particularly graphite. In addition to its obvious theoretical interest, the problem of carbon solubility in copper is of practical importance. In the production of copper and of high-copper alloys, carbonaceous covers are freauerltlv used. If even minute amounts of carbon are dissolved, insoluble carbon oxide gases will be formed when such metals are poured under oxidizing conditions. A mechanism of this kind could well be one of the principal causes of gas porosity in casting copper-base products. Review of Literature In 1823 Vivian1 raised the question as to whether copper by overpoling becomes "combined with a minute portion of carbon." Karsten2 asserted, in 1832, that carbon reduces the high-temperature strength of pure copper, so that when the carbon content has reached 0.2 per cent the metal will be brittle at a dark red heat. According to Karsten, carbon contents of 0.05 per cent make it difficult to hot-work copper. He also reported that the specific gravity of copper is 8.8969 and that it increases to 8.9258 if the copper is cemented with carbon and then melted. He emphasized the difficulty of determining analytically the small amounts of carbon present in copper. The metal was removed by wet methods and the residue considered as carbon. At Percy's request, Dick,3 in 1856, carried out various working tests on copper that had been ill prolonged contact with carbon, and found that the working properties of the metal had not been affected. He also attempted to determine the presence of carbon analytically. In one experiment the copper was dissolved and the residue was fused with litharge, and in another essentially a combustion analysis was made on a copper sample. In a final experiment, a sample was dissolved and the residue subsequently subjected to a combustion analysis. Indications of as much as 0.005 per cent carbon were found, but Dick considered his work inconclusive largely because of the possible interference of sulphur. Percy4 concluded, from Dick's experiments and from some experimental work of his own, that the solubility of carbon in copper had not been established with

Jan 1, 1946

By Norman Brown, J. V. Rinnovatore

Substructures in explosively deformed and annealed ß brass have been examined by electron microscopy. In the explosively deformed condition, the structure contains a large density of straight screw type dislocations. Subsequent annealing up to 300oC produces low angle boundaries, which are characterized by superlattice dislocations, and expanded and contracted nodes. Evidence is given where two a(111) superlattice dislocations combine to form two a(001) superlattice dislocations. It is also shown that annealing at 400°C the networks disappear and that quenching from 400" C produces square and circular prismatic dislocation loops that lie on (100) and (111) planes, respectively. THE purpose of this work was to determine the effects of explosive deformation and subsequent annealing in a superlattice using electron microscopy. One of the first observations of explosively deformed structures was made by Hornbogen1 on a iron. Hornbogen found that screw dislocations were most prominent in the explosively deformed structure. He explained this result by suggesting that the edge components of dislocation loops move with the velocity of the shock front leaving a trail of extended screw components. Kressel and Brown2 observed explosively deformed Fe3A1, which is basically a body-centered type of superlattice in terms of dislocation geometry, and found that, as in the case of iron, screw dislocations were most prominent. It was also observed2 that, in cold-rolled and explosively deformed nickel, screw dislocations did not predominate, but rather a uniform network of dislocations was present in which the orientation of the dislocations was random. (Cell structures also have been observed by Nolder and Thomas3 for copper and by Johari and Thomas* for nickel). Kressel and Brown2 discussed the difference between dislocation morphology for bee and fee metals in terms of dislocation mobilities. They suggested that edge dislocations have a greater mobility than screw dislocations in bee metals but not in fee metals. Thus, the idea offered originally by Hornbogen1 is not valid since it should apply equally to fee and bee systems but does not. The results of recent work by Mikkola and cohens on explosively deformed Cu2Au are consistent with other observations for fee metals. They found that dislocations were randomly arranged but there was no significant cell formation. At high shock pressures, deformation twins are produced in fee metals.' High pressures in bee metal should induce the bee — fee transformation while the metal is under pressure. EXPERIMENTAL PROCEDURE The Cu-Zn alloy used in this work contained 51.4 wt pct Cu. Specimens of 0.5 in. diam and 0.012 in.

Jan 1, 1968

By Carl F. Floe, Michael B. Bever

THE possibility that carbon may be soluble in copper to a limited extent has been recognized for over a century. The quantitative investigation of this problem, however, requires more sensitive techniques than have formerly been available. Three recent developments have made possible more accurate determinations: the vacuum-fusion method of analysis, the production of copper of high purity and the availability of high-purity refractories, particularly graphite. In addition to its obvious theoretical interest, the problem of carbon solubility in copper is of practical importance. In the production of copper and of high-copper alloys, carbonaceous covers are frequently used. If even minute amounts of carbon are dissolved, insoluble carbon oxide gases will be formed when such metals are poured under oxidizing conditions. A mechanism of this kind could well be one of the principal causes of gas porosity in casting copper-base products. REVIEW OF LITERATURE In 1823 Vivian1 raised the question as to whether copper by overpoling becomes "combined with a minute portion of carbon." Karsten2 asserted, in 1832, that carbon reduces the high-temperature strength of pure copper, so that when the carbon content has reached 0.2 per cent the metal will be brittle at a dark red heat. According to Karsten, carbon contents of o.05 per cent make it difficult to hot-work copper. He also reported that the specific gravity of copper is 8.8969 and that it increases to 8.92 58 if the copper is cemented with carbon and then melted. He emphasized the difficulty of determining analytically the small amounts of carbon present in copper. The metal was removed by wet methods and the residue considered as carbon. At Percy's request, Dick,3 in 1856, carried out various working tests on copper that had been in prolonged contact with carbon, and found that the working properties of the metal had not been affected. He also attempted to determine the presence of carbon analytically. In one experiment the copper was dissolved and the residue was fused with litharge, and in another essentially a combustion analysis was made on a copper sample. In a final experiment, a sample was dissolved and the residue subsequently subjected to a combustion analysis. Indications of as much as o.005 per cent carbon were found, but Dick considered his work inconclusive largely because of the possible interference of sulphur. Percy4 concluded, from Dick's experiments and from some experimental work of his own, that the solubility of carbon in copper had not been established with

Jan 1, 1945

By L. D. Wooddy, Robert Moscrip

The simultaneous solution of the volumerric balance and the unsteady-state equation has been used for several years to make performance calculations for combination drive reservoirs. This method makes possible the calculation of volumetric changes of fluids in the gas cap, oil zone, and aquifer which occur as a result of withdrawals and reservoir pressure changes. It does not provide a means for the determination of reservoir fluid distribution changes corresponding to these vollrmetric changes. A knowledge of the fluid saturation distribution in the reservoir at various stages of depletion is important for the determination of the efficiency of gas and water as oil-displacement media and, therefore, for the reliable predicrion of ultimate oil recovery. To provide this knowledge, the displacement equations are solved simultaneously with the volumetric balance and unsteady-state equations. The described calculation procedure has been used satisfactorily to analyze the past performance and to predict the future behavior of combination drive reservoirs under both primary and pressure-maintenance operations. INTRODUCTION The three basic mechanisms by which oil is displaced from a reservoir are: (1) dissolved gas drive—the displacement of oil by the expansion of liberated solution gas, (2) water drive—the displacement of oil by water which enters the oil zone from the aquifer, and (3) gas cap drive—the displacement of oil by gas which ex- pands into the oil zone from the gas cap. The action of gravitational forces may be effective in increasing the efficiency of the basic drive mechanisms. Gravitational forces favor the segregation both of gas and oil and of oil and water, thus tending to shorten the transition zone between oil and displacing fluids. Most reservoirs produce under the influence of a combination of these drives and are designated "combination drive reservoirs". Fig. 1 is a cross section of a typical combination drive reservoir. A calculation procedure for analyzing the performance of combination drive reservoirs has been developed by combining the displacement equations' with the volumetric balance equation' and the unsteady-state equations. The pressure-production performance and the positions of the gas-oil and oil-water contacts are calculated for several stages of reservoir depletion by solving these equations simultaneously, thus affording a basis for: 1. Determining instantaneous and ultimate oil, gas, and water production under various operating conditions. 2. 'Establishing a maximum efficient rate of production, 3. Determining the advantages of pressure maintenance and unitization, and 4. Designing surface installations necessary for primarv and pressure-maintenance operations. DEFINITIONS The calculation procedure for combination drive res-

Jan 1, 1957

By H. Bloom, H. E. Hawkes

STREAMS and rivers are the principal channels into which the weathering products of rocks and their contained ores are funneled. The inorganic load of a stream system is a crude sample of all the earth materials in the drainage basin of the stream, and the heavy mineral assemblage of sediments is one of the oldest and most successful guides to certain kinds of bedrock ore in unexplored terrain. Early application of this method was made possible by the ease of separation and identification of heavy minerals in the field with the simplest equipment. Water analysis for traces of base metals became a practical possibility about eight years ago with the development of rapid chemical tests that could be carried out at the field site.' , Since that time the water method has been widely used in mineral reconnaissance, and a substantial number of discoveries have been reported. Here again, the techniques developed for this work were relatively simple and could be performed easily at the field site. Sediment analysis by chemical methods, as distinguished from mineralogical, has received less at- tention. Some experimental work was done by Lovering and others," but to the authors' knowledge, chemical analysis of sediment samples has not been used in routine exploration programs until very recently. In spite of the obvious promise of this method, it was not pursued vigorously because of the lack of a simple and portable chemical test that could be used conveniently at the field site or in a field camp. Procedures that had been developed for trace analysis of soils all called for a rigorous chemical attack with hot acids—tests more conveniently applied in processing large volumes of routine soil samples at an established field headquarters. Recently an extremely rapid and simple test was developed by Bloom.4,5 The extractant used in this procedure is a cold solution of ammonium citrate. Elements measured are the heavy metals, principally zinc, lead, and copper. This method differs from the established procedures for soil analysis in that it measures only a small fraction, about 5 pct, of the total metal content of the sample. It has been found, however, that the significant pattern of metals in the sediments of streams below a base-metal deposit can be brought out as well and sometimes better by this simple cold-extraction procedure than by the more tedious methods requiring hot acids. To understand fully the significance of the relation between the readily extractable and the total

Jan 1, 1957

By Waldemar Lingren

CONTENTS. PART I.-GENERAL FEATURES. [ ]

Jan 1, 1902

By Emby Kaye

IT is the purpose of this paper to outline briefly some of the considerations that enter into the economics of so-called recycling, the generic designation of the relatively recently developed process by which a condensate† is separated from gas-distillate gas at high pressure and the residual gas returned to the reservoir. This subject necessarily embraces not only a discussion of factors that should be considered in projecting a recycling operation, such as estimating reserves, investment and operating costs, but also a comparison of condensate with other types of petroleum. The place of condensate in its relation to the total supply of crude oil is pointed out as well as certain logical methods of product disposal. The cost of drilling wells and lease maintenance is not pertinent to this discussion because income and revenue are in this paper confined to that retained by the plant or plant operator for supplying processing facilities for the gas. Before the development of recycling a great many gas-distillate gas fields in Louisiana and. Texas provided no income to their owners. When gas was sold from these reservoirs it was accompanied by irretrievable losses of condensate in the formation. The understanding of the function of retrograde condensation resulted in the introduction of a new commercial petroleum recovery process for these hitherto unexploited fields and now permits the conditioning of this type of wet gas field for the sale of dry gas therefrom without waste. SOME ECONOMIC FACTORS The study of a gas-distillate field for possible exploitation necessarily involves the critical appraisal of a number of elements, chief of which will be discussed here: (I) estimate of distillate in place, (2) estimate of distillate that can be brought to the surface, (3) available market, (4) costs. The considerations affecting the estimating of distillate reserves. in place are in the main subject to the same errors as are involved in determining dry gas reserves. Determinable data including acreage, sand thickness, reservoir pressure, reservoir temperature, porosity and connate water provide the basis for calculating the volume of gas in place. Ample allowance must be made for connate water, which may occupy from 20 to 35 per cent of the pore space of the sand. The factor of supercompressibility is to a considerable extent nullified by the reservoir temperature. It has been considered well advised to allow this factor to serve as a cushion. With the gas reserves calculated, it remains only to assay the distillate content of the gas. Those familiar with the handling of "wet" gas at high pressure readily appreciate the variables in sampling gas from

Jan 1, 1941

By V.K. Zworykin

Throughout its development the science of electronics, like so many other branches of science and industry, has been indebted to the metallurgist. Metallurgy has provided the electronic engineer with conductors to furnish passage for electrons outside of his evacuated tubes: it has developed tungsten and tantalum wires for emitting electrons and various refractory metals and alloys suitable for electrodes, which receive them and guide them within the tube; finally it has supplied ferromagnetic materials both for shielding electronic apparatus from magnetic fields and for forming highly concentrated fields for deflecting electron . Today I hope to show you that electronics has not been altogether ungrateful for this assistance. More specifically, I wish to indicate the role that the electron microscope, a relatively recent product of electronic engineering, is playing even now in the study of metals. Every metallographer is aware that his standard metallographic microscope will not reveal structural detail involving separations smaller than a certain fraction —at the very best a tenth—of a micron. This limitation, he knows, is a consequence of the fact that the wave length of the light employed for forming the image has this order of magnitude. It is, thus, a property of all light microscopes. TO overcome it, a different imaging medium must be employed, The existence of such a medium became evident when it was demonstrated1 that electrons were affected by magnetic and electric fields with axial symmetry just as light is affected by glass lenses; these fields, or "electron lenses," curve the paths of electrons reaching them from an object located on the axis of symmetry in such a manner that, at some distance from the lens, a true image of the object is formed. Furthermore, although a wave length may . be ascribed to electron beams just as to light, this wave length is much shorter; for electrons accelerated through a difference of potential of 50 kilovolts, the wave length is only about one hundred-thousandth of that of visible light. Actually, the elcctron microscopes of today resolve detail one hundred times as fine as light microscopes; if the maximum useful magnification of the latter is taken to be a thousand, that of electron microscopes is one hundred thousand. The Electron Microscope Since electrons are readily scattered and absorbed by matter, specimens to be observed in the electron microscope must be prepared to be less than one micron in thickness; furthermore, the interior of the microscope must be carefully evacuated to prevent collisions between the clectrons and the molecules of the air. Finally, as already mentioned, the lenses are formed by axially symmetric magnetic or electric fields, and not by any material medium such as glass. Apart from these basic differences, the electron microscope closely

Jan 1, 1943