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By Max Littlefield, Godbold A. C., Gray L. L.

The West Edmond pool of Central Oklahoma, a limestone reservoir, has an area in excess of 29,000 acres and as of Sept. 15, 1946, had produced 53 million barrels of oil from 731 wells at an average depth of 6900 ft. Water has encroached into the reservoir along the west side of the pool and although the area of water invasion is large the net volume of water influx is small, because encroachment has been primarily into a fracture system. The most significant part of this study concerns the character of the Hunton reservoir. Geological study of cores of the producing section was made to supplement core-analysis data. It was determined that approximately 90 pct of the pore volume was contained in intergranular or sand-like porosity and 10 pct in fractures (intermediate porosity). The porous limestone is divided into blocks by the fractures, although in the strongly dolomitic parts of the producing section, fractures are less well developed. The low-permeability intergranular porosity, largely subsidiary to the high-permeability fractures, will produce oil into the fractures by evolution of solution gas. The fractures in effect serve as drainage channels for production of oil from the inter-granular porosity. Because of such a large difference in permeabilities of the two com-ponents, a high degree of by-passing will occur, and, accordingly, the economics involved in undertaking full-scale high pressure gas injection operations have been seriously questioned. Introduction The West Edmond Hunton pool, which covers portions of Canadian, Logan, Oklahoma, and Kingfisher Counties in Central Oklahoma, is the largest reservoir producing oil from a limestone in the state. The total area of the pool comprises about 29,240 acres and development is considered to be essentially complete. In all, 731 producing wells have been completed in the Hunton reservoir at an average depth of approximately 6900 ft, and have yielded a cumulative oil production in excess of 53 million barrels as of Sept. 15, 1946. In addition to wells completed in the Hunton limestone, 21 wells have been completed in the Bartlesville sand at a depth of approximately 6500 ft, which have produced a total of 730,000 bbl of oil. One small producer has been completed in the Cleveland sand at a depth of 5700 ft. However, a study of only the Hunton limestone reservoir will be presented in this paper. The most significant phase of this study concerns the special type of geological core examination that was made in an effort to ascertain the type and degree of porosity in the rock in accordance with lithologic types. Results of this geological study showed the west Edmond pool to be of such a complex nature as to appreciably affect the behavior normally associated with homogeneous reservoirs. Recognition of this condition in the

Jan 1, 1948

By E. E. Schumacher

IN a laboratory devoted to the furtherance of the science of communication, the breadth and variety of the problems encountered are challenging to a metallurgist. In my own long association with the Bell Telephone Laboratories, our metallurgical group has dealt with a vast number of alloys, both ferrous and nonferrous, and with many materials in the border range of metallic properties., The objectives of our design engineers embrace every phase of telephony, and the properties they desire in metals are generally unusual, frequently unique, and often conflicting. Commercial alloys have not always been available with properties to meet a special requirement in the telephone plant, and many alloys have had, therefore, to be custom-made. Anyone who has had the opportunity to observe the results of tests of all types on numerous such alloys, both commercially and specially produced, or who has taken part in the development of an alloy of some necessary, but new or unusual combination of properties, could not fail to be impressed by the frequency with which a desired goal has been reached or adequately approached through the presence of decimal quantities of alloying elements. Nor could One fail to be struck by the occasions when, conversely, of a minute amount Of impurity element has rendered an alloy useful. It is no exaggeration to state that the content be- hind the decimal point often spells success or fail-ure, and the critical content is sometimes far to the right of the decimal point as I shall later illustrate. The great effects of small additions have long been recognized and have, in fact, been described by many investigators. The importance of the minute, however, cannot be overemphasized. Therefore, in this discussion, I propose to illustrate for you some of the startling instances, drawn primarily from our own experiences, wherein small, even vanishingly small, proportions of stranger elements in otherwise common aggregates have com-pletely changed the customary pattern of behavior. No one property has a monopoly as to being dis-proportionately affected by minor elements. Nearly all properties are affected, but there is time here to include only a selected few. I have chosen, there-fore, three of general interest: strength, magnetic, and electrical properties. I shall inquire into both the mechanisms and consequences of these disproportionate effects and try to share with you the fascination and challenge of this field. Strength Properties of Lead and Lead Alloys To illustrate the effect of the minute on strength properties I have selected lead and its alloys, with which we have worked extensively for many years. Lead has the advantages of being available in quantity in a state of high purity and of being fairly easy to melt and fabricate without contamination to any extent detectable by the spectrograph. It has the interesting disadvantages of recovery and recrystallization at room temperature. Whether I

Jan 1, 1951

By H. H. Reamer, B. H. Sage

Attempts have been made to predict the volumetric and phase behavior of naturally occurring hydrocarbon mix-turesl-6 but these methods have not been extended to the higher pressures and tem-peratures that are currently encountered in some producing formations. Furthermore, the methods of prediction at present avail-able have not been tested in a sufficient number of cases to ensure their applica-bility to all naturally occurring hydrocar-bon mixtures, even at the lower pressures and temperatures. For these reasons the behavior of a number of hydrocarbon mix-tures from a field in which the subsurface pressures are above 4500 lb. per sq. in.t and the temperatures are in the neighbor-hood of 250°F. was investigated. Method The objective of this program was to determine the volumetric behavior of ma-terial as it existed in the reservoir as a function of pressure, temperature and com-position. Strictly speaking, this cannot be accomplished in any simple fashion. How- ever, the variations in composition that are encountered within a producing reservoir may be approximated roughly by means of mixtures made up of two arbitrarily chosen constituents. Experience indicates that the liquid and gas phases from a high-pressure gas trap afford a simple source of material for this purpose. Throughout this discus-sion the samples of the gas phase and liquid phase from the production trap will be called the "trap-gas sample" and the "trap-liquid sample," respectively. The volumetric behavior of both of the trap samples was determined throughout the temperature interval between 100" and 250°F. at pressures up to 5000 lb. per sq. in. In addition, the behavior of eight different mixtures containing varying proportions of the two trap samples was studied throughout the same temperature and pressure intervals. The experimental results yielded information concerning the specific volume of the material as a function of pressure, temperature and the relative quantity of the trap samples. The relative amount of each of the paraffin hydrocarbons of lower molecular weight than n-hexane was determined for each of the trap samples. In addition, the specific weight, viscosity and average molecular weight of the hexanes-and-heavier fraction of the trap-liquid sample were determined as well as similar information for each of five fractions separated from this material by distillation. From these data the weight fractions of each of the components from methane through pentane were determined for the trap samples and eight systematically chosen mixtures. Materials The gas and liquid samples were obtained from the production trap of a well in the Rio Bravo field in California during the fall of 1939. Information concerning the condi- 70

Jan 1, 1941

By H. H. Reamer, B. H. Sage

Attempts have been made to predict the volumetric and phase behavior of naturally occurring hydrocarbon mix-turesl-6 but these methods have not been extended to the higher pressures and tem-peratures that are currently encountered in some producing formations. Furthermore, the methods of prediction at present avail-able have not been tested in a sufficient number of cases to ensure their applica-bility to all naturally occurring hydrocar-bon mixtures, even at the lower pressures and temperatures. For these reasons the behavior of a number of hydrocarbon mix-tures from a field in which the subsurface pressures are above 4500 lb. per sq. in.t and the temperatures are in the neighbor-hood of 250°F. was investigated. Method The objective of this program was to determine the volumetric behavior of ma-terial as it existed in the reservoir as a function of pressure, temperature and com-position. Strictly speaking, this cannot be accomplished in any simple fashion. How- ever, the variations in composition that are encountered within a producing reservoir may be approximated roughly by means of mixtures made up of two arbitrarily chosen constituents. Experience indicates that the liquid and gas phases from a high-pressure gas trap afford a simple source of material for this purpose. Throughout this discus-sion the samples of the gas phase and liquid phase from the production trap will be called the "trap-gas sample" and the "trap-liquid sample," respectively. The volumetric behavior of both of the trap samples was determined throughout the temperature interval between 100" and 250°F. at pressures up to 5000 lb. per sq. in. In addition, the behavior of eight different mixtures containing varying proportions of the two trap samples was studied throughout the same temperature and pressure intervals. The experimental results yielded information concerning the specific volume of the material as a function of pressure, temperature and the relative quantity of the trap samples. The relative amount of each of the paraffin hydrocarbons of lower molecular weight than n-hexane was determined for each of the trap samples. In addition, the specific weight, viscosity and average molecular weight of the hexanes-and-heavier fraction of the trap-liquid sample were determined as well as similar information for each of five fractions separated from this material by distillation. From these data the weight fractions of each of the components from methane through pentane were determined for the trap samples and eight systematically chosen mixtures. Materials The gas and liquid samples were obtained from the production trap of a well in the Rio Bravo field in California during the fall of 1939. Information concerning the condi- 70

Jan 1, 1941

By J. Hunter

LouisiaNa ranks fifth among the oil-producing states. In 1941 the state-wide production was slightly in excess of 118,000,000 bbl. of crude oil and conden-sate—an increase of 15,000,000 bbl. over the total production for the year 1940. During 1941, south Louisiana produced approximately 90,900,000 bbl. of oil, while north Louisiana produced approximately 27,000,000. South Louisiana, therefore, produced about 3¼ times more oil than north Louisiana. During the past year, 574,800,000 M cu. ft. of natural and casinghead gas were produced in Louisiana; thus 1941 gas production exceeded the 1940 production by 104,900,000 M cu. feet. Completion records for the year 1941 show that 1512 wells were completed in or adjoining producing fields. These wells, which were drilled to extend known producing areas or were located within producing areas, are not considered as wildcat wells. Of the total number of field wells drilled, 1152 wells found production; the remaining 360 were junked or dry and abandoned. This means that 76 per cent of the wells drilled were successful. Considering the precarious nature of oil-field development, this percentage of new producing wells is exceedingly satisfactory. Of the total number of field welis com-pleted as producers, approximately 86 wells found new and distinct producing sands. During the past year, 30 new fields were found. Four parishes—namely, Caldwell, Catahoula, Orleans, and Natchitoches— entered the ranks of oil-and-gas-producing parishes in the state during that period. This brings the total number of oil-and-gas-producing parishes in the state up to 48. Thus, 75 per cent of the parishes in Louisiana now contain one or more oil and/or gas fields. Although sufficient data are not available to list the addition reserves found in Louisiana during 1941, it is felt that such reserves undoubtedly exceed twice the total production for that year, or at least 200 million barrels. In reserves, therefore, Louisiana ranks third among the various oil-producing states. South Louisiana Although 16 new fields were found in south Louisiana, the outstanding developments in that part of the state were not limited to new discoveries. In fact, most of the increase in reserve in that area has been most consistently accumulated through extensions of known producing sands and through the finding of new sands in already productive fields, especially at depths below the presently producing sands. Since data concerning most of the new extensions and sands are too extensive for discussion here, the more important developments arc briefly outlined below: Abbeville, Vermilion Parish.—Production extended ½ mile to the west. Anse La Butte, St. Martin Parish.—New oil sand discovered at 9400 ft., thus extending production to east flank. West flank defined by dry holes. Barataria, Jefferson Parish.—New oil sand discovered on east side of field at 7620 ft. New

Jan 1, 1942

By J. Hunter

LouisiaNa ranks fifth among the oil-producing states. In 1941 the state-wide production was slightly in excess of 118,000,000 bbl. of crude oil and conden-sate—an increase of 15,000,000 bbl. over the total production for the year 1940. During 1941, south Louisiana produced approximately 90,900,000 bbl. of oil, while north Louisiana produced approximately 27,000,000. South Louisiana, therefore, produced about 3¼ times more oil than north Louisiana. During the past year, 574,800,000 M cu. ft. of natural and casinghead gas were produced in Louisiana; thus 1941 gas production exceeded the 1940 production by 104,900,000 M cu. feet. Completion records for the year 1941 show that 1512 wells were completed in or adjoining producing fields. These wells, which were drilled to extend known producing areas or were located within producing areas, are not considered as wildcat wells. Of the total number of field wells drilled, 1152 wells found production; the remaining 360 were junked or dry and abandoned. This means that 76 per cent of the wells drilled were successful. Considering the precarious nature of oil-field development, this percentage of new producing wells is exceedingly satisfactory. Of the total number of field welis com-pleted as producers, approximately 86 wells found new and distinct producing sands. During the past year, 30 new fields were found. Four parishes—namely, Caldwell, Catahoula, Orleans, and Natchitoches— entered the ranks of oil-and-gas-producing parishes in the state during that period. This brings the total number of oil-and-gas-producing parishes in the state up to 48. Thus, 75 per cent of the parishes in Louisiana now contain one or more oil and/or gas fields. Although sufficient data are not available to list the addition reserves found in Louisiana during 1941, it is felt that such reserves undoubtedly exceed twice the total production for that year, or at least 200 million barrels. In reserves, therefore, Louisiana ranks third among the various oil-producing states. South Louisiana Although 16 new fields were found in south Louisiana, the outstanding developments in that part of the state were not limited to new discoveries. In fact, most of the increase in reserve in that area has been most consistently accumulated through extensions of known producing sands and through the finding of new sands in already productive fields, especially at depths below the presently producing sands. Since data concerning most of the new extensions and sands are too extensive for discussion here, the more important developments arc briefly outlined below: Abbeville, Vermilion Parish.—Production extended ½ mile to the west. Anse La Butte, St. Martin Parish.—New oil sand discovered at 9400 ft., thus extending production to east flank. West flank defined by dry holes. Barataria, Jefferson Parish.—New oil sand discovered on east side of field at 7620 ft. New

Jan 1, 1942

By J. Brian Eby

As is generally understood, the word geophysics means literally ?the physics of the Earth? and the science of geophysics is therefore that which treats of the study and measurements of the various physical properties of the Earth. The broad and general study of the elastic, the gravimetric. or the magnetic properties of the Earth as a whole belongs to the general science of geophysics. The detailed application of this science to rocks of shallow depth and in small areas for the purposes of ascertaining data on their character and structural attitude gave rise to the present well-known science of ?applied geophysics.? Since the discovery of enormous new quantities of oil, gas, and sulphur has been by far and wide the principal benefaction of geo-physics in the United States, this paper will refer only to geophysical methods employed in the search for these particular minerals. The application of methods and appliances originally used for geophysical research to the solution of the practical problems of finding new oil-fields, plus the counterflow or new and highly refined techniques and Instruments from the company and consulting geophysical research laboratories and into non-economic geophysical research, has provided another case of that gen-eral cycle of events which is familiar to all scientists. That this closed-circuit flow or scientific current has been tremendously important to the whole science of geophysics is probably well known to all members of this audience, but the gen-eral status of the exploratory geophysical arts as now used In the search for new oil-fields, the scales on which different methods are being used, the magnitude of the costs involved, and the far greater magnitude of the practical results achieved may not necessarily have come so directly to your attention. It is, I understand, for this reason that this paper has been sug-gested, and I shall seek to provide the information requested by using as case-illustrations those changes in the oil-reserve picture for the United States as a whole, and for the Gulf Coast, California, and Illinois Basin regions in particular, which have occurred in the period of the past 17 years, during which time oil-field discoveries have proceeded at a rate which served to build up known and readily-available (or proven) oil supplies to a reasonable figure, and have dispelled the fears of a serious oil shortage during any period for which valid fore-casts can be made. Not that geophysical-prospecting methods have alone been responsible for this transformation, but they have an indispensable and leading part in the picture of exploration and production-to which geophysics, geology, engineering, and general technical progress have jointly made contribution. So far as the United States as a whole is concerned, its total proven, probable, and possible oil reserves (discoverable and recoverable by then-known methods) were estimated at about nine billion barrels in 1920, whereas proven reserves alone are now com-puted at about 16 billion. In 1920 the driller in ?wild-cat? territory was faced with the knowledge that for every new oil-field opened by a successful well, from 20 to 100 unsuccessful wells would have to be drilled and, in some territories, that the chances for a discovery were really less than one in 100 for new drilling, in contrast to which may be cited the record for the past year in parts of Louisiana where the 67 wells drilled opened 16 new oil-fields, that is to say, where the score of hits to misses was increased to approximately one out of four.

Jan 1, 1940

By W. S. CAYPLESS, H. O. Hofman, E. E. HARRINGTON

I. INTRODUCTION. LIME-ROASTING is a term proposed by Ingalls 1 for the operation of forcing air under pressure through a mixture of galena and lime at the kindling-temperature with the object of oxidizing lead and sulphur and of fritting or fusing the charge. If, finely-divided galena were treated in this manner without the addition of lime, the heat set free by the oxidation of part of the lead and the sulphur would be sufficiently great to fuse undecomposed sulphide, and thus stop desulphurization. Besides the chemical action that the addition of lime, limestone or gypsum to the charge may have, the admixture has the physical effect that it keeps the particles of galena separated from one another and accessible to the oxidizing effect of the air. At present, three methods of lime-roasting are carried out on a working-scale, the Huntington-Heberlein, the Carmichael-Bradford and the Savelsberg2 processes. In the last, which interests us here, an 8-ton charge is made up of galena, limestone and perhaps some siliceous or ferruginous flux; the whole is crushed to pass a screen with 3-mm. holes and moistened with 5 per cent of water. It is fed gradually into a bowl-shaped converter, 6.56 ft. in diameter, supported by trunnions attached to a truck. On the .bottom the converter has a grate with blast-inlet beneath. In starting, the truck with the converter

Jan 1, 1907

By R. J. Hopkins, L. B. Haney

On the basis of limited experimental work conducted at the Port Pirie smelter, it would appear that, by increasing the specific surface of sinter, and possibly that of coke as well, a marked increase in the rate and degree of sinter reduction in the furnace shaft can be achieved. Fusion-point tests have shown that this increased reduction means a much higher sinter fusion point and narrower plastic zone, while the more efficient utilization of coke in the furnace is inherent in the intensification of reduction by the provision of a more reactive sinter surface. Investigations aimed at increasing the ability to operate the blast furnace with a higher lead tenor of sinter reducing fuel cost proportionately, and at eliminating the loss in reduction potential in coke entering the furnace, as shown by the presence of appreciable proportions of CO in the top gases, are reported. Several lines for future investigations that could result in improved smelting methods are proposed. A SOMEWHAT informal presentation of ideas on lead blast-furnace smelting will be given in this paper. These ideas have been developed during observations of furnace behavior at Port Pirie and earlier at Mt. Isa, and have been guided by the results of laboratory experiments at Port Pirie. The authors do not intend to propound any particularly new theories, but present their ideas as a basis for discussion which may help toward a better understanding and improved control of blast-furnace operation. Performance variations of considerable magnitude occur from time to time at most lead blast-furnace plants. While Port Pirie is fortunate in having a very regular supply of high grade concentrates, it is no exception in this respect. Such irregularities are of considerable economic importance and they constitute a challenge to present-day metallurgists in their efforts to obtain an ever greater degree of control over furnace operation. In operating as Port Pirie does with a relatively high lead charge, it has been recognized for a long time that shaft conditions are ,of the greatest importance. A practical, or engineering, attack on the problem of accretions consisted of changes in furnace design, e.g., by widening the shaft to 10 ft above the bottom row of tuyeres, and by the provision of curved ends and vertical walls.' That this attack has had a great measure of success is shown by the fact that barring down of these wide furnaces is rarely necessary, shaft conditions have greatly improved, and sensitivity to charge variations has been markedly reduced. These modifications, followed by some metallurgical changes (chiefly the incorporation of pig iron into the furnace charge in 1948), have brought furnace operation to a point where some variables which were previously masked can now be studied. Accordingly, over different periods of time during the last five years, such variables as could be given numerical values have been recorded and subjected to statistical examination. The objectives of this work were: 1—to reveal the true importance of the different variables and 2—to show the proportion of total furnace variation which is unexplained and therefore referable to causes not measured at present? e.g., shaft accretions, sinter structure, coke structure, and others. Statistical Study of Variables In this work factors relating to furnace speed and lead reduction have been examined: 1—slag com-

Jan 1, 1955

By B. G. Reisdorf

This paper describes the microstructural changes that occur when quenched ultrahigh-strength steels containing OA pet C and various amounts of nickel, silicon, and cobalt are tempered. The changes that occur in hardness, yield strength, and martensite diffraction-peak widths when these steels are tempered are related to the precipitation of the carbide phases. An unea$ectedly high silicon content (about 30 pct) was found in the E -carbide phase in a steel containing only 1.5 pct Si. TEMPERED martensitic steels have such wide-spread utility that they have been the subject of numerous investigations, and a sizable amount of literature has developed on this subject.M This investigation, which is a part of a larger program to correlate microstructure with mechanical properties at a variety of strength levels, is limited to the microstructural changes that occur when a quenched 0.40 pct carbon steel (USS Airsteel X-200 steel) is tempered, and to the effects of the alloying elements—nickel, cobalt, and silicon—on these microstructures. Used in this investigation were electron microscopy, electron-diffraction identification of the carbide phases, electron-probe micro-analysis of the carbides, X-ray determinations of retained austenite, and measurements of martensite X-ray diffract ion-peak widths. MATERIALS AND METHODS The chemical analyses of the eight heats examined eats No. 30 through 37) are shown in Table L Heat No. 30 has the chemical com~osition of Airsteel X-200, and the remaining seven heats contain various amounts of nickel, chromium, cobalt, and silicon. The heats were air-melted in an induction furnace and cast into 8 by 8 in. ingots that were subsequently heated to 2300 and rolled to 1-in.-thick plate. Oversize 0.505-in.-diam tensile specimens were rough-machined from the plates and austenitized in air at 1700° F for half an hour and oil-quenched. The specimens were then tempered in air at temperatures of 400° to 1000 for tempering times of 1, 4, and 16 hr, and finish-machined to 0.505-in.-diam tensile specimens. Electron micrographs were prepared from Formvar replicas of the midthickness of tensile-specimen shanks that had been electrolytically polished and etched in nital. Electron-diffraction patterns were obtained from carbon-extraction replicas. The replicas were prepared by etching the sample surface in the same manner as for microscopy, evaporating carbon on the etched surface, and re-etching the sample to free the carbon film and the precipitate particles. Electron-probe microanalysis was performed on some of the extraction replicas. To obtain adequate fluorescent X-ray intensities, several thicknesses of replica were exposed to the electron beam so that the results represent an average composition of the extracted particles rather than an analysis of single precipitate particles. The retained austenite contents of the specimens were determined by an empirical X-ray diffraction

Jan 1, 1963

By W. Bonfield

The microstrain characteristics of a polycrystal-line Cu 1.9 wt pet Be precipitation-hardening alloy have been determined for various conditions of aging. The friction stress remained constant for all the conditions investigated, whereas the microscopic yield stress (the stress to produce a plastic strain of 2 x 10-8 in. per in.) and the three-stage stress-strain curve in the microstrain region were sensitive to changes in dislocation and precipitate distribution. Correlations between the measurements of microplasticity and electron-nzicroscope observations of substructure are considered. ALTHOUGH the macroscopic mechanical properties of Cu 1.5 to 2.0 wt pet Be precipitation-harden ing alloys were established' in some detail, there has been no previous investigation of the nature of microyield-ing in these alloys. This paper describes a high-sensitivity extensometer determination of microplasticity in polycrystalline Cu 1.9 wt pet Be, in which the friction stress, the microscopic yield stress (the stress to produce a plastic strain of 2 x 10-6 in. per in.), and the rate of strain hardening in the micro-strain region were measured for various conditions of precipitation. The structural changes accompanying aging in this alloy were examined using transmission electron microscopy, a study which differed from previous investigations as, in order to minimize grain boundary precipitation effects,' the solution-treated alloy was cold-rolled to 40 pet reduction prior to aging. Hence the extent of recovery and recrystalliza-tion, as well as the variation of precipitate morphology and distribution, were assessed. From these results possible correlations between the microstrain characteristics and the observed precipitate and dislocation structure are considered. EXPERIMENTAL PROCEDURE The material investigated was a commercial copper beryllium alloy (Berylco 25), which had a com- position of 1.9 wt pet Be and 0.2 wt pet Co. The alloy was solution-treated at 800°C, quenched in water, and then cold-rolled to 40 pct reduction. Tensile specimens of gage length 1 in. and rectangular cross section of 0.18 by 0.06 in. were prepared from the solution-treated, cold-rolled material and aged for 15 min, 2, 24, and 100 hr at 315°C and 24 hr at 425°C to produce a range of precipitate structure. The hardness values associated with these conditions are listed in Table I. It can be seen that a maximum value is obtained after 2 hr at 315oC, which decreases with continued time at temperature to a minimum after 24 hr at 425°C. For comparison some as-solution-treated specimens were also aged for 2 hr at 315°C. The specimens heat-treated to a given condition were examined in two ways. First, the nature and distribution of the precipitate and dislocation structure was characterized using transmission electron microscopy. Thin foils were obtained from the specimens by electrolytic polishing in a 30 pet nitric acid-alcohol solution at -20oC, and were examined in an RCA EMU 3 electron microscope. Second, the mi-croplastic behavior of the specimens was measured with a Tuckerman strain gage, using the load-unload technique previously described2, 3 to determine the friction stress, the microscopic yield stress, and the variation of plastic microstrain with stress. RESULTS 1) Structural Changes During Aging. a) Annealing Processes. The solution-treated, cold-rolled Cu 1.9 wt pet Be had an irregular dislocation-cell structure,

Jan 1, 1968

By W. R. McMillan, E. A. Gulbransen, K. F. Andrew

Annealed and electrolytically polished pure iron was oxidized between 650° and 850°C at oxygen pressures of 0.1 to 2 microns Hg. Electron optical studies showed that oxidation occurs discontinuously over the surface and orients crystallographically with the substructure of the metal grains. IN previous papers', " the authors described the formation of oxide films on high purity iron at norrnal pressures and at temperatures below 300°C. Electron optical studies showed that the oxide film consisted of many individual oxide crystallites having nearly random orientation on each metal grain. The size of the oxide crystallites depended upon the temperature and upon the extent of oxidation. In these studies the crystallite size varied from 250 to 1800Å. Recently, Bardolle and Benard3 studied the crystal habit of the oxide crystallites formed on Armco iron between 650" and 850°C in what might be defined as a "poor vacuum" atmosphere in which the pressure could be varied between 10-1 to 10-3 mm of Hg. Their results showed that, at 850°C and a vacuum of l0-2 to 10-3 mm of Hg, a few well oriented nuclei of oxide were formed on the metal grains. At pressures between l0-1 to 10-2 mm of Hg, many oriented nuclei of oxide were formed. At 750°C the metal surface was bright although an oxide was present. Unfortunately, the extent of oxidation, the oxygen pressure, and the influence of carbon in the metal were not determined, and it was, therefore, impossible to give a theoretical interpretation to the very beautiful light micrographs. Bardolle and Benard used the light microscope to determine the crystal habit of the oxide and X-ray diffraction to determine the orientation relationships. It was believed that the use of controlled amounts of oxidation at high temperature is an important method for the study of the initial stages of oxidation of metals at high temperatures. This paper presents the first results of an electron optical study of this problem for iron. Since the electron microscope and electron-diffraction methods using stripped oxide films and surface replicas yielded finer details of the crystal habit and structure of oxide film, these methods were used in this study. Two types of iron having different carbon contents were used: Puron and Armco* iron. A com- parison of the results for these materials made possible a study of the influence of the surface oxide-carbon reaction on the initial stages of oxidation. Before discussing the experimental results, the thermodynamic equilibria of 1—the oxidation reaction, 2—the surface oxide-carbon reaction, and 3—the solubility of oxygen in iron, will be considered. In addition, it is important to consider the kinetic-theory predictions on the rate of collision of oxygen with the iron surface. Thermodynamic and Kinetic-Theory Calculations Only one type of reaction is usually considered in the oxidation of iron at normal pressures at high temperatures: Fe(a) + 1/2O2(g) = FeO(s) 3Fe(a) + 2O2(g) = Fe3O4(s) 2Fe(a) +3/2O2(g) = a-Fe2O3(s). [11 However, two other reactions may occur: FeO(s) + C (solid solution in Fe) + Fe(a) + CO(g) [2] and Fe(a) + O2(g) e Fe(a) (solid solution of 0,). [ 3 ] In addition, iron will react with the higher oxide at certain temperatures to form FeO. For a complete interpretation of the oxidation of iron at low pres-

Jan 1, 1955

By William F. List, Marvin A. Schuster

Monolithic electrooptical mosaics of 2500 photo-transistor elements with internal row and surface column interconnections have been fabricated by epitaxial-planar diffsion techniques. Unique access to any elemed of the mosaic is provided through one of the fifty X and one of the fifty Y external leads. The sensor mosaic can be used for imaging applications and has a 1:1 aspect ratio, a resolution of 100 lines per in., a dynamic range in excess of lo3, a sensitivity of 0.5 per pw, element response within a 2:l range over 75 pct of the mosaic, and a minimum detectable signal of the order of 10-' w. Design considerations which ilnpose particclar fabrication yequirements are disctussed along with some of the problems peculiar to the epitaxial and planar-dijfision techniqes by which this device is fabricated. The solid-state silicon monolith has an imaging area of 0.5 by 0.5 in. and an element center -to- center spacing of 0.010 in. J monolithic solid-state electrooptical device has been developed as the photon-sensing mosaic for use in an image-converter system.' This system is the solid-state equivalent of the vidicon and can image radiation in the visible and near-infrared regions of the spectrum. The electrooptical image converter has the desirable size, weight, reliability, and low-power characteristics inherent in solid-state devices. It is read out by direct-wire means rather than by beam-scan techniques. The packaged unit is shown in Fig. 1. A selection of material for the sensor was based on considerations of both reliable fabrication techniques and material spectral response. Silicon was selected both for its response from the lower end of :he visible to the long-wavelength cut-off above 11,000A and for its well-developed epitaxial planar-diffused technology. The electrical image is composed of M x N discrete information bits with each bit emanating from one of the individual phototransistor sensors. The interconnected mosaic concept was introduced to provide a structure which is both manageable in its number of leads and compatible with conventional viewing systems which accept XY data. Interconnections along the Y direction are provided by internally diffused strips, while interconnections along the X direction are formed by vacuum-deposited metal surface bars. Unique access to any individual element of the M x N mosaic is available through one of the M and one of the N external leads. PHOTOTRANSISTOR DESIGN A phototransistor structure2 was selected for the discrete photon detectors of which the mosaic is com- posed. Basically, the mode of phototransistor operation is such that incident quanta are absorbed in the base area of the element where they generate electron-hole pairs. If the electrons are liberated within a diffusion length of the depletion region around the collector junction, they will diffuse to this depletion region and be swept across the junction where they account for a small component of the photocurrent. Similarly, the holes which are created within a diffusion length of the emitter junction will diffuse to this region where they forward bias the emitter and so induce injection of minority carriers into the base. This accounts for the substantial transistor photocurrent. This mechanism of operation implies several design and fabrication goals for the individual sensor elements: high electrooptical conversion efficiency, sufficient carrier lifetime in the base regions, and a maximum volume in which photons can be absorbed within a diffusion length from the depletion layer about the junction. Moderately high transistor gain is desirable to permit readout at low light levels; however, very high gain has a deleterious effect on mosaic dynamic range. The mosaic must also be characterized by good uniformity of element response as well as by good isolation between elements. The above set of conditions imply that junction depths must be optimized with respect to photon ab-

Jan 1, 1967

By F. Weinberg, L. MacAulay

DAVIS,' in an investigation of solute redistribution along molten rods of dilute silver in tin, concluded that at horizontal temperature gradients below approximately 5°C per cm very little convective mixing takes place. Cole and winegard2 observed temperature oscillations in horizontal melts of tin, with temperature gradients of several deg per cm. They associated the temperature oscillations with the presence of convective flow in the melt. At temperature gradients less than 1°C per cm they did not detect convective flow. In the present work, direct measurements of con-vective flow in liquid tin have been made using a radioactive tracer technique. The results indicate that extensive convective flow occurs at temperature gradients below those previously reported. The apparatus used to determine the extent of con-vective flow is shown in Fig. 1. The graphite boat Fig. l(a), has two rectangular channels both of which contain molten tin. Radioactive Ag110 in the form of Sn-0.2 pct Ag alloy was introduced at the end of one channel, by rotating the cylinder shown. A series of fixed thermocouples were positioned along the center of the second channel to determine the temperature gradient. It was assumed that the two channels had identical temperature distributions. The graphite boat was inserted into a vycor tube which was surrounded by a multiple winding tube furnace as shown in Fig. l(b). The tin was melted in an argon atmosphere. The distribution of Ag110, as a function of position along the boat at a given time after introduction of the ~g"', was determined with the

Jan 1, 1970

By Raymond Ward

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

Jan 1, 1945

By Randolph C. Specht

A two year study was made of the waste disposal of the pebble rock phosphate industry. Solid slimes are impounded in large settling areas and the process water is re-used. Clear effluent was not found to be toxic to fish or animal life in field tests or in controlled experiments. Survey: The pebble rock phosphate mining and washing operations in Florida (fig. 1) are along the river basins of the Alafia to the west and the Peace to the east. The elevation of the area varies between 40 and 170 ft above sea level. Effluents from the operations find their way into one of the two river systems (fig. 2), the Peace River which flows into Charlotte Harbor and the Alafia into Tampa Bay, both along the Gulf of Mexico. There are no major industries along these rivers below the phosphate operations. On the Peace River, the town of Arcadia, approximately 50 miles below the phosphate operations, obtains its water from the river. No other communities along the rivers use them as a source of water supply. Small communities, farms, and ranches are located along the rivers and both rivers drain vast swamp areas. Complaints had been received at the office of the Chief Sanitary Engineer, of the Florida State Board of Health,' that both rivers were turbid at various times and that fishing in the Alafia River was "not as good as it used to be." Tests made by another agency on the dissolved oxygen content of the Alafia River revealed that the oxygen content, at times, was comparatively low.= However, it was not shown that the phosphate wastes had any effect upon the oxygen content of the stream. The river waters are normally brown in color due to drainage from vast swamp areas and are very shallow, from 2 to 6 ft in depth. Turbid waters have been noted in streams coming from the present phosphate operations and also from streams along which there are no operations at the present time. It was learned from "old timers" that, when many more companies than at present were operating along both the Alafia and Peace Rivers forty or fifty years ago, no attention was paid to prohibiting the disposal of slimes along the river basins. During dry periods now in some of the river swamps where drainage ditches have been dug, it is indicated clearly that phosphate slimes were disposed of directly into the river swamps for many years past. Places have been observed where there were alternating strata of phosphate mud, leaf mold, and quartz sand. The former practice of indiscriminate disposal of wastes accounts for some turbidity, particularly after heavy rains and washouts and during clearing of land and digging of drainage ditches. During a six months' period in which a large tract of land was being cleared and drainage ditches dug, a small stream (Six Mile Creek), which previously had been clear, showed a turbidity of 600 ppm and remained turbid until the clearing was completed; after which the stream again flowed clear. An interview with the operator of the municipal water plant, which is about 50 miles below the phosphate operations on the Peace River and which used this river as a source of supply, revealed that there had been no taste in the water for the past ten years, other than that occasionally encountered from increased growth of algae. The operations of each of the cooperating com-

Jan 1, 1951

By Randolph C. Specht

A two year study was made of the waste disposal of the pebble rock phosphate industry. Solid slimes are impounded in large settling areas and the process water is re-used. Clear effluent was not found to be toxic to fish or animal life in field tests or in controlled experiments. Survey: The pebble rock phosphate mining and washing operations in Florida (fig. 1) are along the river basins of the Alafia to the west and the Peace to the east. The elevation of the area varies between 40 and 170 ft above sea level. Effluents from the operations find their way into one of the two river systems (fig. 2), the Peace River which flows into Charlotte Harbor and the Alafia into Tampa Bay, both along the Gulf of Mexico. There are no major industries along these rivers below the phosphate operations. On the Peace River, the town of Arcadia, approximately 50 miles below the phosphate operations, obtains its water from the river. No other communities along the rivers use them as a source of water supply. Small communities, farms, and ranches are located along the rivers and both rivers drain vast swamp areas. Complaints had been received at the office of the Chief Sanitary Engineer, of the Florida State Board of Health,' that both rivers were turbid at various times and that fishing in the Alafia River was "not as good as it used to be." Tests made by another agency on the dissolved oxygen content of the Alafia River revealed that the oxygen content, at times, was comparatively low.= However, it was not shown that the phosphate wastes had any effect upon the oxygen content of the stream. The river waters are normally brown in color due to drainage from vast swamp areas and are very shallow, from 2 to 6 ft in depth. Turbid waters have been noted in streams coming from the present phosphate operations and also from streams along which there are no operations at the present time. It was learned from "old timers" that, when many more companies than at present were operating along both the Alafia and Peace Rivers forty or fifty years ago, no attention was paid to prohibiting the disposal of slimes along the river basins. During dry periods now in some of the river swamps where drainage ditches have been dug, it is indicated clearly that phosphate slimes were disposed of directly into the river swamps for many years past. Places have been observed where there were alternating strata of phosphate mud, leaf mold, and quartz sand. The former practice of indiscriminate disposal of wastes accounts for some turbidity, particularly after heavy rains and washouts and during clearing of land and digging of drainage ditches. During a six months' period in which a large tract of land was being cleared and drainage ditches dug, a small stream (Six Mile Creek), which previously had been clear, showed a turbidity of 600 ppm and remained turbid until the clearing was completed; after which the stream again flowed clear. An interview with the operator of the municipal water plant, which is about 50 miles below the phosphate operations on the Peace River and which used this river as a source of supply, revealed that there had been no taste in the water for the past ten years, other than that occasionally encountered from increased growth of algae. The operations of each of the cooperating com-

Jan 1, 1951

By D. R. Parrish, V. J. Berry

Reverse combustion is one thermal method of recovering hydrocarbons from porous undergrortnd formations containing oil or tar. In applying this method, air is introduced via an injection well and the mixture of air and hydrocarbons is ignited in the production well. A combustion zone then recedes toward the injection well, counter-current to the air flow. If the combustion-zorie temperature is sufficiently high, the oil or tar irz place is distilled arid cracked. The hydrocnrhon flows as a vapor to the production well and subsequently is condensed at the surface. Maximum temperature and velocity of morcment arc the two dependent variubles defining the progress of the combustion zone. A theoretical analysis has been made of heat flow in the reverse-comhustion process as.srtrning linear flow in a homogeneous system. The differentirll equatious, which include the oxygen-hydrocar-hon rctrction rate, have been solved numerically. Rescllts indicate that the maximum temperature reached and he cornbustion-zone relocity both increase with an incrense in air-injection rote. Heat loss to surroundings has little effect on the maximum comhustion-zone ten?perature achieved, but it is reflected in a reduced com-bustion-zorzc, velocity. It is also predicted that an increase in the oxygen-hydrocarbon reaction rate results in a reduction in the maximum temperature reached. The calculated results are in agreement with results from reverse-combustion experinments using samples of a tar sand. INTRODUCTION Reverse combustion is one thermal method of recovering hydrocarbons from porous underground forma-tions containing oil or tar.' In applying this method, air is introduced into the underground formation via an in-jection well. In one or more adjacent production wells, the mixture of air and hydrocarbons is ignited at the sand face. The combustion zone thus formed recedes toward the injection well, counter-current to the air flow (Fig. 1). Under certain conditions, the rate of recession of the combustion zone is sufficiently rapid that only a small fraction of the hydrocarbon at any point in the formation is consumed by combustion. If the combustion-zone temperature is sufficiently high, the uncon-sumed oil or tar in place may be partially distilled or cracked. This material then can flow as a vapor with the gaseous combustion products to the production well and subsequently be condensed at the surface. Under other conditions, the combustion-zone temperature may be so low that little, if any, of the hydrocarbon is vaporized. Nevertheless, the viscosity of the hydrocarbon may be reduced enough so that other recovery methods subsequently can be applied to produce oil at attractive rates. The maximum temperature achieved in the combustion zone and the velocity of movement are the two dependent variables defining the progress of the combustion zone. Presumably. knowledge of these factors will permit estimates to be made of oil recovery efficiency, oil and gas producticn rates and average amount of injection air required per barrel of oil recovered. The maximum temperature and combustion-zone vclocity are, in turn, expected to be dependent upon air flow rate, heat losses to surrounding formations, physical properties of the rock and the hydrocarbon. the extent to which the porous formation is saturated with the hydrocarbon, the rate of oxidation of the hydrocarbon and the amount of heat released. It is desirable that the relative importance of each of these factors be understood so that the results of laboratory tests of oil recovery by reverse combustion can be properly interpreted in terms of expected field performance. It is particularly desirable to assess the importance of heat lcsses because these are difficult to control or eliminate

By G. Y. Chin, W. L. Mammel

The problem of selection of the active slip systems for a crystal undergoing an arbitrary strain has been analyzed by Taylor and by Bishop and Hill. The Taylor analysis is based on a principle of' virtual work, and involves finding, among numerous cotnbinalions of slip systems that satisfy the imposed strain, the combination in which the sum of the glide shears is a minimum. Previously, Taylor has treated the case of axisymmetric flow when slip occurs on (111)(110) (or {110)(111)) systems only. His analysis has now been extended by computer methods to the cases of slip on {112}(111) and {123)(111) systerns and of mixed slip on {110), {1 12), and (123) planes with a common (111) slip direction, all of which are important in the deformation of bcc crystals. The results are computer-plotted as contours of the ratio of the floe strength to the critical resolved slzea-r stress for slip, for axial orientations distributed throughout the standard stereographic triangle. Implications of the computer results to texture develop,merit, texture hardening, and dislocation theories oj work hardening are discussed. WhEN a single crystal is extended in the usual tension test, the lateral dimensions can change relatively freely. In this case, the glide shear produced by slip on a single slip system is sufficient to accommodate the (tensile) deformation. Since slip is governed by a critical resolved shear stress law (the Schmid law'), the single active slip system is one for which the stress, resolved on the slip plane and in the slip direction, is the highest among the several equivalent slip systems. This amounts to saying that a value M = U/t = y/~ is a minimum among the equivalent systems, where M is the inverse of the familiar Schmid factor (a and E refer to tensile stress and strain, and T and y refer to resolved shear stress and shear strain). A grain embedded in a polycrystalline aggregate, on the other hand, cannot freely change its shape due to constraint from its neighbors. In this case, slip from five independent slip systems (to accommodate five independent strains) is generally required.' Based on the principle of virtual work and assuming that the critical resolved shear stress for slip is the same for all systems, Taylor hypothesized that, among all combinations of (five) slip systems which are capable of accommodating the imposed strain, the active combination is that one for which the sum of the absolute values of the glide shears is a minimum. Again, this is equivalent to saying that the value of M = CjlyjI/ is a minimum, in analogy to the single slip case. Taylor aminimum,analyzed the case of {111)(110) slip for fcc metals, and applied the analysis to crystals undergoing axisymmetric flow, that is, the same macroscopic shape change as the poly crystalline aggregate under uniaxial tension (or compression). For the twelve equivalent {111}( 110) slip systems, there are 384 independent combinations of selecting five systems to satisfy the five independent linear equations of imposed strain.4 Taylor calculated the value of M for each combination* and obtained the active com- *A number of the independent combinations were omitted from consideration in Taylor's original work (see Ref. 5). bination (minimum M) for a number of axial orientations distributed throughout the standard stereographic triangle. Later work by Bishop and Hill*'8 showed that Taylor's least-shear hypothesis was equivalent to a maximum work principle which they advanced. Using the simplified Bishop and Hill method for {111)(110) slip, Hosford and Backofen' obtained detailed contours of constant minimum M for the same axisymmetric flow case. In contrast to {111}(110) slip in fcc metals, slip in bcc metals is generally described as occurring on {ll~)(lll), {112)(111), {123) (111) systems as well as mixed slip composed of all three. Since the direction cosines of the slip plane normal and the slip direction enter as a product in the Taylor analysis, the Taylor solutions of ,M for {110)(111) slip are identical to those for { 111} 110) slip. The other three cases of slip, however, have not been solved. In view of the numerous combinations of slip systems involved in the calculations, the Taylor analysis is clearly oriented toward computerized solutions. THE TAYLOR ANALYSIS In order to obtain the active combination of (five) slip systems by solving for the minimum value of M = we first express the (small) strain components E,, with respect to the cubic axes 1, 2, 3 ([loo], [010], [001], respectively) of the crystal, in terms of the sum of the glide shears yj from slip systems j: where n, and n,j refer to direction cosines of the slip plane normal, and dri and dsi to direction cosines of the slip direction, of slip system j, all referred to the cubic axes. In practice, the strain components are given with respect to the specimen axes X, y, 2. These components are readily converted to ers through the tensor transformation where irk and 1,~ are the direction cosines between the two sets of coordinate axes.

Jan 1, 1968

By J. E. Burke, C. W. Mason

In attempting to study precipitation from a tetragonal lattice, using solid solutione of bismuth in tin, it was found that although a Widmanstätten pattern is observed1,4 only a qualitative analysis of the orientation relationships is possible, because of the unusual structural changes that accompany the precipitation process. Microscopical Studies Alloys were made from Chempur tin (Standard samples 42b and 426, National Bureau of Standards), and bismuth (Kahl-baum C.P.) by melting weighed quantities together under palm oil, stirring well, and castilig in a heated graphite mold. The polishing and etching techniques employed largely govern the visibility of the structural changes. The preliminary surfacing operations were similar to those recommended by Villela and Bergekoff,5 through Behr-Manning 3/0 abrasive papers, lubricated by a solution of paraffin in kerosene. A rough metallographic polish was next given, using a thin cotton cloth charged with relevigated alumina (maximum particle size of about 4µ) and soap solution; repeated etching and polishing served to remove disturbed metal. For high-power examination better preparation was necessary. It was found that on such soft metals the threads of the fabric, rather than the abrasive, cause most of the scratching. Cotton outing flannel, which had been brushed so that the nap lay down, was fairly satisfactory, but a heavy grade of silk velvet (not the noncrushable kind) was found to be better, especially after some use. A better procedure was as follows: The metal lap was warmed slightly, and a 4-in. circle of woolen broadcloth was cemented to its center by a thin film of melted paraffin. The broadcloth was then moistened with water, and a 30 to 40 per cent solution of sodium hydroxide heated to about 50°C. was poured over it, allowed to stand for I to 2 min. and then washed off. It was neither necessary nor desirable to remove all the sodium hydroxide from the cloth, since its etching action aided in the removal of the flowed layer from the sample. The cloth was then charged with a paste of the relevigated alumina in water. Since this lap did not remove deep scratches, it was necessary previously to polish the specimen on some material such as the silk velvet. The sodium hydroxide softens and partly gelatinizes the woolen lap covering, permitting a scratch-free polish, but its action continues, and the cloth deterioratcs after about 24 hr. This is not serious, because a new lap can be prepared in about 5 min., and only small pieces of cloth are used. Etching with a strongly acid solution of ferric chloride was found satisfactory for removing the flowed layer. For the final etching, the most satisfactory reagent was that of Tafls,7 the formula for which is: FeC13.6H2O, 2 grams; HC1, 5 c.c.; H2O, 30 c.c.; C2H5OH (95 per cent), 60 C.C. This etchant reveals differences in com-

Jan 1, 1942