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By T. M. Williams

DURING the year just ended we have had three great fires in the mines in the Wilkes-Barre district. One at the Empire Colliery, one at the Prospect shaft, and the other at the Baltimore old mine. It is proposed in this paper to give a brief history of the fire at the Empire Colliery, and the methods employed in extinguishing it. The fire was first discovered breaking out in the air-stack, alongside what is known as the " Kidder Plane," about one o'clock on the morning of December 31st, 1873. Subsequently it was ascertained that the fire originated in the return airway somewhere near the steam boiler, located inside the mine, near the head of No. 5 slope. The coal from this slope was hoisted to the shaft gangway, at a point nearly four thousand feet distant from the foot of the shaft. As there were from four to five hundred mine cars hoisted per day from this slope the steam boilers were located at this place. The mines being of considerable extent required a large volume of pure air for ventilation, and no fan having been erected at this slope at the time, the heat from the boiler was made use of to assist ventilation, by conveying the return air from No. 5 slope into the large airway made from these boilers to the surface through the old "Kidder slope" to the stack where the fire was first discovered. The length of this slope or airway was about one thousand feet, with a sectional area of about sixty feet. The quantity of air passing through it must have been over sixty thousand cubic feet per minute

Jan 1, 1875

By T. L. Joseph

THE United States Bureau of Mines has been studying the blast-furnace process for, about ten years. An experimental furnace was developed by the bureau in cooperation with the Minnesota School of Mines Experiment Station, University of Minnesota. Many data have been obtained and published.1 Royster, Joseph and Kinney§(48) found that the particle size of ore had an important effect upon the blast-furnace, process. Kinney(28) stated: Economy in blast-furnace practice depends largely upon efficient gas-solid contact in the shaft of the furnace. If efficient work is not done in the shaft, the hearth and bosh will not function properly. A condition may be readily imagined where the particles of ore in the shaft are so large that the time entailed in the descent of these materials into the bosh is not sufficient to permit proper reduction and preparation prior to the time the ore enters the bosh of the furnace. Another condition may be pictured where the density of the stock column and the flow of stock is such that the ore will take one course and the gas another. Both of these examples will result in insufficient contact between the gas and the ore. Unreduced ore will reach the hearth, and the gas which has not been efficiently oxidized will reach the stock line. The result is the use of an excess of carbon in the smelting process. It is obvious that fine ore particles occurring in the ore as charged, or . formed in the furnace due to heat and mechanical action, place a definite limitation upon the efficiency of the operation. There is also an economic loss of fine material as dust.

Jan 1, 1930

By A. S. Eve

This paper gives a brief summary of theory on radiation waves and describes experiments by the United States Bureau of Mines and by the Canadian Geological Survey at the Mammoth Cave, Kentucky. Dr. D. A. Keys, Dr. F. W. Lee and the writer did the experimental work, and Dr. L. V. King some of the theoretical work. In prospecting for orebodies underground it is a usual practice to employ a loop of wire carrying an alternating current that induces an electromotive force in good conductors beneath the earth. The conduc-tars are usually of such low resistance and impedance that currents of considerable magnitude may result in these orebodies or conductors, and these currents in turn induce an electromotive force in a detecting coil placed near the surface of the ground. By using amplifiers it is possible so to enhance the effect of this electromotive force in the detecting coil that the currents in the underground conductors are detected in spite of the powerful effects coming directly to the coil from the primary loop. In such cases distance or depth has primary importance, for the effects have to pass down to the orebody and the secondary effects induced therein have again to pass back through the ground to the observer's detection coil on the surface. However, there is another factor to consider—absorption of the electromagnetic disturbances by the intervening soils and rocks. This absorption will vary with their composition. Thus the main factors that determine the possibility of detecting ore underground are: 1. Its depth beneath the surface, 2. The magnitude of the conducting orebody, 3. The excellence of the conductivity of the orebody as compared with that of the surrounding strata, 4. The frequency of the alternating current,

Jan 1, 1932

By T. M. Williams

DURING the year just ended we have had three great fires in the mines in the Wilkes-Barre district. One at the Empire Colliery, one at the Prospect shaft, and the other at the Baltimore old mine. It is proposed in this paper to give a brief history of the fire at the Empire Colliery, and the methods employed in extinguishing it. The fire was first discovered breaking out in the air-stack, alongside what is known as the " Kidder Plane," about one o'clock on the morning of December 31st, 1873. Subsequently it was ascertained that the fire originated in the return airway somewhere near the steam boiler, located inside the mine, near the head of No. 5 slope. The coal from this slope was hoisted to the shaft gangway, at a point nearly four thousand feet distant from the foot of the shaft. As there were from four to five hundred mine cars hoisted per day from this slope the steam boilers were located at this place. The mines being of considerable extent required a large volume of pure air for ventilation, and no fan having been erected at this slope at the time, the heat from the boiler was made use of to assist ventilation, by conveying the return air from No. 5 slope into the large airway made from these boilers to the surface through the old "Kidder slope" to the stack where the fire was first discovered. The length of this slope or airway was about one thousand feet, with a sectional area of about sixty feet. The quantity of air passing through it must have been over sixty thousand cubic feet per minute

By F. W. Gordon

Since the waste gases of the blast-furnace came to be generally utilized in heating the blast and raising steam, the gradual improvement in the economy of fuel, mainly through the nse of higher temperature in the blast, has impoverished the gases. The increased output per unit of measurement of the furnace, and the increased height of the furnace, have markedly increased the resistance to the blast, thus enormously increasing the duty required from the gases. In other words, a gas reduced in heating power by a further dilution of CO, is required to raise the temperature of the blast to 1800' Fahr., where formerly 600' was a good temperature, and at the same time to raise steam enough to drive the air into the furnace at a pressure of from four to eight pounds in coke practice, and from eight to twelve pounds in anthracite practice, and also pump at least double the water formerly used at furnaces. Hence the necessity for the employment of the best scheme for thoroughly consuming these gases with the least dilution of air, and the use of the best device for absorbing the heat prodnced for the purposes above mentioned. In a former paper before this Society the writer called attention to such improvements as had been made by his firm, by which it was claimed 1400' Fahr. could be maintained in the blast by a less consumption of gas than was required to maintain 900' when using pipe-ovens; and it would not be too much to say that 1600' Fahr. might now be written in place of the 1-400. The object of this paper is to give the practice of our firm in the

Jan 1, 1884

By W. F. Hosford

W. F. Hosford, (Massachusetts Institute of Technology) —evelopment of methods for predicting the plastic anisotropy of textured metals is an important step toward the improvement of properties by texture control. The engineering value of the present analysis is indicated by the good agreement between prediction and experimental findings. The purpose of this discussion, however, is to point out the weakness of the assumptions on which the analysis is based. The authors state that "the relative width and thickness strains are believed to depend only on the slip direction" and accordingly they disregard the orientation of the active slip plane. where E,, cW, and et are the tensile, width, and thickness strains, A,, A,, and At are the angles between the tensile axis x, the width direction w, and the thickness direction t, respectively; and G,, GW, and 4 are the angles between the slip-plane normal and x, w, and t, respectively. Therefore, the ratio of width to thickness strains resulting from slip on a single system would be These relations hold regardless of whether the slip plane is a crystallographic plane of the {110}, (1121, or (123) type or whether noncrystallographic slip occurs. If noncrystallographic slip occurs, it might be reasonable to assume that the effective slip plane is the most highly stressed plane containing the slip direction. In this case the slip direction, S.D., the slip plane normal, S.P.N., and the tensile axis, x, are coplanar (Fig. 19) and the angles are related by following expressions: where 9 is the angle between t and the projection of the slip direction in the w-t plane (igs. 1 and 2). The normal strains, Eq. [9], become

Jan 1, 1963

By Z. F. Oszter, D. Vincent, W. K. Behrands

With the expansion of open pit operations, belt conveyors are going to be used in the 13 608 to 18 144 t/h (15,000 to 20,000 stph) capacity range, which calls for a review of some of the horsepower calculation methods. This paper presents methods (based on German research data, field tests and theoretical considerations) for the evaluation of the Ky factor in the CEMA formula for belt conveyors of large carrying capacity, which fall beyond the limits of the data given in tables in the CEMA book. (The CEMA limits are 407 N\\m (300 lb ft) and Tave = 7.3 Mg (16,000 lb). At these large loads, the impression resistance of the belting on the idlers plays a major role, which in turn influences the magnitude of the drive horse power required. An example will illustrate the order of magnitude difference of the horsepower values obtained by using a conventional calculation method and the suggested method, as well as the beneficcia1 influence of the 4-roll idler in comparison to the standard 3-roll unit for a large caving capacity belt conveyor. This paper concerns itself with the analysis of the resistance to motion of belt conveyors, emphasizing the evaluation of the frictional resistance to motion due to load and belt pressure on the idlers and the flexing resistance of the belt and material when passing over the idlers. In the case of long and heavily loaded belt conveyors, the aforementioned resistances reach extremely high values calling for close analysis of the phenomena, presently not calculable with normally used formulas. This paper establishes correlation between experimental and empirical data presenting practical formulas a tool for the designer of high-capacity belt conveyors. The application of the formula is illustrated in an example in the Appendix.

Jan 1, 1981

By F. E. Bash

A GREAT many industrial operations require the application of heat to carry on or complete processes, in which cases the temperatures must often be controlled within very narrow limits. For the lower temperatures, this control is not, as a rule, difficult as a number of types of reliable pyrometers are available for the work; for example, the mercury and resistance thermometers and the thermocouple. For temperatures above a red heat, thermocouples, platinum resistance thermometers, and total radiation and optical pyrometers may be used, depending on conditions. It is often undesirable, and sometimes impossible, to take temperatures of material by immersing the pyrometer in it or by placing the temperature-measuring device in a position in which it will attain the temperature of the material. The pyrometer may contaminate the product; the temperature may be so high that the pyrometer will not hold its calibration, clue to ineffectual protection and consequent contamination; the object may be inaccessible, as a lamp filament, etc. In such cases, a total radiation or optical pyrometer must be used. The disappearing-filament, or Morse, type of optical pyrometer works on the following principle: An objective lens, Fig. 1, focuses the image of the object whose temperature is desired in the plane of the lamp filament at F, which is at the principal focus of the ocular lens shown in the eye-piece. By this arrangement the eye will not have to accommodate itself first to the lamp filament and then to the object at a distance, and the lamp filament will appear superposed on the object. To balance the instrument, the current is adjusted by means of a rheostat until the tip of the lamp filament just disappears against the object as a background. Figs. 2, 3, and 4 show the appearance of the filament when too cold, too bright, and just balanced.

Jan 8, 1919

By R. L. Wilcox, M. L. Fuller

Owing to the nature of the die-casting process, fresllly cast alloys are undoubtedly not at equilibrium from the standpoint of alloy phase relationships. After casting, therefore, they tend to undergo phase changes, with the ultimate effeet of reaching a state of equilibrium at the aging temperature, beyond which no fnrther change takes place. This phase alteration undoubtedly is one of the primary causes of the changes in dimensions and physical properties that zinc-alloy die castings undergo during aging. It is planned to report on this problem in a series of papers of which this is the first. The writers have made a study of commercial zinc die-casting alloys over a period of several years, utilizing the X-ray diffraction technic of determining the phase composition changes in the alloys. Up to the present, two principal phase changes have been observed which are capable of causing dimensional changes: (I) the segregation of secondary constituents from the zinc-base solid solution and (2) the beta aluminum-zinc decomposition. The latter is the subject of the present paper and studies on the former will be reported upon at a future time. Scope of Study In the present investigation a special technic for the study of the beta phase in zinc-alloy die castings has been developed, making possible the determination of the period of existence of the beta phase after casting. The pure beta constituent and its decomposition have been studied in detail. The effect of magnesium and copper on the velocity of the decomposition is reported. The heat of decomposition, the eutectoid temperature arid the accompanying density change have been measured. The density change lias been calculated from data on crystal structure and the result thus obtained has been compared with the actual change.

Jan 1, 1935

By R. L. Wilcox, M. L. Fuller

Owing to the nature of the die-casting process, fresllly cast alloys are undoubtedly not at equilibrium from the standpoint of alloy phase relationships. After casting, therefore, they tend to undergo phase changes, with the ultimate effeet of reaching a state of equilibrium at the aging temperature, beyond which no fnrther change takes place. This phase alteration undoubtedly is one of the primary causes of the changes in dimensions and physical properties that zinc-alloy die castings undergo during aging. It is planned to report on this problem in a series of papers of which this is the first. The writers have made a study of commercial zinc die-casting alloys over a period of several years, utilizing the X-ray diffraction technic of determining the phase composition changes in the alloys. Up to the present, two principal phase changes have been observed which are capable of causing dimensional changes: (I) the segregation of secondary constituents from the zinc-base solid solution and (2) the beta aluminum-zinc decomposition. The latter is the subject of the present paper and studies on the former will be reported upon at a future time. Scope of Study In the present investigation a special technic for the study of the beta phase in zinc-alloy die castings has been developed, making possible the determination of the period of existence of the beta phase after casting. The pure beta constituent and its decomposition have been studied in detail. The effect of magnesium and copper on the velocity of the decomposition is reported. The heat of decomposition, the eutectoid temperature arid the accompanying density change have been measured. The density change lias been calculated from data on crystal structure and the result thus obtained has been compared with the actual change.

Jan 1, 1935

By C. C. Furnas, T. L. Joseph

It is well known that particles of different sizes are not distributed evenly throughout the average charge in an iron blast furnace. Just how great the disparity in particle size in different parts of a single plane in a furnace may be is indicated by the results of some recent investiga-tion1,2 conducted by the Bureau of Mines on a furnace operating on Lake ores. The wide variations found in gas velocity, gas composition, and temperature from the periphery to the center of the upper charge column were caused by the great variation in particle size of the raw materials used and were also greatly influenced by the methods of charging. This paper summarizes the results of an investigation of the influence of different methods of charging and of the treatment of raw materials upon the size distribution of the solid particles in the blast furnace. A more complete report will appear later as a Bureau of Mines technical paper. Importance of Gas-solid Contact One of the authors has pointed out in a previous report? that the operation of the blast-furnace process is entirely dependent on contact between the gas stream and the solid particles in the stock. The gas stream carries the necessary heat as well as the carbon monoxide molecules that do the work of rednction. In the parts of the furnace in which there is little or no contact between the gas stream and the solids there can be little work of reduction. Obviously, the part of the apparatus that is not doing the work for which it is intended is inefficient; the ideal condition is one in which all portions of the stock column are

Jan 1, 1929

By Morris Muskat

TEe method of R. W. Moore' for determining subsurface interfacial depths by means of integrated curves of apparent resistivity has been analyzed theoretically. It is found that the only unique tangents that can be drawn to such curves are the asymptotes at infinite electrode spacing and the tangents through the origin at vanishing electrode spacing. Explicit expressions have been derived for the relationship between the electrode spacing at the points of intersection of these tangents and the thickness of the surface strata as a function of the conductivity parameters for the two-layer and three-layer earths. It is found that in all cases the electrode spacing at the points of intersection will exceed % of the thickness of the surface layer, and may even become indefinitely large as the resistivity of the deepest layers increases as compared with that of the surface layer. These results do not agree with the empirical findings of Moore that the intersection of the tangent lines fall at an electrode spacing very approxirnately equal to the thickness of the surface layer. Introduction In a recent paper, R. W. Moore1 proposed a new method for the analysis and interpretation of earth-resistivity measurements. This consists essentially in plotting against the electrode separation of a Gish-Rooney system the integral of the apparent resistivity with respect to the electrode spacing, and observing the breaks in the integral curves. Specifically, tangents are drawn to the various segments of the integral curves, which show appreciably different slopes, and the intersections of these tangents are used as indications of the depths of the various underlying strata. By numerous examples Moore has shown that the electrode separation at the first intersection so found agrees very closely with the depth of the bottom of the surface layer. Moreover, in a number of instances the intersections for greater electrode spacings seemed to correspond to the depths of deeper beds. From a strictly empirical point of view, the procedure proposed and demonstrated by Moore appears to be particularly interesting because of its simplicity as well as its apparent accuracy, Moreover, such a simple method would be especially valuable in view of the well-known difliculties heretofore encountered in the quantitative interpretation of resistivity data. It therefore seems appropriate to attempt a mathematical analysis of the problem to see whether the integral method of Moore has a sound basis. Such an analysis is presented here. Even on cursory consideration, it is clear that the remarkable successes observed by Moore in the application of his method are indeed surprising. For it depends upon the determination and choice of the slopes of smooth and continuous curves, which by their nature must show even more gradual- variations than the original apparent-resistivity plots that are already so difficult to interpret quantitatively. It is well established, of course,

Jan 1, 1946

By Morris Muskat

TEe method of R. W. Moore' for determining subsurface interfacial depths by means of integrated curves of apparent resistivity has been analyzed theoretically. It is found that the only unique tangents that can be drawn to such curves are the asymptotes at infinite electrode spacing and the tangents through the origin at vanishing electrode spacing. Explicit expressions have been derived for the relationship between the electrode spacing at the points of intersection of these tangents and the thickness of the surface strata as a function of the conductivity parameters for the two-layer and three-layer earths. It is found that in all cases the electrode spacing at the points of intersection will exceed % of the thickness of the surface layer, and may even become indefinitely large as the resistivity of the deepest layers increases as compared with that of the surface layer. These results do not agree with the empirical findings of Moore that the intersection of the tangent lines fall at an electrode spacing very approxirnately equal to the thickness of the surface layer. Introduction In a recent paper, R. W. Moore1 proposed a new method for the analysis and interpretation of earth-resistivity measurements. This consists essentially in plotting against the electrode separation of a Gish-Rooney system the integral of the apparent resistivity with respect to the electrode spacing, and observing the breaks in the integral curves. Specifically, tangents are drawn to the various segments of the integral curves, which show appreciably different slopes, and the intersections of these tangents are used as indications of the depths of the various underlying strata. By numerous examples Moore has shown that the electrode separation at the first intersection so found agrees very closely with the depth of the bottom of the surface layer. Moreover, in a number of instances the intersections for greater electrode spacings seemed to correspond to the depths of deeper beds. From a strictly empirical point of view, the procedure proposed and demonstrated by Moore appears to be particularly interesting because of its simplicity as well as its apparent accuracy, Moreover, such a simple method would be especially valuable in view of the well-known difliculties heretofore encountered in the quantitative interpretation of resistivity data. It therefore seems appropriate to attempt a mathematical analysis of the problem to see whether the integral method of Moore has a sound basis. Such an analysis is presented here. Even on cursory consideration, it is clear that the remarkable successes observed by Moore in the application of his method are indeed surprising. For it depends upon the determination and choice of the slopes of smooth and continuous curves, which by their nature must show even more gradual- variations than the original apparent-resistivity plots that are already so difficult to interpret quantitatively. It is well established, of course,

Jan 1, 1946

By R. Casting, J. Philibert, and C. Crussard

APPARATUS described in this paper uses the properties of X-radiation, emitted by substances under electron bombardment, as a means of rapid chemical point analysis. The method is based upon the principles of emission X-ray spectrography pioneered by Moseley in 1913. A very finely focused beam of electrons—the electron probe—is projected on the surface of a sample, which has a very large area compared with the beam diameter, at the point where it is desired to know the chemical composition. The minute volume of the sample which is thus irradiated emits a complex X-ray spectrum consisting principally of the characteristic radiations of the elements present in the volume. Measurement of the wavelength and intensity of each component of this spectrum thus affords a simple method of determining the chemical identity and concentration of these elements. The volume of sample which is analyzed at each position of the beam is limited by the diffusion of electrons in the sample. For an accelerating potential of the electron beam of about 30 kv, which is a convenient value for producing the characteristic radiation, this diffusion extends over a diameter of about 1 µ normal to the beam, and about 2 µ in the direction of the beam. Thus a beam of 1 µ in diameter leads to a volume of about 2 µ in diameter being irradiated. The limits of the analyzed region are thus considerably smaller than those obtained by using spark or arc emission spectrometry, which must extend to about 50 µ at right angles to the beam, and those obtained in X-ray fluorescence analysis, where the penetration of the specimen is considerably greater. The apparatus itself consists of three main parts: an electron optical system. an X-ray spectrograph and an optical microscope. The electron opticai system consists of a tungsten cathode emitting the electrow and a pair of magnetic lenses which focus the electron beam on the specimen to be analyzed. The specimen is prepared in the usual way, as in optical micrography. The X-radiation, emitted at the focal spot where the electrons strike the sample, is analyzed with a curved crystal, Geiger-Müller counter, vacuum spectrograph. The light microscope, designed to observe the surface of the sample in the region to be analyzed, is provided with a reflecting objective placed on the axis of the second magnetic lens. Its magnification is X450. The quantitative determination of an element A in the analyzed region is made by measuring the intensity I, of a strong characteristic line of the element, as emitted from the sample, and then the intensity I (A) of this same line as emitted from a

Jan 1, 1958

By M. T. Simnad, G. Derge, Ling Yang

STUDY of diffusion in molten substances is important in at least two respects. Diffusion data, combined with thermodynamic and kinetic information, throw light on the structure of the liquid state. Moreover, a knowledge of diffusion coefficients and their temperature dependence is useful in ascertaining the controlling step in many metallurgical reactions. Although diffusion measurements have been made on a number of molten salts, slags, metals, and alloys,'-'" the results available are still limited and widely scattered, especially for the high temperature melts. It is the purpose of this investigation to establish reliable procedures for the measurement of self-diffusion coefficients in high temperature melts and to use these procedures to determine the self-diffusion coefficients of iron in molten Fe-C alloys of different carbon contents. Experimental Measurement of self-diffusion coefficients in high temperature melts is usually carried out by using one of two methods. In the first, diffusion takes place between two cylindrical samples of the same material, one of which is made radioactive. The diffusion coefficient is calculated from the radioactivity penetration curve in the solidified sample after the diffusion. In the second method, samples contained in capillaries of an inert substance are immersed in an infinite reservoir of the same material. Either the material in the capillary or that in the reservoir is made radioactive and the diffusion coefficient is calculated from the change of the radioactivity of the sample in the capillary after the diffusion. The second method is simpler because a radioactivity penetration curve is not needed for the calculation of the diffusion coefficient; however,.it is valid only when no convection has occurred in the capillary during the diffusion. A radioactivity penetration curve is therefore always useful in indicating that the required conditions for the diffusion are ful- filled. Towers and Chipman" recently studied the self-diffusion of calcium and silicon in CaO-Al,O,-SiO, melts by using the capillary method. Instead of measuring the change of the radioactivity of the sample in the capillary, they autoradiographed the sample after the diffusion and calculated the diffusion coefficient from the intensity distribution of the autoradiograph. Their method is useful when the radioactive isotopes are weak ß-emitters, but is very difficult, if not impossible, to apply to cases involving strong ß or y-emitters. For such cases, sectioning of the sample according to the method of Morgan and Kitchener' may be used for the construction of the radioactivity penetration curve. The self-diffusion of iron in molten Fe-C alloys has been studied in this manner and the experimental procedures are described as follows: The diffusion apparatus is shown schematically in Fig. 1. The bath consisted of about 200 g of an Fe-C

Jan 1, 1957

By E. A. Gulbransen, J. W. Hickman

ONE of the important factors that determine the resistance of a metal or alloy to further chemical reaction is the structure of the superficial oxide film A thorough understanding of the physical and chemical structure as well as the stability of the oxide film formed on the surface as a function of time and temperature of the chemical reaction might furnish clues as to the nature of the reaction process and the protective nature of the film A comprehensive program has been undertaken to study these phenomena This paper summarizes the structure of the oxide films formed on the metals iron, cobalt, nickel, chromium and copper at temperatures up to 700°C Before the introduction of the electron diffraction technique, it «as necessary to use either direct chemical analyses or X-ray diffraction analyses to determine the nature of the oxide film formed on the metal or alloy Chemical analyses yields information on the percentages of the several atomic species present in the film while X-ray diffraction analyses yield information on the atomic geometry In special cases the information obtained may be identical, but in general both view-points are necessary Much of, the early work was carried out on the oxidation of bulk samples where thick films were obtained The products were identified after cooling to room temperature by X-ray diffraction and chemical analyses Although much useful information has been obtained in this manner, little could be learned about the character of the protective oxides during the period when the films were actually protective Evidence concerning the chemical structure of thin oxide films has been made possible by the development of the electron diffraction reflection technique In this method the most fruitful investigations have been made by carrying out the reaction in situ at the temperature at which the film is actually protective LITERATURE The oxidation of iron has been extensively investigated by X-ray and electron diffraction Jackson and Quarrell1 found that oxide films formed and examined at the same temperature differed considerably from those allowed to cool to room temperature The results showed that below 400°C the oxide that was stable in intimate contact with iron was Fe304, between 515° and 900°C the stable film was FeO Above the upper change point of iron the oxide was found to be Fe304 prom 400° to 515°C , FeO, Fe304 or a mixture of the two oxides was found Recrystallization of the air-formed film below 400° and above 900°C led to the formation of Fe304 In the range where thicker films consisted of FeO, the air-formed film was converted to a new hexagonal oxide not previously described

Jan 1, 1946

By J. W. Hickman, E. A. Gulbransen

One of the important factors that determine the resistance of a metal or alloy to further chemical reaction is the structure of the superficial oxide film. A thorough understanding of the physical and chemical structure as well as the stability of the oxide film formed on the surface as a function of time and temperature of the chemical reaction might furnish clues as to the nature of the reaction process and the protective nature of the film. A comprehensive program has been undertaken to study these phenomena. This paper summarizes the structure of the oxide films formed on the metals iron, cobalt, nickel, chromium and copper at temperatures up to 700°C. Before the introduction of the electron diffraction technique, it was necessary to use either direct chemical analyses or X-rav diffraction analyses to determine the nature of the oxide film formed on the metal or alloy. Chemical analyses yields information on the percentages of the several atomic species present in the film while X-ray diffraction analyses yield information on the atomic geometry. In special cases the information obtained may be identical, but in general both viewpoints are necessary. Much of the early work was carried out on the oxidation of bulk samples where thick films were obtained. The products were identified after cooling to room temperature by X-ray diffraction and chemical analyses. Although much useful information has been obtained in this manner. little could be learned about the character of the protective oxides during the period when the films were actually protective. Evidence concerning the chemical structure of thin oxide films has been made possible by the development of the electron diffraction reflection technique. In this method the most fruitful investigations have been made by carrying out the reaction in situ at the temperature at which the film is actually protective. Literature The oxidation of iron has been extensively investigated by X-ray and electron diffraction. Jackson and Quarrelll found that oxide films formed and examined at the same temperature differed considerably from those allowed to cool to room temperature. The results showed that below 400°C the oxide that was stable in intimate contact with iron was Fe³O4; between 515° and 900°C. the stable film was FeO. Above the upper change point of iron the oxide was found to be Fe³O4. From 400' to 515°C., FeO, Fe³O4 or a mixture of the two oxides was found. Recrystallization of the air-formed film below 400' and above 900°C. led to the formation of Fe3O4. In the range where thicker films consisted of FeO, the air-formed film was converted to a new hexagonal oxide not previously described.

Jan 1, 1947

By E. A. Gulbransen, J. W. Hickman

One of the important factors that determine the resistance of a metal or alloy to further chemical reaction is the structure of the superficial oxide film. A thorough understanding of the physical and chemical structure as well as the stability of the oxide film formed on the surface as a function of time and temperature of the chemical reaction might furnish clues as to the nature of the reaction process and the protective nature of the film. A comprehensive program has been undertaken to study these phenomena. This paper summarizes the structure of the oxide films formed on the metals iron, cobalt, nickel, chromium and copper at temperatures up to 700°C. Before the introduction of the electron diffraction technique, it was necessary to use either direct chemical analyses or X-rav diffraction analyses to determine the nature of the oxide film formed on the metal or alloy. Chemical analyses yields information on the percentages of the several atomic species present in the film while X-ray diffraction analyses yield information on the atomic geometry. In special cases the information obtained may be identical, but in general both viewpoints are necessary. Much of the early work was carried out on the oxidation of bulk samples where thick films were obtained. The products were identified after cooling to room temperature by X-ray diffraction and chemical analyses. Although much useful information has been obtained in this manner. little could be learned about the character of the protective oxides during the period when the films were actually protective. Evidence concerning the chemical structure of thin oxide films has been made possible by the development of the electron diffraction reflection technique. In this method the most fruitful investigations have been made by carrying out the reaction in situ at the temperature at which the film is actually protective. Literature The oxidation of iron has been extensively investigated by X-ray and electron diffraction. Jackson and Quarrelll found that oxide films formed and examined at the same temperature differed considerably from those allowed to cool to room temperature. The results showed that below 400°C the oxide that was stable in intimate contact with iron was Fe³O4; between 515° and 900°C. the stable film was FeO. Above the upper change point of iron the oxide was found to be Fe³O4. From 400' to 515°C., FeO, Fe³O4 or a mixture of the two oxides was found. Recrystallization of the air-formed film below 400' and above 900°C. led to the formation of Fe3O4. In the range where thicker films consisted of FeO, the air-formed film was converted to a new hexagonal oxide not previously described.

Jan 1, 1947

By B. J. Nelson, F. N. Rhines

STUDIES upon the rates of oxidation of copper alloys containing small quantities of the alloying elements1,2 have shown that steady growth of the scales at predictable rates is limited to a small concentration range and to oxidation at temperatures above 600°C., whereas unpredictable and erratic oxidation behavior is found with alloys containing larger additions and at low temperatures. The latter effect appears to be associated with modifications in the geometric disposition of the oxides. At low concentrations of the baser elements in copper, simple oxidation behavior is typified by the formation of two distinguishable zones of oxidation: (I) a subscale composed of discrete particles of the oxide of the alloying element embedded in substantially pure copper and (2) an external scale composed of cuprous oxide (with a very thin layer of cupric oxide on the outside) containing particles of the alloying element distributed throughout, but most profusely near the metal surface (see Fig. 2, top). Where this type of structure obtains, the process of oxidation is believed to be implemented, and its rate controlled, by the diffusion of the reacting elements through a continuous matrix phase; i.e., through the alpha (metallic) phase of the subscale and alloy and through the cuprous oxide of the external scale. Copper is presumed to diffuse outward through the cuprous oxide layer to the external surface, where it reacts to form more cuprous oxide.3 Oxygen is delivered at the oxide-metal interface in the form of cuprous oxide, which may either react with the alloying element to deposit its oxide at the inner limit of the external scale or dissolve in the pure copper that remains at the surface of the metal after it has become depleted in its oxidizable alloying elements. Both oxygen and the alloying element are pictured as diffusing through the metal, the oxygen inward and the alloying element outward. Where the two diffusion streams meet in sufficient concentration the oxide of the subscale is precipitated. If the oxygen pressure in the surrounding atmosphere is just below the pressure necessary to maintain cuprous oxide undecomposed, no cuprous oxide can be formed; some of the oxide of the alloying element may form upon the external surface, if its decomposition pressure is below that of cuprous oxide, and a normal subscale appears. This condition is achieved experimentally by enclosing the alloy with cuprous oxide together with an excess of copper. At temperatures from 600°C. downward, the precipitated oxides tend to accumulate at the grain boundaries of the alpha phase where a relatively small volume establishes a partial barrier to the diffusion of the reactants. Similarly, large volumes of precipitated oxides tend to deposit in various patterns that may be expected to hinder the diffusion of the reactants in the

Jan 1, 1943

By G. R. Hodgson, M. P. Lebourg

The introduction in the field of a new type well completion called for the setting of tubing open-ended in the well before perforating the casing. This paper describes a new perforating tool of the shaped charge expendable type, small enough to pass through tubing and powerful enough to perforate the casing. The perforations are produced at an angle and are large enough for optimum production. Performance of this tool in targets and under various well conditions is described. Very often no lifting equipment will be available at the well. In some cases, pressure will exist in the well at the time of the perforating operation (workover wells or multiple trip perforation) ; therefore, new equipment and new technique for the perforating operation were devised. This paper describes this equipment and technique, particularly casing collar recording, sheave support, and cable pull-down device. this last item being necessary for wells under pressure. Results obtained with this tool in the field are given. INTRODUCTION One of the key requirements for the introduction in the field of a new method of permanent well completion was the development of a new perforating method involving the use of a perforating gun small enough to go through tubing and with enough penetrating power to perforate the casing satisfactorily. The equipment described in this paper was basically designed to go through open-ended two-in. tubing and to perforate 5 1/2 in. casing. The equipment is illustrated in accompanying figures. NEW COMPLETION METHOD With the new permanent type well completion, the production string of casing is run and cemented through the potential producing zone. Open-ended tubing is -then run into the well and used to replace the drilling fluid with oil or water. The amount of the oil or water "cushion" can be varied according to the expected bottom hole pressure. Thus, if desired, the hydrostatic head can be greater, equal to, or less than the expected pressure within the zone to be perforated. Mud having been displaced, the tubing is -then positioned so that the end is above the zone to be perforated. The Christmas tree and flow lines are installed and tested. The drilling rig can now be removed from the well since it is not necessary for the perforating operation, thus resulting in a saving in rig tme. The perforating equipment is then moved to the well and the gun lowered through the tubing. After the gun passes out of the open end of the tubing, the depth measurements are correlated with casing collars and the gun placed opposite the zone to be perforated. Upon firing, the gun body is shattered and falls to the bottom of the well. Since the lubricator has been closed before firing, it is possible to withdraw the casing collar locator and head and then open the well immediately to the tanks. DESCRIPTION OF GUN An investigation of two basic types of Perforators, namely a bullet perforator and a shaped charge gun, was undertaken towards the development of a gun to meet the aforementioned requirements. Preliminary tests on various bullet perforator designs within the diameter limitations did not give results encouraging enough to warrant further study. Somewhat better results were obtained by using conventional shaped charges; but, as in the case of the bullet types, the necessarily small overall diameter proved to be a severe limitation and resulted in insufficient penetration. A shaped charge employing a new design was developed which gave excellent penetration. These shaped charges were designed to produce a large hole directed upward at a 45" angle. In order to obtain the maximum space possible for these charges, it was decided to use an expendable carrier made of drillable material, usually aluminum, which would shatter at the time of firing, leaving only harmless fragments at the bottom of the hole. The fixed spacing is five shots per ft. wit11

Jan 1, 1952