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By Jan Law

Problems of oil recovery are attacked from the approaches dictated by the two strikingly dissimilar complexes that comprise an oil reservoir—the fluid complex and the interstitial complex. Knowledge of the fluid complex, due to labors in the fields of fluid mechanics and physical chemistry, has far outdistanced knowledge of the interstitial characteristics of the sand complex. This paper is concerned with the latter and applies the technique of statistics to petrographic facts—namely, porosity and permeability—dealing with what might be called petrometry. Statisticians have long worked within the problem of reconstruction of a universe oi variables by means of samples that comprise a small percentage of the universe from which the samples were drawn. Core-analysis data comply with the requisite of random sampling as stipulated by theoretical statistics. A basic concept of statistics employs t.he following substitution: 1. The results of sampling are arranged as a frequency distribution. 2. The observed frequency distribution is compared with a mathematically precise distribution. 3. If a sufficiently good agreement is found between the two, the precise distribution is substituted in all subsequent operations involving characteristics of the sampled material. This mathematically precise distribution is also known as the normal curve, curve of error, the probability, the Gaussian, and the bell-shaped curve and is describable with but two figures. Further, these two figures, the arithmetic average and the standard deviation, are subject to mathematical manipulation. This paper demonstrates that, in some cases in the Dominguez field of Southern California, if sufficient core-analysis samples are taken over not too great a thickness of sediments, the resultant permeability and porosity assemblages give satisfactory agreement with ilormal curves. It is shown that the indications are strong that oil wells wherein a satisfactory agreement is found are predictable as to productivity. Since the predictions are made by employing the laws of chance that are operative within sedimentation, it follows that the mechanism by which the predictions were made is a basic concept of reservoir mechanics. Therefore, tentative examples are given of the application of normal curves to the solution of problems of primary and secondary recovery. Nature of Permeability Frequency Distributions Core-analysis data are made available as a tabulated depth vs. permeability profile. The nature of the distribution of permeability values within a given strati-graphic interval may be approximated from an array constructed with samples plotted in the order of their appearance with depth (accession number) against their permeability value in millidarcys. A wide variation in the nature of the distribution of K (permeability) values for

Jan 1, 1944

By Jan Law

Problems of oil recovery are attacked from the approaches dictated by the two strikingly dissimilar complexes that comprise an oil reservoir—the fluid complex and the interstitial complex. Knowledge of the fluid complex, due to labors in the fields of fluid mechanics and physical chemistry, has far outdistanced knowledge of the interstitial characteristics of the sand complex. This paper is concerned with the latter and applies the technique of statistics to petrographic facts—namely, porosity and permeability—dealing with what might be called petrometry. Statisticians have long worked within the problem of reconstruction of a universe oi variables by means of samples that comprise a small percentage of the universe from which the samples were drawn. Core-analysis data comply with the requisite of random sampling as stipulated by theoretical statistics. A basic concept of statistics employs t.he following substitution: 1. The results of sampling are arranged as a frequency distribution. 2. The observed frequency distribution is compared with a mathematically precise distribution. 3. If a sufficiently good agreement is found between the two, the precise distribution is substituted in all subsequent operations involving characteristics of the sampled material. This mathematically precise distribution is also known as the normal curve, curve of error, the probability, the Gaussian, and the bell-shaped curve and is describable with but two figures. Further, these two figures, the arithmetic average and the standard deviation, are subject to mathematical manipulation. This paper demonstrates that, in some cases in the Dominguez field of Southern California, if sufficient core-analysis samples are taken over not too great a thickness of sediments, the resultant permeability and porosity assemblages give satisfactory agreement with ilormal curves. It is shown that the indications are strong that oil wells wherein a satisfactory agreement is found are predictable as to productivity. Since the predictions are made by employing the laws of chance that are operative within sedimentation, it follows that the mechanism by which the predictions were made is a basic concept of reservoir mechanics. Therefore, tentative examples are given of the application of normal curves to the solution of problems of primary and secondary recovery. Nature of Permeability Frequency Distributions Core-analysis data are made available as a tabulated depth vs. permeability profile. The nature of the distribution of permeability values within a given strati-graphic interval may be approximated from an array constructed with samples plotted in the order of their appearance with depth (accession number) against their permeability value in millidarcys. A wide variation in the nature of the distribution of K (permeability) values for

Jan 1, 1944

By Wilson D. Michell

The Magma copper vein trends east-west, dips 70" south, and cuts through a 6000-ft thickness of limestones, quartzites,. shale, diabase, and schist. The vein is itself a fault with a horizontal offset of 500 ft on the formation contacts in the two walls. There are two principal faults of large displacement and numerous smaller steep and flat faults that complicate the prediction of ore occurrence. A study of the geology, its systematic recording to facitliate ready reference, and graphic methods of interpretation of mineralization have aided the exploration, development, 2nd mining of the ore. In making predictions of the distribution of mineable ore bodies and their shape in critical areas, studies are made of "mineralization contours" and "mineralization trends," which are developed on a longitudinal section of the vein from variations in the concentration of the combined base metal content as shown by assays of available openings in the mine. Introduction This paper describes an example of geological work applied directly to mining and exploration problems in a deep vein deposit, and it is presented as being of interest especially to those engaged in working more or less similar veins. In 1944 to 1945 the writer spent a year as assistant to J. K. Gustafson in a thorough geological examination of the Magma mine. Much of the writer's subsequent independent work described in the present paper had its inception in ideas originated by Gustafson during that examination. Objectives of Geological Work at Magma Mine The objectives of geological work at Magma, as at operating vein mines of a similar nature, can be summarized as follows: 1. Direct assistance to the mining department by means of predictions as to the size, shape, grade, and location of ore bodies; by solution of fault problems and irregularities in the veins; by prepara-?ion of detailed ore-reserve estimates in specific areas; by keeping a complete record of the geology and assay results in the mine; and by guiding development work. In short, geology can aid in the realization of the prime purpose of the mining department, which is that of producing the greatest amount of ore in the most economical and expeditious manner possible. 2. Guidance for exploration, especially diamond drilling, in undeveloped areas of the mine. 3. Contributions to the understanding of the general geology of the deposit and its regional setting, including ore genesis, structure, and mineral relationships. Magma Ore Deposit The east-west trending Magma vein, dipping about 70" south, cuts through a 6000-ft thickness of concordant limestones, quartzites, shale, diabase, and schist, named in descending order. These

Jan 1, 1949

By Wilson D. Michell

The Magma copper vein trends east-west, dips 70" south, and cuts through a 6000-ft thickness of limestones, quartzites,. shale, diabase, and schist. The vein is itself a fault with a horizontal offset of 500 ft on the formation contacts in the two walls. There are two principal faults of large displacement and numerous smaller steep and flat faults that complicate the prediction of ore occurrence. A study of the geology, its systematic recording to facitliate ready reference, and graphic methods of interpretation of mineralization have aided the exploration, development, 2nd mining of the ore. In making predictions of the distribution of mineable ore bodies and their shape in critical areas, studies are made of "mineralization contours" and "mineralization trends," which are developed on a longitudinal section of the vein from variations in the concentration of the combined base metal content as shown by assays of available openings in the mine. Introduction This paper describes an example of geological work applied directly to mining and exploration problems in a deep vein deposit, and it is presented as being of interest especially to those engaged in working more or less similar veins. In 1944 to 1945 the writer spent a year as assistant to J. K. Gustafson in a thorough geological examination of the Magma mine. Much of the writer's subsequent independent work described in the present paper had its inception in ideas originated by Gustafson during that examination. Objectives of Geological Work at Magma Mine The objectives of geological work at Magma, as at operating vein mines of a similar nature, can be summarized as follows: 1. Direct assistance to the mining department by means of predictions as to the size, shape, grade, and location of ore bodies; by solution of fault problems and irregularities in the veins; by prepara-?ion of detailed ore-reserve estimates in specific areas; by keeping a complete record of the geology and assay results in the mine; and by guiding development work. In short, geology can aid in the realization of the prime purpose of the mining department, which is that of producing the greatest amount of ore in the most economical and expeditious manner possible. 2. Guidance for exploration, especially diamond drilling, in undeveloped areas of the mine. 3. Contributions to the understanding of the general geology of the deposit and its regional setting, including ore genesis, structure, and mineral relationships. Magma Ore Deposit The east-west trending Magma vein, dipping about 70" south, cuts through a 6000-ft thickness of concordant limestones, quartzites, shale, diabase, and schist, named in descending order. These

Jan 1, 1949

By Carl F. Floe, Michael B. Bever

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

Jan 1, 1945

By A. D. Smigelskas, E. O. Karenna

This is the third paper in a series on the diffusion of zinc in alpha brass.' At the time of the first paper it was accepted that diffusion in a substitutional type of solid solution depended upon an equal interchange of solute and solvent atoms across the diffusion interface (or past a given lattice reference point). Discrepancies in the size of the areas under the diffusion curves on each side of the interface, if observed, were explained on some other basis than the fact that the solute atoms might cross the diffusion interface without an equal number of solvent atoms diffusing across the interface in the opposite direction. The second paper presented evidence indicating that zinc atoms in alpha brass diffuse across the interface more rapidly in one direction than the copper atoms diffuse across the interface in the opposite direction. This phenomenon forced the interface to move in the opposite direction of the diffusion of zinc atoms to provide space for the additional zinc atoms dissolved in the alpha brass. That the interface and columnar grain structure on one side would remain intact during this mass movement was not expected; how ever, it is gratifying that they did. While the evidence was sufficiently satisfying to the author, it was decided that additional experiments were in order to prove that zinc diffuses more rapidly than copper in alpha brass. It is the purpose of this paper to present the results of these experiments. Procedure A bar of 70-30 wrought brass was selected, to avoid the relatively large volume change in going from beta to alpha brass as in the previous investigation. A bar 7 in. (18-cm.)* long and about 3/4 in. (1.9 cm.) wide was surface ground and polished with abrasive paper on plate glass to 0.4184 0.0002 in. (1.062j + 0.0005 cm.) thick. Six0.00j-in. (0.013-cm.) diameter molybdenum wires, chosen because of their very low solubility in coppcr and alpha brass, were strctched lengthwise along each of the two plane surfaces. Glass tubes placed at right angles to the wires every 1/2 in. held the wires tightly against the brass. The sample was then emersed in an acid copper sulphate plating bath and electroplated to a depth of about 0.020 in. (0.050 cm.) copper on all sides. The glass tubes were no longer necessary to hold the molybdenum wires in place and were removed. The sample was then electroplated to a depth of

Jan 1, 1947

By T. R. Graham, R. S. Dean. J. R. Long

Although considerable information has been published concerning manganese additions to the aluminum bronzes, these data refer principally to the two-phase alloys containing 8 to II pet aluminum, with some incidental information on the single-phase alpha solid solution alloys. Straussl gives an excellent review of the literature on aluminum bronzes up to 1927 and a bulletin2 of the Copper Development Association brings the bibliography up to 1938. The most extensive work on manganese addition is that of Rosenhain and Lantsberry,3 who investigated alloys ranging up to 10 pct aluminum and up to 10 pct manganese, and presented data on the physical properties of sand-cast, chill-cast, and several wrought alloys. The greater portion of the work, however, concerns alloys ranging from 7 to 10 pct aluminum in the cast condition and sheds little light on the properties of wrought single-phase alloys. Corson4 notes that alloys containing 10 pct manganese and 4 pct aluminum are not hardenable by heat-treatment, while one with 15 pct manganese and 5 pct aluminum can be hardened, but he gives no tensile data on it. In fact, no systematic study of the properties of single-phase wrought alloys containing substantial amounts of manganese has been reported. It should also be noted that most of the investigators worked with alloys containing significant amounts of iron and silicon, and that these impurities, whether intentionally added or accrued from the raw materials used in the preparation of the alloys, may be expected to have a direct bearing on the resultant properties. In the work on alloys made with electrolytic manganese, the Bureau of Mines has undertaken an investigation of the copper-manganese-aluminum system for the purpose of establishing the constitution and properties of high-purity alloys. In a recent paper6 the authors reported a metallographic investigation of the alpha solid solution area and the adjoining fields of the copper-manganese-aluminum system up to 50 pct manganese. This study established the alpha-phase boundaries at 50" temperature levels from 400' to 850°C. It was found that the addition of manganese to copper-aluminum alloys decreases the solub%ty of aluminum in the alpha phase (Fig I), curving the boundary toward the copper-manganese base line. The greatest change occurs in the first 20 to 25 pct manganese, which decreases the solubility of aluminum to approximately 4 pct. With larger amounts of manganese the alpha boundary tends to parallel the copper-manganese binary. At 13oo'F and higher,

Jan 1, 1947

By E. O. Karenna, A. D. Smigelskas

This is the third paper in a series on the diffusion of zinc in alpha brass.' At the time of the first paper it was accepted that diffusion in a substitutional type of solid solution depended upon an equal interchange of solute and solvent atoms across the diffusion interface (or past a given lattice reference point). Discrepancies in the size of the areas under the diffusion curves on each side of the interface, if observed, were explained on some other basis than the fact that the solute atoms might cross the diffusion interface without an equal number of solvent atoms diffusing across the interface in the opposite direction. The second paper presented evidence indicating that zinc atoms in alpha brass diffuse across the interface more rapidly in one direction than the copper atoms diffuse across the interface in the opposite direction. This phenomenon forced the interface to move in the opposite direction of the diffusion of zinc atoms to provide space for the additional zinc atoms dissolved in the alpha brass. That the interface and columnar grain structure on one side would remain intact during this mass movement was not expected; how ever, it is gratifying that they did. While the evidence was sufficiently satisfying to the author, it was decided that additional experiments were in order to prove that zinc diffuses more rapidly than copper in alpha brass. It is the purpose of this paper to present the results of these experiments. Procedure A bar of 70-30 wrought brass was selected, to avoid the relatively large volume change in going from beta to alpha brass as in the previous investigation. A bar 7 in. (18-cm.)* long and about 3/4 in. (1.9 cm.) wide was surface ground and polished with abrasive paper on plate glass to 0.4184 0.0002 in. (1.062j + 0.0005 cm.) thick. Six0.00j-in. (0.013-cm.) diameter molybdenum wires, chosen because of their very low solubility in coppcr and alpha brass, were strctched lengthwise along each of the two plane surfaces. Glass tubes placed at right angles to the wires every 1/2 in. held the wires tightly against the brass. The sample was then emersed in an acid copper sulphate plating bath and electroplated to a depth of about 0.020 in. (0.050 cm.) copper on all sides. The glass tubes were no longer necessary to hold the molybdenum wires in place and were removed. The sample was then electroplated to a depth of

Jan 1, 1947

By R. S. Dean. J. R. Long, T. R. Graham

Although considerable information has been published concerning manganese additions to the aluminum bronzes, these data refer principally to the two-phase alloys containing 8 to II pet aluminum, with some incidental information on the single-phase alpha solid solution alloys. Straussl gives an excellent review of the literature on aluminum bronzes up to 1927 and a bulletin2 of the Copper Development Association brings the bibliography up to 1938. The most extensive work on manganese addition is that of Rosenhain and Lantsberry,3 who investigated alloys ranging up to 10 pct aluminum and up to 10 pct manganese, and presented data on the physical properties of sand-cast, chill-cast, and several wrought alloys. The greater portion of the work, however, concerns alloys ranging from 7 to 10 pct aluminum in the cast condition and sheds little light on the properties of wrought single-phase alloys. Corson4 notes that alloys containing 10 pct manganese and 4 pct aluminum are not hardenable by heat-treatment, while one with 15 pct manganese and 5 pct aluminum can be hardened, but he gives no tensile data on it. In fact, no systematic study of the properties of single-phase wrought alloys containing substantial amounts of manganese has been reported. It should also be noted that most of the investigators worked with alloys containing significant amounts of iron and silicon, and that these impurities, whether intentionally added or accrued from the raw materials used in the preparation of the alloys, may be expected to have a direct bearing on the resultant properties. In the work on alloys made with electrolytic manganese, the Bureau of Mines has undertaken an investigation of the copper-manganese-aluminum system for the purpose of establishing the constitution and properties of high-purity alloys. In a recent paper6 the authors reported a metallographic investigation of the alpha solid solution area and the adjoining fields of the copper-manganese-aluminum system up to 50 pct manganese. This study established the alpha-phase boundaries at 50" temperature levels from 400' to 850°C. It was found that the addition of manganese to copper-aluminum alloys decreases the solub%ty of aluminum in the alpha phase (Fig I), curving the boundary toward the copper-manganese base line. The greatest change occurs in the first 20 to 25 pct manganese, which decreases the solubility of aluminum to approximately 4 pct. With larger amounts of manganese the alpha boundary tends to parallel the copper-manganese binary. At 13oo'F and higher,

Jan 1, 1947

By F. N. Rhines

STUDIES upon the sintering of metal powders, in the solid state, have led to the proposal that the surface energy of the powder particles provides the driving force that causes points of contact between pairs of particles to grow into broad welds which isolate the residual vacant space into pores that tend to spheroidize and gradually to diminish in total volume.' Investigators differ with regard to the mechanism of the movement of the metal, under the influence of surface energy, to accomplish these changes. One school asserts that there is a mass movement of the metal, referred to as a "viscous flow," while the other school prefers to view the movement as a self diffusion process, wherein individual atoms are, transferred without disturbance of the basic pattern of the crystal lattice. Extensive experimental studies upon the sintering of copper, conducted recently by A. J. Shaler,2 have been in- terpreted by their author as support for the viscous flow mechanism of transport, the theory of which was developed originally by J. Frenkel.3 Duplicating a portion of this work with minor changes, G. C. Kuczynski4 is led to the alternate view, namely, that the initial stages of sintering, at least, proceed as a self-diffusion process. Both of these investigations were designed to deal with an isolated unit of sintering, i.e., with the shrinkage of a single pore, or with the growth of a single point weld. It remains to ascertain the behavior of a typical metal powder compact composed of a large number of particles of varying size and sintering to a body with a multiplicity of pores. The observation of density changes alone during sintering is not sufficient in such a case; it is essential to know how the internal geometry of the compact changes. This has been the object of the present investigation, the results of which are used to support the self-diffusion mechanism of sintering. The present studies consist in the measurement of the number of pores as a function of size and time at temperature during the sintering of a copper compact made from a commercial copper powder lightly pressed and sintered in several different atmospheres. A brief survey was made also of the change in shape of the pores, under the influence of the same variables. All of this was done by direct observation with the microscope. Densities were measured on the same sample. It is found that, while the compact is exhibiting an overall shrink-

Jan 1, 1951

By J. T. Norton, J. G. McMullin

An 1820°C isothermal cross section of the Ti-Ta-C ternary diagram was prepared from X-ray diffraction and metallographic data. No phases other than those appearing in the three binary diagrams were observed. At temperatures above the titanium transition temperature titanium and tantalum form a complete series of solid solutions containing up to 2 atomic pct C. The phases Tic and TaC also form a continuous series of solid solutions extending across the diagram. PREVIOUS work on this alloy system was very limited. Of the three binary constitution diagrams involved, only one, the Ta-C system was available in the literature. Preliminary data on the other two systems was received from the investigators during the course of the investigation and both have been published in recent months. It had been shown that Tic and TaC formed a continuous series of solid solutions, but the range of carbon content in this phase was not known. While Ta2C had been described, its solubility for or reactions with other carbides had not been reported. It was not known whether or not any ternary compounds occurred in the system. The present program was undertaken to determine experimentally the general form of the ternary diagram. It is hoped that the results will be of value in furthering the development of sintered carbide cutting materials and high temperature ceramets, many of which contain combinations of Tic and TaC. The Binary Systems Of the three binary diagrams involved only that of Ta-C was available at the time this project was started. The diagram of Ellinger¹ redrawn in Fig. 1, shows a hexagonal phase Ta2C having a very small composition range and a cubic TaC phase having a composition range of from 40 to 50 atomic pct C. The authors made a separate determination of the composition range of TaC using lattice constant values and found the range to extend from 40 to 49.7 atomic pct C in good agreement with Ellinger's diagram. Two determinations of the Ti-Ta system have appeared recently.2,3 These two diagrams are in good agreement and show that ß titanium and tantalum form a complete series of solid solutions. The Ti-C diagram by Cadoff and Nielsen4 shows a very limited solubility of carbon in both a and ß titanium. The single carbide formed persists over a wide range of carbon contents. Several values for the upper limit of carbon content of this phase have been reported."' The highest value obtained in the M.I.T. Laboratory was 47.5 atomic pct C with a lattice constant of 4.328?.5 Fattinger7 describes a gas carburization method which he claims produces stoichiometric Tic although he does not present any data showing that he actually had 50 atomic pct combined carbon. Several complete analyses on

Jan 1, 1954

By C.H. Lorig, M.C. Udy

Through the years much interest has been centered in attempting to develop a direct method of iron-ore reduction, to replace or supplement the present indirect blast-furnace process. It would not be difficult to produce a list of more than 500 patents dealing with the direct production of iron and steel, but the few of this type of process that have proved successful do not produce in competition with the blast furnace; they produce special products. A survey of the literature reveals that the equilibrium conditions for the reduction reactions (iron oxides with carbon monoxide and with hydrogen) have been fairly well established but that data on the rate of reaction are discordant, although the genera1 effects of the variables are known. This dissertation deals with the rate of reduction of a magnetite concentrate with hydrogen. The following variables have been studied: bed depth, gas velocity, particle size and temperature. The behavior of a single particle was also studied. Literature Two general factors should be considered in a study of reduction of iron oxide: (I) equilibrium relations, and (2) rate of reaction. The first factor, equilibrium, has received the attention of many investigators and the equilibria Fe304-FeO-H2-H2O, Fe3O4-FeO-CO-CO2, FeO-Fe-H2-H2O, FeO-Fe-CO-CO2 are fairly well established. Of the second factor, the rate of reaction, much less is known. Data are comparatively scarce and there is very little concordance. The discordance probably results from the large number of variables influencing the reactions. However, the general effect of the variables is known. Among these variables are temperature, gas velocity, particle size, porosity, gas composition (distance from equilibrium), presence of impurities, greater or less prevalence of side reactions, and even design of the apparatus itself. Wetherill and Furnasl published an excellent paper in 1934. They point out that any one or more of five processes (the chemical reaction, diffusion of the reactant through the gas film, diffusion of the reactant through the solid phase, diffusion of the reaction product through the solid phase, or diffusion of the reaction product through the gas film) may be the slow process, and thus the rate-controlling process. It is regretted that the work of these authors was limited to experiments at One temperature, and that the range of gas compositions was limited. Langmuir2 has shown that heterogeneous reactions take place at phase boundaries.

Jan 1, 1943

By M. C. Udy, C. H. Lorig

Through the years much interest has been centered in attempting to develop a direct method of iron-ore reduction, to replace or supplement the present indirect blast-furnace process. It would not be difficult to produce a list of more than 500 patents dealing with the direct production of iron and steel, but the few of this type of process that have proved successful do not produce in competition with the blast furnace; they produce special products. A survey of the literature reveals that the equilibrium conditions for the reduction reactions (iron oxides with carbon monoxide and with hydrogen) have been fairly well established but that data on the rate of reaction are discordant, although the genera1 effects of the variables are known. This dissertation deals with the rate of reduction of a magnetite concentrate with hydrogen. The following variables have been studied: bed depth, gas velocity, particle size and temperature. The behavior of a single particle was also studied. Literature Two general factors should be considered in a study of reduction of iron oxide: (I) equilibrium relations, and (2) rate of reaction. The first factor, equilibrium, has received the attention of many investigators and the equilibria Fe304-FeO-H2-H2O, Fe3O4-FeO-CO-CO2, FeO-Fe-H2-H2O, FeO-Fe-CO-CO2 are fairly well established. Of the second factor, the rate of reaction, much less is known. Data are comparatively scarce and there is very little concordance. The discordance probably results from the large number of variables influencing the reactions. However, the general effect of the variables is known. Among these variables are temperature, gas velocity, particle size, porosity, gas composition (distance from equilibrium), presence of impurities, greater or less prevalence of side reactions, and even design of the apparatus itself. Wetherill and Furnasl published an excellent paper in 1934. They point out that any one or more of five processes (the chemical reaction, diffusion of the reactant through the gas film, diffusion of the reactant through the solid phase, diffusion of the reaction product through the solid phase, or diffusion of the reaction product through the gas film) may be the slow process, and thus the rate-controlling process. It is regretted that the work of these authors was limited to experiments at One temperature, and that the range of gas compositions was limited. Langmuir2 has shown that heterogeneous reactions take place at phase boundaries.

Jan 1, 1943

By B. M. Larsen, T. E. Brower

THIS discussion is based on statistical manipulation and evaluation of operating data from several commercial blast furnaces which include rather wide variations in practice. We are concerned here mainly with the effect of manganese on sulphur elimination under operating conditions in commercial blast furnaces, but this effect can be outlined more clearly by including certain other variables such as silicon in iron and slag basicity, which are all in part interrelated. Real progress in understanding all of the smelting-zone reactions in this process requires more laboratory studies of slag-metal melts similar to those in the blast furnace, with careful control of oxygen pressure. Such experimental work is very difficult, however, and in the meantime, with the present scarcity of more fundamental data, such statistical trends and correlations as can be obtained from commercial furnace operating records may help in choosing laboratory test conditions as well as adding to our knowledge of operating procedures. We do not know just why the furnace data are apparently so irregular that statistical treatment of large numbers is needed to obtain accurate trends. It is partly caused, no doubt, by the many simultaneous variables present, but there are perhaps also such factors as: (I) the con- tinual swings up and down so characteristic of the process; (2) difficulty of accurate sampling of co-existing phases, as well as (3) the presence of both equilibrium and rate factors as a result of the fast driving of the process. In desulphurization, for example, the flow of thin layers of slag and metal over solid coke surfaces, plus the contact between droplets of iron falling through the slag layer in the hearth, would lead one to expect a close approach to equilibrium. On the other hand, most of the critical part of sulphur removal may occur in a short time and distance below the tuyeres with perhaps an accompanying decrease in oxygen pressure and the concurrent reduction of much of the silicon and manganese, so its degree of approach to equilibrium may be quite variable. Probable Chemistry of Desulphurization Since there is little evidence that sulphur atoms in the iron solution are aasociated to any appreciable extent in molecules such as MnS, the transfer from slag to metal and back again can be written:* (FeS) ? [FeS], [I] hence the following reactions seem most probable in the slag phase, (FeS) + (CaO) ? (CaS) + (FeO), [2] and, (FeS) + (MnO) ? (MnS) + (FeO). 131

Jan 1, 1949

By B. M. Larsen, T. E. Brower

THIS discussion is based on statistical manipulation and evaluation of operating data from several commercial blast furnaces which include rather wide variations in practice. We are concerned here mainly with the effect of manganese on sulphur elimination under operating conditions in commercial blast furnaces, but this effect can be outlined more clearly by including certain other variables such as silicon in iron and slag basicity, which are all in part interrelated. Real progress in understanding all of the smelting-zone reactions in this process requires more laboratory studies of slag-metal melts similar to those in the blast furnace, with careful control of oxygen pressure. Such experimental work is very difficult, however, and in the meantime, with the present scarcity of more fundamental data, such statistical trends and correlations as can be obtained from commercial furnace operating records may help in choosing laboratory test conditions as well as adding to our knowledge of operating procedures. We do not know just why the furnace data are apparently so irregular that statistical treatment of large numbers is needed to obtain accurate trends. It is partly caused, no doubt, by the many simultaneous variables present, but there are perhaps also such factors as: (I) the con- tinual swings up and down so characteristic of the process; (2) difficulty of accurate sampling of co-existing phases, as well as (3) the presence of both equilibrium and rate factors as a result of the fast driving of the process. In desulphurization, for example, the flow of thin layers of slag and metal over solid coke surfaces, plus the contact between droplets of iron falling through the slag layer in the hearth, would lead one to expect a close approach to equilibrium. On the other hand, most of the critical part of sulphur removal may occur in a short time and distance below the tuyeres with perhaps an accompanying decrease in oxygen pressure and the concurrent reduction of much of the silicon and manganese, so its degree of approach to equilibrium may be quite variable. Probable Chemistry of Desulphurization Since there is little evidence that sulphur atoms in the iron solution are aasociated to any appreciable extent in molecules such as MnS, the transfer from slag to metal and back again can be written:* (FeS) ? [FeS], [I] hence the following reactions seem most probable in the slag phase, (FeS) + (CaO) ? (CaS) + (FeO), [2] and, (FeS) + (MnO) ? (MnS) + (FeO). 131

Jan 1, 1949

By A. H. Daane, J. J. Hanak, F. H. Spedding

IN the study of the rare earths at the authors' laboratory, methods have been devised for preparing pure rare earths and many of their properties'- have been determined. Very little information is found in the literature on the properties of europium metal, which is the scarcest of the naturally occurring rare earths. Since we have recently prepared europium in appreciable quantities, we are in a position to describe the method of preparation and some of the properties of this metal. Metallic europium was first prepared by Klemm and Bommera who heated a mixture of potassium and EuC1, in vacuo, and obtained a mixture of europium metal and KC1. Trombe4 electrolyzed a molten salt bath containing NaC1, KC1 and EuC1, and collected the europium in a molten cadmium electrode as a cadmium alloy. The cadmium was subsequently removed by distillation but the properties of the residue indicate that pure europium was not obtained. McCoy attempted to prepare europium by distilling mercury from europium amalgam, but the stability of the Eu-Hg intermetallic compounds prevented a complete separation of the two elements. The preparation of very pure europium was suggested by previous work in this laboratory1,4 in which ytterbium and samarium were prepared by heating the respective sesquioxides with lanthanum metal turnings to 1450°C in vacuo and distilling ytterbium and samarium from the mixtures. Subsequently, small test experiments showed that europium also could be prepared by this method. A more detailed version of this method was used in the work described in this paper. Klemm and Bommer3 found by X-ray analysis that the metal had a body-centered cubic (bcc) structure with a lattice constant a, = 4.582 ± 0.00A (converted from kX units), with a bulk density of 5.30 g per cu cm. They found europium to be weakly ferromagnetic. Spedding, et al,7 found a,, to be 4.606 ± 0.001A. Barrett' showed that the bcc structure persists throughout the temperature range 5 to 3000K with a, at 5, 78, and 300°K being 4.551 ± 0.003, 4.551 ± 0.004 and 4.577 ± 0.001A, respectively. Trombe1 described europium as being iron gray, malleable, about as hard as neodymium and not attacked by cold water. He estimated the melting point to be between 1100 and 1200°C. Previous work in this laboratory indicated that the pure metal corrodes rapidly in air and reacts with cold

Jan 1, 1959

By J. H. Frye, C. P. Sun

A PRIMARY substitutional solid solution is a solution that has the same crystalline structure as the solvent metal, and in which solute atoms have replaced solvent atoms at random on the host lattice. This replacement usually results in an increase in hardness as measured by conventional penetration tests. The factors controlling this hardness increase have been investigated in some detail for copper and silver aneys.1-5 It has been shown that at least, four factors are involved: (I) concentration of solute, (2) row of the periodic table from which the solute is taken, (3) increase in lattice parameter of the solvent produced by the solute, and (4) work-hardening produced by penetration of the hardness indenter.2,4 The last factor is of the utmost importance. An investigation of the available data2.4 leads to the conclusion that the solutes that produce large hardness increases in copper or silver do so principally because they increase the rate of work-hardening. Furthermore, it is doubtful whether any solute produces appreciable hardening in the absence of plastic deformation and hence work-hardening. Thus it is clear that an understanding of the effect of solutes on rate of work hardening is essential to an understanding of the hardness of solid solutions. This effect of solutes is also important in forming operations such as rolling or deep drawing. The presence of elements that confer rapid rates of work-hardening will increase power consumption and may well decrease the amount of deformation possible between anneals. This paper is the report of an investigation of the factors that control rates of work-hardening in copper and silver solid solutions. The silver and copper alloys considered are those in which all solutes are from the B subgroups or second short period of the periodic table. Experience with hardness, with structure of alloys, and with electrical conductivity has proved that results of a fundamental nature are most likely to be obtained if alloys are made up on the basis of the positions of the constituent elements in the periodic table. In previous work, Meyer analysis data on high-purity copper and silver solid solutions were obtained through careful measurements with fully calibrated equipment and these data were corrected to correspond to a standard grain size. From these corrected Meyer analysis data rates of work-hardening have now been calculated. CALCULATION OF RATES OF WORK- HARDENING The Meyer analyses, on which this study of rates of work-hardening is based, consisted in determining impression

Jan 1, 1944

By Otto H. Henry, J. J. Cordiano

Though powder metallurgy is one of the oldest of metallurgical processes, it is in its infancy as a branch of the modern field of metallurgy. As early as 3000 B.C., the ancients produced implements and weapons of iron by reducing iron ore in a charcoal fire and forging the resultant sponge while still hot into the desired shape. Melting and casting soon superseded the powder metallurgy practice, and it was not until the turn of the twentieth century that powder metallurgy was applied to the commercial manufacture of tungsten lamp filaments. From this beginning, the use of the powder metallurgy process spread" to the manufacture of porous oil-impregnated bearings, cemented carbide tools, contact points, diamond grinding wheels, clutch facings, starter brushes, resin-bonded radio cores, magnets, metallic filters, and other parts. More recently, and particularly during the present war, there has been a definite trend toward the manufacture of machine parts by this process in competition with the more conventional fabricating methods. Notwithstanding these many developments, scientific progress has been slow. While many articles on powder metallurgy have appeared in the press and various publications, there have been too few contributions to our technical societies, with the result that there is a dearth of the type of information necessary for the full development of this science. It is of primary importance that the results of research and development be freely disseminated if powder metallurgy is to realize its fullest potentialities. Purpose of Investigation Excluding the refractory metal field, all commercial powder metallurgical products made by a cold compressing and sintering operation contain voids. These voids can be substantially eliminated by subsequent severe working and heat-treatment, but ' such practice has not proved economical in most applications. By applying heat during the compressing operation, plastic deformation of the powder particles is substantially increased, and the resultant compact or briquette is practically free of voids. However, hot-pressing has many attendant problems, which at present preclude its use in the manufacture of precision parts. The more important of these are to devise: 1. A die steel capable of withstanding high pressures at elevated temperatures. 2. A high-temperature lubricant capable of preventing excessive die wear and welding of the compact to the die walls. 3. A method of retaining a neutral or reducing atmosphere in the compacting zone of the die assembly. 4. A means of ejecting the hot-pressed specimen into a neutral atmosphere until reasonably cold.

Jan 1, 1946

By Otto H. Henry, J. J. Cordiano

Though powder metallurgy is one of the oldest of metallurgical processes, it is in its infancy as a branch of the modern field of metallurgy. As early as 3000 B.C., the ancients produced implements and weapons of iron by reducing iron ore in a charcoal fire and forging the resultant sponge while still hot into the desired shape. Melting and casting soon superseded the powder metallurgy practice, and it was not until the turn of the twentieth century that powder metallurgy was applied to the commercial manufacture of tungsten lamp filaments. From this beginning, the use of the powder metallurgy process spread" to the manufacture of porous oil-impregnated bearings, cemented carbide tools, contact points, diamond grinding wheels, clutch facings, starter brushes, resin-bonded radio cores, magnets, metallic filters, and other parts. More recently, and particularly during the present war, there has been a definite trend toward the manufacture of machine parts by this process in competition with the more conventional fabricating methods. Notwithstanding these many developments, scientific progress has been slow. While many articles on powder metallurgy have appeared in the press and various publications, there have been too few contributions to our technical societies, with the result that there is a dearth of the type of information necessary for the full development of this science. It is of primary importance that the results of research and development be freely disseminated if powder metallurgy is to realize its fullest potentialities. Purpose of Investigation Excluding the refractory metal field, all commercial powder metallurgical products made by a cold compressing and sintering operation contain voids. These voids can be substantially eliminated by subsequent severe working and heat-treatment, but ' such practice has not proved economical in most applications. By applying heat during the compressing operation, plastic deformation of the powder particles is substantially increased, and the resultant compact or briquette is practically free of voids. However, hot-pressing has many attendant problems, which at present preclude its use in the manufacture of precision parts. The more important of these are to devise: 1. A die steel capable of withstanding high pressures at elevated temperatures. 2. A high-temperature lubricant capable of preventing excessive die wear and welding of the compact to the die walls. 3. A method of retaining a neutral or reducing atmosphere in the compacting zone of the die assembly. 4. A means of ejecting the hot-pressed specimen into a neutral atmosphere until reasonably cold.

Jan 1, 1946

By John L. Boardman

BECAUSE of the attention that has recently been given to the health and safety of miners by various organizations such as the A.I.M.E., The American Congress, Mining Section, National Safety Council, as well as the Bureau of Mines and various state mining departments, your committee on health and safety deemed it best to call attention this year to the mine-accident cause that is by far the most important; namely, injuries due to falls of ground, rock, roof and coal. Each of several members of the committee contributed a brief outline of the importance of this accident cause in his district. While these papers were brief, it would require too much time and space to give them in full, therefore we present an outline of each and summation of all. REPORT OF M. D. COOPER, HILLMAN COAL AND COKE CO. M. D. Cooper, Division superintendent, Hillman Coal and Coke Co., Pittsburgh, Pa., contributed the following: During the period from 1930 to 1939. accidents from falls of roof in bituminous mines average 54.3 per cent of all accidents. In mechanized mining, there is a tendency toward reduction in this class of accidents because the operator of the machine is usually at a distance of 10 to 20 ft. from the face, whereas in hand loading the miner is close to the face during most of the shift. No doubt the use of aluminum and light steel beams supported at regular intervals by jacks, a common practice in mechanical mining, has contributed to the favorable record so far developed. REPORT OF M. H. FIES, DE BARDELEBEN COAL CORPORATION Milton H. Fies, Vice-President, DeBardeleben Coal Corporation, Birmingham, Ala., says: With reference to the types of mining, it is suggested that a clear understanding be had as to the character and thickness of the directly overlying strata, with especial consideration to the strength and in some cases an analysis of it. In coal mining, generally speaking, overlying strata higher in silica than others is stronger. In changing from narrow to wide places, the procedure should be experimental, both as to the width and depth of places and as to the nature of the necessary timbering. Since most of the accidents in coal mining particularly are due to falls of roof and coal, this phase of mining should be attacked with vigor There is no substitute for discipline and, in this connection, under present conditions it is important that cooperation by the labor organizations be sought and that a spirit of fairness prevail. Frequent and thorough inspection of all active working places should be made.

Jan 1, 1941