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By Richard A. Walker, John P. Hager

The thermodynamic properties of the Pb-Au system have been determined between 750" and 1075°C by means of the cell Mo, Pb(1) |(PbO-SiO2){l) , SiO2(s) |Pb-Au(1), Mo The activities of lead and gold exhibit negative deviations from ideal behavior; the values of ? pb and ? the raoultain activity coefficients at infinite dilution, being 0.24 and 0.25, respectively, at 1200°K. The liquidus curve for the gold-rich region of the Pb-Au phase diagram has been determined from measure-ments on seven alloy compositions in the two phase region (liquid + Au(s)). The standard free energies of formation of Au2O(l) and Ag2O (1) have been estimated from cell measurements obtained by replacing the alloy electrode with pure liquid gold and silver. A new integral molar heat of mixing curve for the liquid Pb-Au system is presented and the results of previous studies discussed. The contribution of HM to FE was found to be small relative to TSE. THE use of galvanic cells of the type A(l) |A+Za|A - B(l) [I] provides an accurate means for the thermodynamic study of liquid alloy systems. In Part 1&apos; it was shown that cells of type [I] may be extended to higher temperatures and to a wider range of alloy systems if the ion A+Za is incorporated in an appropriate molten oxide phase, rather than in the classical fused salt electrolyte. In the following investigation the experimental method is extended to an investigation of the thermo-dynamic properties of the Pb-Au system by use of the cell: Mo, Pb(l) | (PbO-SiO2)(l), SiO2(S) |Pb-Au(l), Mo [] Previous measurements on liquid Pb-Au alloys were obtained by Kleppa2 by electromotive force measurements on a galvanic cell involving a molten chloride electrolyte. These measurements were confined to temperatures less than 830°C and compositions with X Pb > 0.2 because of the instability of the cell at higher temperatures. Later measurements by Kleppa3 on the heats of formation in the composition range 0.67 < Xpb < 0.98 were not consistent with the results by electromotive force measurement. The purpose of the present study is to extend the temperature and composition range of the thermodynamic properties and to obtain an independent measure of the integral molar heat of mixing over the entire composition range.

Jan 1, 1970

By W. T. Bishop, G. A. Crowe

While the literature in the United States on general polarographic technique is extensive, very little appears to be directly applicable to the analysis of flotation tailings. For this reason, it seemed worth while to present a few polarographic methods of ore analysis that have been in constant use in the laboratories of the Hercules Experiment Station for the past few years. At the time of our initial investigation of the polarographic method, there was little or no mention of its specific application to flotation tailings. It was therefore necessary for us to establish suitable conditions for the analysis of our flotation tailings and to consider possible interfering constituents. The polarograph, or dropping mercury electrode, method was discovered in 1925 by J. Heyrovsky and M. Shikata,1 of the Charles University, Prague. This method has since received extensive development and the literature contains many articles on the use of the polarograph for the quantitative determination of metals as well as anions, oxygen in solution, and reducible organic compounds. Kolthoff and Lingane,² by the publication of their book, "Polarography," in 1941 did much to advance the knowledge and use of the polarograph. In chapter 25 of that book, methods for the polarographic analysis of brass, steel and iron products, alloys, and zinc ore are given. Aluminum,³ cadmium,³,4 cobalt,4 cop-per,³-9 gold,10 iron,3,11 lead,³,l2,l³ molybdenum,14 nickel,4,8,9 tin," and zinc³,4,5,7 in ores have been analyzed by the polarograph. However, most of the work on tailing samples has been published in Russian journals and translations are not yet readily available. In this paper we will describe the method that was developed and used in our laboratory for the determination of copper, zinc, and lead in flotation tailings. Principle OF the Method The polarograph is an instrument for applying a potential to a mercury pool and a dropping mercury electrode separated by a solution, and for measuring the resultant electrical current. The procedure is essentially a small-scale electrolysis, in which the voltage required to reduce or oxidize the material identifies it qualitatively and the current measures the concentration quantitatively. Different constituents in a sample may often be determined simultaneously provided they reduce at sufficiently different voltages. An example is the determination of copper and zinc in the same solution. The reduction potentials are quite far apart, as shown in Fig. I. The polarographic method is particularly useful in the range of concentration between those normally determined by spectographic and chemical methods. In

Jan 1, 1947

By G. A. Crowe, W. T. Bishop

While the literature in the United States on general polarographic technique is extensive, very little appears to be directly applicable to the analysis of flotation tailings. For this reason, it seemed worth while to present a few polarographic methods of ore analysis that have been in constant use in the laboratories of the Hercules Experiment Station for the past few years. At the time of our initial investigation of the polarographic method, there was little or no mention of its specific application to flotation tailings. It was therefore necessary for us to establish suitable conditions for the analysis of our flotation tailings and to consider possible interfering constituents. The polarograph, or dropping mercury electrode, method was discovered in 1925 by J. Heyrovsky and M. Shikata,1 of the Charles University, Prague. This method has since received extensive development and the literature contains many articles on the use of the polarograph for the quantitative determination of metals as well as anions, oxygen in solution, and reducible organic compounds. Kolthoff and Lingane,² by the publication of their book, "Polarography," in 1941 did much to advance the knowledge and use of the polarograph. In chapter 25 of that book, methods for the polarographic analysis of brass, steel and iron products, alloys, and zinc ore are given. Aluminum,³ cadmium,³,4 cobalt,4 cop-per,³-9 gold,10 iron,3,11 lead,³,l2,l³ molybdenum,14 nickel,4,8,9 tin," and zinc³,4,5,7 in ores have been analyzed by the polarograph. However, most of the work on tailing samples has been published in Russian journals and translations are not yet readily available. In this paper we will describe the method that was developed and used in our laboratory for the determination of copper, zinc, and lead in flotation tailings. Principle OF the Method The polarograph is an instrument for applying a potential to a mercury pool and a dropping mercury electrode separated by a solution, and for measuring the resultant electrical current. The procedure is essentially a small-scale electrolysis, in which the voltage required to reduce or oxidize the material identifies it qualitatively and the current measures the concentration quantitatively. Different constituents in a sample may often be determined simultaneously provided they reduce at sufficiently different voltages. An example is the determination of copper and zinc in the same solution. The reduction potentials are quite far apart, as shown in Fig. I. The polarographic method is particularly useful in the range of concentration between those normally determined by spectographic and chemical methods. In

Jan 1, 1947

By D. W. G. White

The surface tension of zinc has been determined by the sessile-drop method in a progvam emphaszzing detailed experimental care. The surface tension oj. the pure metal was measured over a range of ternperature from the melting point (419.6"C) to 540°C. At the melting point, the suvface tension of zinc was found to be: 1) 99.99+ pct Zn - 757.0 5 dynes per cm 2) 99.999+ pct Zn - 761.0 5 dynes per CI 3) 99.9999 pct Zn - 76&apos;7.5 5 dynes pev cna From experiments carried out in a closed, isothermal cell, the temperatuve coejyicient of the surface tension (6y/6T)p, , of zinc xas found not to be negative but to be postiue. A positive tenzperatre coefficient indicates a greater depee of order in the surface than in the body of the lquid. Houlezer, by delibevately inducing continuous zaporization, a temperature coefficient of su)face tension with a negative slope can be produced. The work reported herein was undertaken as part of a larger program of fundamental research on the properties of molten zinc and zinc alloys. This program grew out of a continuing interest at the Mines Branch in the behavior of liquid metals in the foundry and of a desire on the part of the zinc industry for reliable basic data. The work was originally begun in cooperation with the Consolidated Mining and Smelting Co. Ltd., Trail, B.C., and was subsequently continued from 1960 to date in association with the Canadian Zinc and Lead Research Committee and the International Lead and Zinc Research Organization. Although the surface tension of liquid zinc has of course, been measured before, as Table I and Fig. 1 demonstrate, there is not good agreement among the existing values. Such disparities arise because sources of experimental error are insufficiently controlled. This situation places the reader in doubt. One result may be correct within narrow limits—even fortuitously—yet, because there is not agreement between several values, none can be accepted with conviction and all become suspect. It seemed, therefore, in the circumstances, that there was room for further work embodying considerable emphasis on experimental care in order that, within a small margin of error, an accurate value might be obtained. It was in this spirit that the work was undertaken. METHOD The sessile-drop method -as adopted for this work. In this method, when applied to liquid metals at elevated temperatures, the outline of the meridional section through a drop resting freely on a horizontal surface is recorded photographically. Certain parameters

Jan 1, 1967

By Helmut Thielsch

MeTallographic specimens whose surfaces are to be investigated are too thick to allow either light or electrons to pass through them for microexamination by transmission. This difficulty is overcome with optical microscopes by illuminating the surface through the objective lens. For electron microscopes best results are obtained by preparing thin replicas of the surface of the specimen, placing them in the microscope and passing the electron beam through them. Since electron microscopes represent a rather recent invention, they have found little application as compared with optical microscopes. This is true because, aside from the cost of new equipment and development of new techniques, some of the older replica methods necessitated the destruction of the surface from which a thin transparent replica was obtained. In other processes in which the surface is preserved, either too tedious a procedure is required, unsuited to "mass-production" requirements of industrial laboratories, or replicas of insufficient contrast and sharpness are produced. In general, investigations with the electron microscope involve five steps: (I) polishing the surface of the metal specimen, (2) proper etching of the surface, (3) preparing the suitable replica from the surface, (4) examination and phorography in electron microscope and (5) interpretation. Preparation of Metal Surfaces Usual metallographic polishing is generclly satisfactory. It is important though that the final polish be applied very carefully, since otherwise evidence of a small amount of deformation might show up even on relatively deeply etched surfaces. A high-power microscope should be used to determine the suitability of the polish and etch. This, of course, is not different from optical examinations, but in these, if a deep etch is used, the problem is less serious. It is frequently difficult to detect with optical microscopes poor polishing aside fiom superficial scratches before etching. Figs. I and 2 show micrographs of "well" and "poorly" polished nickel etched by immersing the sample for 20 min. in a solution containing 8 grams cupric sulphate in 40 C.C. of concentrated HCl and 40 C.C. of Hz0 (Marble&apos;s reagent). The sample shown in Fig. I was polished in its final stages for 5 min. on a carborundum wheel followed by ro min. on a rouge wheel, whereas the sample shown in Fig. 2 was polished only I min. on the rouge wheel. Generally, this procedure does not guarantee that the surface of the specimen will be either undistorted or deformed. It was applied here merely to show the effects Of good and poor polishing. To the experienced investigator, plastic deformation is

Jan 1, 1946

By Helmut Thielsch

MeTallographic specimens whose surfaces are to be investigated are too thick to allow either light or electrons to pass through them for microexamination by transmission. This difficulty is overcome with optical microscopes by illuminating the surface through the objective lens. For electron microscopes best results are obtained by preparing thin replicas of the surface of the specimen, placing them in the microscope and passing the electron beam through them. Since electron microscopes represent a rather recent invention, they have found little application as compared with optical microscopes. This is true because, aside from the cost of new equipment and development of new techniques, some of the older replica methods necessitated the destruction of the surface from which a thin transparent replica was obtained. In other processes in which the surface is preserved, either too tedious a procedure is required, unsuited to "mass-production" requirements of industrial laboratories, or replicas of insufficient contrast and sharpness are produced. In general, investigations with the electron microscope involve five steps: (I) polishing the surface of the metal specimen, (2) proper etching of the surface, (3) preparing the suitable replica from the surface, (4) examination and phorography in electron microscope and (5) interpretation. Preparation of Metal Surfaces Usual metallographic polishing is generclly satisfactory. It is important though that the final polish be applied very carefully, since otherwise evidence of a small amount of deformation might show up even on relatively deeply etched surfaces. A high-power microscope should be used to determine the suitability of the polish and etch. This, of course, is not different from optical examinations, but in these, if a deep etch is used, the problem is less serious. It is frequently difficult to detect with optical microscopes poor polishing aside fiom superficial scratches before etching. Figs. I and 2 show micrographs of "well" and "poorly" polished nickel etched by immersing the sample for 20 min. in a solution containing 8 grams cupric sulphate in 40 C.C. of concentrated HCl and 40 C.C. of Hz0 (Marble&apos;s reagent). The sample shown in Fig. I was polished in its final stages for 5 min. on a carborundum wheel followed by ro min. on a rouge wheel, whereas the sample shown in Fig. 2 was polished only I min. on the rouge wheel. Generally, this procedure does not guarantee that the surface of the specimen will be either undistorted or deformed. It was applied here merely to show the effects Of good and poor polishing. To the experienced investigator, plastic deformation is

Jan 1, 1946

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.&apos; 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 Grover J. Holt

A DETAILED description of the many variations in iron mining and transportation practice in Minnesota would require much space. Since a fairly detailed description of the practices then in use was published in the guidebook issued in connection with the meeting of the Institute on the iron ranges in I920, and subsequent developments have been described by E. E. Hunner,1 M. H. Barber,2 and A. E. Anderson, J. M. Riddell and G. J. Holt,3 it will not be necessary here to do more than review the highlights of current practice. Details on any points of interest can be obtained through correspondence with the operators involved. [T] The iron ores of Minnesota, which have been formed through enrichment of the iron formation in which they occur, largely by the removal of silica, are usually covered by a blanket of glacial drift known locally as "surface." Surface material, including sand, clay, hardpan and boulders, makes up the greater portion of the stripping in open-pit operations. In some instances, stripping also includes taconite and "paint rock," directly below the surface material and overlying the ore. Taconite is the iron formation, a ferruginous chert with interbedded slate layers. "Paint rock" is a local term for oxidized slate layers interbedded in the iron formation, high in phosphorus, alumina and moisture. The iron ores fall into two classes: (I) direct shipping (merchantable ores or ores requiring no treatment except possibly crushing or screening to make an acceptable sized product), and (2) ores requiring beneficiation (such as sintering, drying, washing, jigging, high-density treatment, or magnetic separation in the case of magnetite). The Mesabi Range produces chiefly soft Bessemer and non-Bessemer ores. The Cuyuna Range produces mainly low-manganese brown ore and high-manganese black ores, with some iron ore. The Vermilion Range yields mainly Besse¬mer and non-Bessemer iron ore, with some hard or lump ore that finds use in the open hearth. Open-pit mining is limited to the Mesabi and Cuyuna Ranges but underground mining is done on all three. The choice of mining methods is determined by the relative economics of overburden¬-removal and shaft-mining costs. STRIPPING PRACTICE Common practice has been to remove the bulk of the overburden during the winter season and to mine during the summer. In the present emergency many operators are forced to forego the economies attained by year-round utilization of equipment and to equip for, and carry on, stripping and mining simultaneously. In the normal years or lean years to come, most properties probably will be over-equipped and high depreciation charges will have to be absorbed.

Jan 1, 1942

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

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&apos; 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&apos;F and higher,

Jan 1, 1947

Apparatus and a method for determining the volumetric behavior of hydrocarbons at pressures up to 10,000 psia and at temperatures between 0° and 460°F are described. The equipment is suitable for measuring the total volume of the system and the volume of a liquid phase as functions of state within these ranges of temperature and pressure. Introduction During the past two decades there has been a marked increase in the ranges of temperature and pressure encountered in underground hydrocarbon reservoirs of commercial interest. In addition, greater interest in the intensive characteristics of the fluids found in these reservoirs has developed. Apparatus Several types of apparatus have been developed in the authors&apos; laboratory for volumetric measurements of hydrocarbon systems. The earliest equipment described1 was characterized by constant volume, and the weight of material present was varied systematically in order to attain the different pressures desired in the study. Later another apparatus2 was built in which the effective volume of the cylindrical cell, which confined a hydrocarbon sample of constant weight was varied by injection or withdrawal of mercury. The effective total volume of the equilibrium cell was measured by ascertaining the position of the mercury surface but no measurement could be made which gave knowledge of the volumes of individual phases existing within the hydrocarbon system. A third apparatus3 was designed for use at higher pressures and temperatures than the earlier equipment would tolerate. This apparatus was of the variable volume type but was built in the general form of a U-tube, the mercury level being measured at the surface which was not exposed to the hydrocarbon system. This arrangement avoided the need of subjecting measuring equipment to the extremes of temperature at which studies were made, but it gave no provision for measurement of the volumes of individual phases. Although this last apparatus was satisfactory as to accuracy and convenience for many purposes, need was felt for measurements of the volume of the liquid phase of the hydrocarbon system. For this reason a fourth equilibrium apparatus was designed and constructed, and it is the purpose of the present paper to describe it. The equilibrium cell has a working range of temperature from 0° to 460°F at pressures up to 10,000 psi. Provision for measurement of both total volume and liquid-phase volume makes it particularly suitable for the equilibrium study of heterogeneous systems consisting either of simple mixtures or of complex field samples of hydrocarbons. The general arrangement of the ap-

Jan 1, 1948

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&apos; 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&apos;F and higher,

Jan 1, 1947

By Walter R. Hibbard, Ming-Kao Yen

VARIOUS rationalizations of preferred orientations in cold worked polycrystalline metals have been based on the operation of at least two,1 three,2 five,4 an indefinite number,5 and all,6 slip systems of the type occurring in single crystals. Pickus and Mathewson3 suggested that the cold rolling texture in face-centered cubic metals could be rationalized on the basis of two or more operating slip directions symmetrically disposed about the direction of flow in such a manner that the resolved shear stress factor is equal for all operating slip systems and lattice rotations cancel each other. The importance of the direction of flow, † the necessity for the operation of slip systems capable of producing the required, changes in external dimensions, the maintenance of a common surface between adjacent grains and a symmetrical arrangement of the operating slip systems in order to produce an end orientation which is stable under additional deformation lead to the following rationalization of textures based on the type of slip systems operative in single crystals. The rationalization is intended to explain why certain orientations are suitable for deformational flow without a change in orientation and thus are stable end orientations or ideal texture orientations. It does not attempt to explain how the grains of a randomly oriented polycrystalline aggregate will reach this orientation. The rationalization is based on the following four postulates: I. The ideal textures for polycrystalline aggregates are the result of reorientations of individual crystals toward the same stable end orientation at which no further reorientation will occur even during additional deformation. Since, in simple slip, - the relative orientations of the stress axis and the active slip system determine the change in orientation during slip, it is considered that the orientation of the stress axis with respect to the ideal texture determines what slip systems must be active to retain the stable end orientation. Therefore the stable end orientation should be a symmetrical one around the stress axis with respect to the active slip systems such that lattice rotations resulting from slip will cancel each other and prevent a resultant change in orientation. (Rotational symmetry only-not translation, inversion, nor others-is considered here.) Thus a metal under a pure stress should develop a texture consisting of one or more of the crystallographically symmetrical directions, <100>, <110> or <111> for cubic metals or <0001>, <1010> or <1120> for hexagonal dose-packed metals, parallel to the stress axis. 2. Since the active slip direction is the direction of glide during simple slip and thus the direction of maximum shear movement, in the ideal texture the active slip

Jan 1, 1948

Apparatus and a method for determining the volumetric behavior of hydrocarbons at pressures up to 10,000 psia and at temperatures between 0° and 460°F are described. The equipment is suitable for measuring the total volume of the system and the volume of a liquid phase as functions of state within these ranges of temperature and pressure. Introduction During the past two decades there has been a marked increase in the ranges of temperature and pressure encountered in underground hydrocarbon reservoirs of commercial interest. In addition, greater interest in the intensive characteristics of the fluids found in these reservoirs has developed. Apparatus Several types of apparatus have been developed in the authors&apos; laboratory for volumetric measurements of hydrocarbon systems. The earliest equipment described1 was characterized by constant volume, and the weight of material present was varied systematically in order to attain the different pressures desired in the study. Later another apparatus2 was built in which the effective volume of the cylindrical cell, which confined a hydrocarbon sample of constant weight was varied by injection or withdrawal of mercury. The effective total volume of the equilibrium cell was measured by ascertaining the position of the mercury surface but no measurement could be made which gave knowledge of the volumes of individual phases existing within the hydrocarbon system. A third apparatus3 was designed for use at higher pressures and temperatures than the earlier equipment would tolerate. This apparatus was of the variable volume type but was built in the general form of a U-tube, the mercury level being measured at the surface which was not exposed to the hydrocarbon system. This arrangement avoided the need of subjecting measuring equipment to the extremes of temperature at which studies were made, but it gave no provision for measurement of the volumes of individual phases. Although this last apparatus was satisfactory as to accuracy and convenience for many purposes, need was felt for measurements of the volume of the liquid phase of the hydrocarbon system. For this reason a fourth equilibrium apparatus was designed and constructed, and it is the purpose of the present paper to describe it. The equilibrium cell has a working range of temperature from 0° to 460°F at pressures up to 10,000 psi. Provision for measurement of both total volume and liquid-phase volume makes it particularly suitable for the equilibrium study of heterogeneous systems consisting either of simple mixtures or of complex field samples of hydrocarbons. The general arrangement of the ap-

Jan 1, 1948

By Gustav S. Preller, A. M. Gaudin

Fox the past 20 years it has been generally accepted that the flotation process is made possible as a result of the action of certain chemical substances on the surface of the mineral particles. In fact, it has been suspected, but never demonstrated, that this action produces on the mineral particles a layer of chemosorbed ions that is of the order of magnitude of a monolayer; that is, of a layer one ion deep. It is the purpose of this paper to present certain initial results on the relationship of mineral surface area and collecting-agent requirements. Up to about eight years ago, all considerations involving the surface area of finely divided solids were-limited by the fact that there was not in existence any general method for determining the extent of such surfaces, especially on mixed materials. However, the method invented by Brunauer, Emmett and Teller1 has changed the situation by providing a general procedure (BET method). This procedure has already been applied to mineral dressing problems2 -4 and has now received confirmation as to accuracy by an entirely independent method.5 This confirmatory or "absolute" method uses a very tedious calorimetric procedure and is not suitable for routine determinations; but still another method6 now is available to relate the results obtained by the BET method to those obtained calorimetrically. This Harkins-Jura method has the advantage that it does not require an assumption concerning the parking area per molecule of adsorbate (nitrogen). In the original work by Brunauer, Emmett and Teller the parking area per nitrogen molecule was calculated to be either 13.8Å2. or 16.2Å2. according as the nitrogen was assumed to be closely packed as in crystalline nitrogen or loosely packed as in liquid nitrogen. The initial experimental work from this laboratory2 supported the 13.8Å2. figure; that work was done on glass spheres of measurable geometric area and it was based on the assumption that the glass spheres were truly smooth; any deviation from this assumption would, of course, have made the calculated parking area higher. Harkins and Jura&apos;s results suggest that the parking area is not the same for all substrata; furthermore, the average of the 87 measurements cited indicates a "preferred" parking area for the nitrogen molecule of about 15.2Å2., with extreme values at 13.7 and 16.9Å2. The average of 21 determinations made in connection with this study&apos; gave a parking area of 14.3 ± 0.27Å2. In view of this result and of the Harkins and Jura

Jan 1, 1946

By H. M. Stewart, R. A. Grange

MANY steel parts may crack if quenched directly into a bath near room temperature, but not if quenched at a temperature just above the range where martensite forms and then allowed to cool slowly to room temperature. This latter procedure, which is the basis for such modern hardening techniques as "martempering " and "isothermal quenching," may entail some sacrifice in depth of hardening but very little, if any, in intensity of hardening. In planning such treatments, it is necessary to know the upper limit of the martensite range, and often desirable to know the proportion of martensite that would form on cooling to any lower temperature; furthermore, the tendency of a particular steel to crack when quenched is unquestionably associated with the temperature range of martensite formation, and consequently knowledge of this range aids in selecting the optimum composition for a given application. Certain puzzling phenomena associated with the properties of quenched and tempered steel may be at least partly clarified as the manner in which martensite forms is more fully under- stood. Information on the temperature range of martensite formation, particularly with respect to how much martensite results from quenching to a given temperature, is lacking for most commercial types of carbon and low-alloy steel. These considerations led us to study martensite formation in 14 carbon and low-alloy steels. The resultant data may be directly used in the following ways: (I) for selecting the lowest quenching temperature at which no martensite will form; (2) for selecting the highest quenching temperature at which virtually dl marten- site will form, thereby avoiding quenching to an unnecessarily lower temperature with attendant danger of cracking; and (3) in producing a mixture of tempered marten- site and bainite, which in high-carbon steels has been found to possess somewhat better ductility than tempered martensite, yet does not require the full transformation time necessary for a completely bainitic (austempered) structure. PART I. OBSERVATIONS OF MARTEN- SITE FORMATION IN FOURTEEN CARBON AND LOW-ALLOY STEELS Transformation of austenite to pearlite or bainite can be conveniently studied by observing the change that occurs over a period of time at constant temperature; such studies are the basis of the isothermal transformation diagram (S-curve). This isothermal technique is not applicable to martensite formation, which occurs within a time interval too small to measure, at least by any ordinary means. For all practical purposes, therefore, martensite may be regarded as forming only during cooling and not during a period of time at constant temperature. As austenite is cooled below

Jan 1, 1946

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 H. M. Otte

Certain choices for the shear elements of the inhomogeneous distortion in the phenomenological theory of martensite formation are examined for their agreement with crystallographic and X-ray data of iron alloys. The assumption that the shear elements must represent slip or twinning systems characteristic of bcc metals is found to covey all observations, even when a small uniform dilatation is taken into consideration. In bct martensite, (011) becomes a possible twinning or faulting plane, in addition to {112), and qualitatively similar X-ray line broadening is to be expected from both. The basic concept inherent in the current theoriesl-4 of the formation of martensite is that the interface between the parent (austenitic) and product (martensitic) phase is an invariant strain plane (i.e., one that is undistorted and unrotated). Experimental evidence that the interface is of such a nature is available in certain transformations2&apos;5&apos;6 but for the transformation in iron alloys direct observation has not proved enlightening. Internal strains resulting from the formation of the small martensite platelets within the parent austenite matrix7 make it difficult to produce the desired evidence. Indirect evidence, however, such as the continuity of scratches in passing from untrans-formed to a transformed region, strongly indicates that the habit plane in iron alloys is an invariant strain interface. The scatter in habit planes in a given specimen8 would suggest that internal stresses have a slight but definite influence. On the other hand, composition changes which affect the lattice parameter can alter the habit plane appreciably, and by an amount greater than the scatter.&apos; The success of the theories depends on the choice made for the "inhomogeneous distortion" or "complementary shear&apos;&apos; in the analysis and also on the choice for the parameter 6 representing a small uniform dilatation. In the approach developed by Wechsler, Lieberman, and Read&apos;," it is implicitly assumed that 6 is unity. In the case of iron alloys, all observations cannot be explained without varying either the inhomogeneous distortion or 6 . Bowles and Mackenzie3 considered only the effect of varying d. They found it difficult to reconcile the wide scatter of habit planes with the theory and were forced to the conclusion that it may also be necessary to consider variations or different choices of the inhomogeneous distortion. Wechsler and Read" considered a limited number of possible choices for the inhomogeneous distortion, but no variation in 6, though this could easily have been introduced if so desired. It is the purpose of the

Jan 1, 1961

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 J. M. Callow

H. A. MEGRAW, New York, N.,Y.-One interesting thing that might be brought out in this connection is the cost of making sulphide gas. I had a communication the other day which suggested that, in view of the high cost of oil, sulphur and sodium sulphide, we might make use of a well-known chemical reaction to form this sulphide gas by the use of aluminum sulphide. It is difficult to see any advantage in this, however, since aluminum has been affected just as much as any other commodity by the rise in prices, due, to war conditions. RUDOLF GAHL, Miami, Ariz. (communication td the Secretary*) Mr. Callow refers to my paper, History of Flotation at Inspiration, which was presented at the Arizona meeting of the Institute. These notes of Mr. Callow&apos;s contain much valuable information on flotation practice, as is to be expected from an article written by an author of Mr. Callow&apos;s experience in this branch of metallurgy. Nevertheless, I cannot help contradicting a number of the statements made in the references to my paper. In passing, I will also say a word about the reference in Mr. Callow&apos;s paper to the article by Messrs. Laist and Wiggin entitled "Flotation Concentration at Anaconda, Mont." Mr. Callow calls attention to the fact that evidently Callow flotation machines are not very sensitive, inasmuch as one man per shift handles four 800-ton sections of Callow machines or 3,200 tons per day at the Inspiration plant. While-it has been the experience of the Inspiration company that the four sections of Callow machines in the Inspiration concentrator are easily handled by one American operator per shift, it is only fair to state that each man operating four sections is assisted by two Mexican helpers who constantly clean the bottoms of the machines. The tonnage per section, by the way, whether equipped with Callow,, Inspiration or Minerals Separation machines, is considerably in excess 4 800 tons.. Mr. Callow further says that local opinion at Inspiration is that, two 800-ton sections consisting of two 10-compartment and four 6-compartment Minerals Separation machines (these machines are of the Hebbard type) is the limit that one man can properly attend. I do not hesitate to say that I consider it perfectly feasible to have four such sections operated by one man, perhaps assisted by "one helper. The Minerals Separation machines of this type have undoubtedly an advantage as far as easiness of operation is concerned,

Jan 4, 1917