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By B. F. Oliver

Equilibrium and kinetic segregation coefficients for the dilute high-temperature system tantalum in iron have been experimentally determined in a levitating zone melter. The equilibrium segregation coefficient, ko, is 0.43 * 0.03. Planar interface solidification is possible up to a freezing velocity of 4 in. per hr but not at 6 in. per hr. Precise concentration control of the solid is possible over this range of freezing velocities. The momentum boundary layer thickness, and the diffusion boundary layer thickness, 6, are such that either 6, > 6 or ALTHOUGH considerable data exists in the literature concerning the stability of planar-solidification fronts, little data exists for high-temperature metallic systems. The study of fundamental aspects of solidification in high-temperature iron-base systems is complicated by the extensive solvent power of liquid iron. In order to minimize such effects a levitating zone melter was used to study the segregation of tantalum in iron.' The solute tantalum was selected because: 1) the ko value was, according to the literature, initially thought to be less than 0.1, thus increasing the precision of the method used;2,3 2) the vapor pressure and is a constant, fixed by induction stirring, 6, the diffusion boundary layer, is 5150 u. At 400 rpm and 6 in. per hr freezing velocity the cast structure exhibits circular macroporosity and banding concentric with the axis of the rotation of the interface. Electron-beam microprobe analyses indicate that the tantalum content is highest at the center of rotation (1.2/1) and decreases with increasing radius as the fine-grained bands become sharper. This entire structure exhibits microseg-regation of tantalum. of tantalum in 1 atm of H2 is small, assuring conservation of solute during redistribution; and 3) spec-troscopic analyses were available for the appropriate range of tantalum considered. Additional objectives were 1) to determine kinetic segregation coefficients for well-stirred zones with constant boundary conditions and thus quantitatively calibrate solute-segregation behavior in the levitating zone melter, and 2) to examine the range of freezing velocities over which smooth solid-liquid interfaces could be controlled in an iron-base alloy under the restrictions of the thermal gradients imposed while levitating a zone. The single-pass zone-melting method was used to calculate individual k values.'

Jan 1, 1964

By C Gunther

Mining examinations are of several kinds and the scope of the investigation depends in each case upon the purpose for which the examination is made. A formal examination of a developed mine is an expensive undertaking; from one to several months are allowed for the work according to the size of the property; many samples are taken; investigation is made of the geological features, including, perhaps, a topographical and geological survey of the surface; the metallurgical treatment of the ore is studied; finally, a determination of costs is demanded. Formal examinations are made for prospective purchasers or as a basis for the consolidation of several properties, and occasionally, in the owner's behalf, to verify the work of resident engineers, or to determine the readiness of a mine for equipment and the kind and capacity of equipment it shall receive. A formal examination of a mine should not be undertaken until a preliminary examination has shown that it is justified. It is regrettable that some engineers are in the habit of prosecuting long and exhaustive examinations of properties whose lack of merit should be, and perhaps is, apparent from the start, or of continuing their investigation long after an unfavorable result is seen to be inevitable. This wasting of a client's money is a species of trickery difficult to prove, and therefore the more contemptible. Preliminary examinations are precisely what the term implies, and are undertaken to determine the advisability of making

Jan 1, 1932

By Thomas S. West

A gravel pack completion is described which, in addition to sand screening, permits the exclusion of water and gas from the oil production. A gravel pack composed of alternate layers of different particle sizes is employed which has horizontal but not overall vertical permeability to drilling mud. A packer is run on the tubing and set in the screen member, around which the gravel layers are placed. The hydrostatic pressure of a mud column prevents the entry of fluid above (or below) the level of the packer. The producing level may be changed by raising or lowering the tubing. Vertical coning is controlled by replacing the mud column with oil and continually injecting oil into the sand section above (or below) the packer. Three well histories with this completion are described in detail. Statistics on the first 100 completions of this general type are given. INTRODUCTION Gravel pack type completions have heretofore been almost exclusively for the purpose of preventing sand production. This paper describes and presents well data on a gravel pack procedure which is primarily a selective completion method. Although complete sand screening is achieved, the exclusion of gas and water is the primary objective. The application of this procedure is therefore not limited to unconsolidated sands. Application to hard sand or limestone reservoirs is equally feasible. GRAVEL PACK PROCEDURE Figs. 1 and 2 illustrate the gravel pack procedure employed. The gravel is placed by means of the frangible disc type dump bailer shown by Fig. 1.' This bailer has its lower end closed by a plate glass or steel rimmed cement disc. This disc breaks when the bailer passes over the liner allowing the gravel to be deposited around the liner. The liner employed is usually 2 3/8 in. to 2 7/8 in. OD and 1.995 in. or 2.07 in. ID (ID of 2-in. tubing or 2-in. line pipe). Two tvDes,. of slotted sections have been employed. One type employs horizontal hacksaw cut or milled slots of about 1/32 in. width opposite the producing section. The other type employs the same type,. of horizontal slot. but slots are placed in groups of six at intervals of about 8 in. A cage composed of half round vertical bars, spaced apart, is then welded to the pipe over the slotted sections. This liner has the bottom end closed, usually by bull plugging. The upper end is closed, while placing the gravel, by a cap which is held in place by means of a shear pin. This cap has a mandrel attached to it which extends downward inside of the liner to within a few inches of its lower end. The top of the liner cap is formed to fit a releasing type wire line core barrel overshot. The liner is lowered to bottom on the wire line by means of this overshot and released. The length of the liner is usually suffi- cient to extend to about 20 ft above the highest level to which gravel is to be placed, the upper end of the liner always being in the casing. The dimensions of the liner and bailer are such with respect to the casing size that the bailer will always pass over the liner. After releasing the liner the bailer is run to bottom. Passage of the empty

Jan 1, 1951

By Thomas S. West

A gravel pack completion is described which, in addition to sand screening, permits the exclusion of water and gas from the oil production. A gravel pack composed of alternate layers of different particle sizes is employed which has horizontal but not overall vertical permeability to drilling mud. A packer is run on the tubing and set in the screen member, around which the gravel layers are placed. The hydrostatic pressure of a mud column prevents the entry of fluid above (or below) the level of the packer. The producing level may be changed by raising or lowering the tubing. Vertical coning is controlled by replacing the mud column with oil and continually injecting oil into the sand section above (or below) the packer. Three well histories with this completion are described in detail. Statistics on the first 100 completions of this general type are given. INTRODUCTION Gravel pack type completions have heretofore been almost exclusively for the purpose of preventing sand production. This paper describes and presents well data on a gravel pack procedure which is primarily a selective completion method. Although complete sand screening is achieved, the exclusion of gas and water is the primary objective. The application of this procedure is therefore not limited to unconsolidated sands. Application to hard sand or limestone reservoirs is equally feasible. GRAVEL PACK PROCEDURE Figs. 1 and 2 illustrate the gravel pack procedure employed. The gravel is placed by means of the frangible disc type dump bailer shown by Fig. 1.' This bailer has its lower end closed by a plate glass or steel rimmed cement disc. This disc breaks when the bailer passes over the liner allowing the gravel to be deposited around the liner. The liner employed is usually 2 3/8 in. to 2 7/8 in. OD and 1.995 in. or 2.07 in. ID (ID of 2-in. tubing or 2-in. line pipe). Two tvDes,. of slotted sections have been employed. One type employs horizontal hacksaw cut or milled slots of about 1/32 in. width opposite the producing section. The other type employs the same type,. of horizontal slot. but slots are placed in groups of six at intervals of about 8 in. A cage composed of half round vertical bars, spaced apart, is then welded to the pipe over the slotted sections. This liner has the bottom end closed, usually by bull plugging. The upper end is closed, while placing the gravel, by a cap which is held in place by means of a shear pin. This cap has a mandrel attached to it which extends downward inside of the liner to within a few inches of its lower end. The top of the liner cap is formed to fit a releasing type wire line core barrel overshot. The liner is lowered to bottom on the wire line by means of this overshot and released. The length of the liner is usually suffi- cient to extend to about 20 ft above the highest level to which gravel is to be placed, the upper end of the liner always being in the casing. The dimensions of the liner and bailer are such with respect to the casing size that the bailer will always pass over the liner. After releasing the liner the bailer is run to bottom. Passage of the empty

Jan 1, 1951

By F. E. Smith, David R. Mitchell, B. M. Bird

DENSE-MEDIA processes utilize the familiar laboratory float-and¬-sink procedure on a commercial scale. Just as wood chips float on water and sand sinks, so coal floats and refuse sinks when placed in a medium intermediate in specific gravity between the coal and refuse. Liquids intermediate in specific gravity between coal and refuse used in commercial plants are of four types: (1) Organic liquids of high specific gravity-halogenated hydrocarbons; (2) dissolved salts in water; (3) pseudo liquids obtained by suspending solids, such as sand, in water, and (4) fluidizing a mass of sand or other solids by air currents. Those most widely used for cleaning coal are solutions of calcium chloride in water and a suspended-sand pseudo liquid. Laboratory float-and-sink testing is an intermittent operation during which every opportunity is given for particles lighter than the medium to float and particles heavier to sink. Commercial processes are con¬tinuous, vertical and horizontal currents of the separating medium occur as either part of the process or unavoidedly produced by the intro¬duction of feed and withdrawal of products, so that the exact separation of the laboratory technique is not duplicated by commercial processes. However, separations close to the theoretical are obtained in commercial machines by careful technical control of the process. Most machines in commercial installations are crowded to get as much out of the equipment as possible, so that careful technical control is necessary to get the recoveries and grade of product desired. Sizes usually cleaned are plus %6-in. or plus 3-in. in the United States and plus 36-in. in Great Britain. Coal as small as 1 mm. has been cleaned in some experimental installations. The separation of coal from refuse in sizes finer than about % in. is made difficult by viscosity effects and hence at the present time cleaning is confined to the coarser . sizes. Technical advances in the art of cleaning coal by dense-media

Jan 1, 1943

By Harry A. Lipsitt, Attwell M. Adair

A number of papers have appeared in the past several years concerning the nature of the fatigue limit. The hypotheses presented in those papers fall into three groups. Some authors attribute the fatigue limit to the distribution of interstitials prior to testing (static group). Others consider the fatigue limit to be due to dislocation-interstitial reactions during testing (dynamic group). Still other propose that the fatigue limit results from a characteristic peculiar to the iron (bee) lattice (inherent group). This communication is an attempt to digest the salient features of each of the hypotheses, discuss them, and present some constructive criticism. It is shown that each of the extant ideas has some merit, and that each of the mechanisms thus far proposed is necessary, but individually insufficient, to provide the desired level of understanding of the fatigue-limit behavior of metals. Static Group. The data of Oates and wilson1 on finegrained (=0.022 mm diam) low-carbon steel indicate that the fatigue limit exists in the absence of sufficient plastic deformation for any dynamic strain-aging mechanism to be operative. Specimens tested just below the fatigue limit showed yield-point behavior typical for unstrained material when removed from the fatigue machine and tested in tension. These results led them to the conclusion that initial dislocation locking controls the fatigue limit in this material, which has a yield stress higher than the fatigue-limit stress. Prestraining this material just prior to fatigue testing would be expected to lower the fatigue-limit stress; this they observed experimentally. Yoshikawa and sugeno2 are of the opinion that the sharp fatigue limit in fine-grained iron is caused by

Jan 1, 1967

By Yves Dardel

THE literature concerning the remelting of aluminum and its alloys is very rich. Unfortunately the greater part of the papers about this subject have no scientific value, for the theories or explanations are too often in opposition to the laws of physical chemistry. Furthermore only a few of the methods of purification1,2 are considered in the literature. Hence it has seemed necessary to the author to sketch a general theory of the purification of secondary aluminum. The purpose of the purification is to eliminate the impurities that the charges and the atmosphere of the furnaces bring into the bath during the successive remeltings. Indeed scrap as well as metal can be used when soiled with oil, greases, water, .. , if it has been sufficiently dried and contains oxides. At the melting point of the metal, the oils and greases are decomposed into their constituent elements H2, 02, H2O, C02, CO, CH4, and others. These gases are added to the corresponding gases in the atmosphere of the furnace. The impurities introduced into the metal during the remelting will accordingly be the products resulting from the action of these gases on the liquid bath. The quantity of hydrogen that is soluble in aluminum and its alloys is given by the relation of Sieverts3 as a function of its partial pressure PH2 in the atmosphere [m = K _%/PH, [I]] where K is a constant, which depends only upon the temperature and increases with it. The experiments of Röntgen and Braun4, Röntgen and Möller5, Bircumshaw6 and Winterhager7 have rendered it possible to determine the value of K, when the temperature is inferior to 1.000°K. One obtains: [log K = - 4,702.5 + 0.238 [2]] Besides its usual signification, the term PH2 represents also the internal pressure of dissolved hydrogen, since in the equilibrium, that is, when no gas exchange occurs between the two phases, the pressures of hydrogen in the metal and in the atmosphere must be equal. Eq I shows that when the partial pressure of H2 increases the amount of dissolved hydrogen in equilibrium increases, and that, if the contrary occurs, the quantity of H2 should diminish. However, if for any reason the diffusion of hydrogen is hindered and the total amount of dissolved gas remains constant while the temperature lowers, the internal pressure of H2 increases until it reaches the value of the hydrostatic pressure. At this point, bubbles of hydrogen appear in the bath and escape out of it. The amount of hydrogen in the metal is then limited by a maximum depending on the hydrostatic pressure, which is practically equal to one atmosphere. Indeed hydrogen does not accumulate in the form of a hydride appearing as a separate solid phase. However, even the mechanism of the solubility is not yet elucidated. One does not know exactly as yet, whether the

Jan 1, 1947

By B. M. Larsen, K. Heindlhofer

THIS paper describes a relatively simple electrical apparatus that, through the close analogy between the flow of heat and of electricity, enables one to solve quickly and with satisfactory accuracy many complex problems in heat flow. This device, developed in 1935, has proved especially useful in the solution of certain practical problems relating to the design and efficiency of regenerators for an open-hearth furnace or coke oven, yielding within a few hours information that would take weeks or even months to acquire by mathematical1.2 or experimental3 methods of comparable accuracy. Its description now is prompted by growing interest in such analogues, as shown by several recent papers.4.5 The analogy between flow of heat and of electricity appears to have been recognized first by Maxwell who, in his famous Treatise on Electricity and Magnetism (1881) says: The analogy between the theory of the conduction of electricity and that of the conduction of heat is at first sight almost complete. If we can take two systems geometrically similar, and such that the conductivity. for heat at any part of the first is proportional to the conductivity for electricity at-the corresponding part of the second, and if we also make the temperature of any part of the first proportional to the electric potential at the corresponding point of the second, then the flow of heat across any area of the first will be proportional to the flow of electricity across the corresponding area of the second. .. Thus, in the illustration we have given, in which flow of electricity corresponds to flow of heat, the electric potential to temperature, electricity tends to flow from places of high to places of low potential, exactly as heat tends to flow from places of high to places of low. temperature He noted, however, that this analogy is restricted: ... there is, however, one remarkable difference between the phenomena of electricity and those of heat. Suspend a conducting body within a closed conducting vessel by a silk thread, and charge the vessel with electricity. The potential of the vessel and of all within it will be instantly raised, but however long and however powerfully the vessel be electrified, and whether the body within be allowed to come in contact with the vessel, or not, no signs of electrification will appear within the vessel, nor will the body within show any electrical effect when taken out. But if the vessel is raised to a high temperature, the body within will rise to the same temperature, but only after a considerable time, and if it is then taken out it will be found hot, and will remain so till it has continued to emit heat for some time. The difference between the phenomena consists in the fact that bodies are capable of absorbing and emitting heat, whereas they have no corresponding property with respect to electricity. According to this statement the application of the analogy would be limited to problems of steady flow that do not involve heat-capacity effects. In spite of this

Jan 1, 1945

By H. W. Weart, S. Sarian

The effect of temperature, impurities, and capillarity on the morphology of solid particles in a liquid matrix is investigated. For the NbC-liquid iron system, at least, it is found that those particles which are dissolving will assume a spherical shape; all others will take the equilibrium shape. An aniso-tropic-isotropic transition in the interfacial tension is observed at about 1725°C and is believed to be due to cooperative roughening of the interface on an atomic scale. The presence of boron as an impurity lowers the transition temperature. It is the purpose of this paper to present some observations on the shape of particles in a system consisting of solid particles of nonuniform size in a liquid matrix and to propose an explanation for these observations. Although qualitative only, these observations, which were made largely in the course of a study of particle-growth kinetics,' are presented separately to draw attention to them. They reveal the effect of particle size, temperature, and surface-active impurities on particle shape in the solid NbC-liquid iron system, and are unique in demonstrating for the first time the reversible effect of temperature and impurity concentration on the anisotropy of the energy of the solid-liquid interfaces involved. Some of the changes are readily demonstrated with the few particles whose shapes can be clearly shown in a single photomicrograph, but others are more subtle, and their recognition depends upon some experience and the study of a much larger sample. For this reason, a certain amount of judgment must be acknowledged to underlie their detection, but every effort was made to maintain proper scientific objectivity in evaluating the observations. The observations will be presented first, and then an explanation rationalizing them will be offered. Brief reminders of the relevant theories will be inserted into the discussion at the appropriate points. EXPERIMENTAL The observations were made of the shape of NbC particles dispersed in liquid iron. All specimens were prepared by pressing NbC powder and car- bony1 iron powder treated according to standard powder-metallurgical procedures. Except as noted, all specimens were heated to 1900°C for 1/2 hr. In investigating the effect of temperature, specimens were quenched from 1900°C to various lower temperatures, and held long enough (48 hr) to allow shape changes to be completed. Boron, in the form of amorphous powder, and oxygen, in the form of niobium oxide powder, were added as impurities to some specimens. Nitrogen was introduced into some specimens as an impurity by heat treating the samples under a partial pressure of nitrogen gas. Effect of Temperature. It was first observed that increasing temperature had a marked effect in rounding the corners and edges of the particles. At 1900°C the particles are all very nearly spherical and remain so even when the holding time is extended to 48 hr. As can be seen from Fig. 1, there is virtually no evidence of the presence of low-index planes. At 1300°C, however, most of the particles are prismatic with very slightly rounded edges and corners, Fig. 2. (In making these shape comparisons, attention should be focused on the larger particles, even though the smaller ones would be expected to be the first to change shape, owing to the shorter diffusion distances involved. The cause of the mixed particle shape will be explored later.) It was established that these structures are re-

Jan 1, 1965

By B. H. Sage, W. N. Lacey

An apparatus is described for the measurement of the pressure-volume-temperature relations of pure substances, simple mixtures and complex mixtures with an over-all absolute uncertainty, which is usually not more than 0.2 per cent. The equipment is suitable for studies in the gaseous, two-phase, and liquid regions. The behavior of such systems may be investigated at pressures as high as 10,000 lb. per sq. in. for temperatures between 70 and 600 F. The methods of measurement and the construction of the apparatus are described in some detail. The measurement of the volumetric behavior of multicomponent systems requires the simultaneous measurement of the pressure, volume, temperature and weight of each component of the system. In the present apparatus a sample having constant weight is investigated at a number of independently controlled pressures and temperatures, therefore it is necessary only to establish the weight of each component added before a given set of measurements. This method is in distinction to that in which the total volume remains constant and the pressure is varied by addition or removal of material, the system having variable weight. An objective in the design of the apparatus to be described was to develop equipment that would yield results involving no uncertainties larger than 0.25 per cent throughout the range of pressures from 150 to 10,000 Ib. per sq. in. at temperatures between 70" and 600" F. Although this over-all absolute uncertainty of measurement may not appear to be small, it necessitated care in the plans for control and measurement of each of the fundamental variables. In general, any uncertainty greater than 0.05 per cent in the pressure, volume, absolute temperature or weight of each component was considered undesirable; therefore the attempt was made to obtain a precision of measurement in each case such that the absolute uncertainty would be only half this amount except in certain regions near the ends of the experimental range of the variable under consideration.

Jan 1, 1940

By W. N. Lacey, B. H. Sage

An apparatus is described for the measurement of the pressure-volume-temperature relations of pure substances, simple mixtures and complex mixtures with an over-all absolute uncertainty, which is usually not more than 0.2 per cent. The equipment is suitable for studies in the gaseous, two-phase, and liquid regions. The behavior of such systems may be investigated at pressures as high as 10,000 lb. per sq. in. for temperatures between 70 and 600 F. The methods of measurement and the construction of the apparatus are described in some detail. The measurement of the volumetric behavior of multicomponent systems requires the simultaneous measurement of the pressure, volume, temperature and weight of each component of the system. In the present apparatus a sample having constant weight is investigated at a number of independently controlled pressures and temperatures, therefore it is necessary only to establish the weight of each component added before a given set of measurements. This method is in distinction to that in which the total volume remains constant and the pressure is varied by addition or removal of material, the system having variable weight. An objective in the design of the apparatus to be described was to develop equipment that would yield results involving no uncertainties larger than 0.25 per cent throughout the range of pressures from 150 to 10,000 Ib. per sq. in. at temperatures between 70" and 600" F. Although this over-all absolute uncertainty of measurement may not appear to be small, it necessitated care in the plans for control and measurement of each of the fundamental variables. In general, any uncertainty greater than 0.05 per cent in the pressure, volume, absolute temperature or weight of each component was considered undesirable; therefore the attempt was made to obtain a precision of measurement in each case such that the absolute uncertainty would be only half this amount except in certain regions near the ends of the experimental range of the variable under consideration.

Jan 1, 1940

By H. H. Kellogg

Equations representing the standard free energy of formation as a function of temperature, for thirty metallic chlorides, are presented and plotted on a free-energy vs. temperature diagram. The use of these data for calculations on reduction of metallic chlorides, refining of metals with chlorine, and chlorination of metallic oxides and sulphides is illustrated. CHLORINE metallurgy' has attracted metallur- gists for more than a century because the unusual properties of the metallic chlorides—low melting point, high volatility, and ease of formation from the oxides—make possible many useful extractive processes. Interest in chlorine processes is undergoing a renaissance due to present availability of chlorine at relatively low prices, and to recent advances in technology. During the present century there have accumulated a considerable number of reliable values of the thermodynamic constants for the metals and their chlorides. These data permit the calculation of free-energy equations for many metallurgically important reactions. Consideration of free-energy values makes possible certain predictions of the direction and extent of a given reaction, as well as the effect of temperature, pressure, and composition upon the result. Reaction rate, although not predictable from free-energy data, is usually sufficiently great at elevated temperatures that diffusion of the reactants and products to and from the zone of reaction determines the actual rate. Thus, if the free-energy indication is favorable, the chances are good that a high temperature metallurgical reaction will proceed at a reasonable rate, if adequate provision for rapid diffusion has been made. This paper presents standard free-energy equations for a number of metallic chlorides, based on data which are scattered throughout the literature. The equations are presented in a form that simplifies their use, and typical examples are given of the application of free-energy data to metallurgical processes. Free Energy of Reaction The free-energy change (AG) of a reaction is the true measure of the "driving force" of the reaction under a given set of conditions, and this is related to the standard free-energy change (AGO) of the reaction as follows: For the reaction: bB + cC = dD + eE ?G = ?G°+RTln ADd. AEA / ABb. ACc where A, = activity of constituent (i) T = absolute temperature, OK R = gas constant The criterion of a spontaneous reaction from left to right, at constant temperature and pressure, is a negative value for the free-energy change (?G). The standard free energy of the reaction is equal to the free energy of the reaction when all the reactants and products are at unit activity, since under these conditions the second term on the right-hand side of eq 1 is equal to zero. The concept of activity is treated fully in many textbooks on chemical thermodynamics1 and in a recent article by Chipman.2 Briefly, the activity (A,) of a constituent (i) is a measure of the reactivity of this constituent relative to its reactivity in some arbitrary standard state. For liquids and solids the standard state most often used is the pure liquid or solid constituent. Thus the activity of a pure liquid or solid in a metallurgical reaction is equal to unity. Gases under moderate pressure and at elevated temperatures behave very nearly as 'idea1 gases,' and the standard state is chosen as the gas at 1 atm pressure. The activity of an ideal gas is therefore equal to its partial pressure, and this relation is sufficiently exact for real gases in most metallurgical reactions. For a liquid or solid solution there is in general no simple way to express the activity of a constituent as a function of its concentration, and activity must be determined by experiment. A few solutions follow a so-called 'ideal' behavior, and if the pure constituent is chosen as the standard state, the activity of a constituent in an ideal solution becomes equal to its mol fraction. When a reaction reaches a state of thermodynamic equilibrium at constant temperature and pressure, AG becomes equal to zero and eq 1 reduces to: [ADd . AEe ?G°=RTln Abb ¦ Ac c equilibrium [2] The brackets surrounding the activity term are used to emphasize that each of the activities is an activity under equilibrium conditions—not just any arbitrarily assigned value. The bracketed term is the equilibrium constant (K) of the reaction. Eq 2 makes possible the calculation of equilibrium activities for a given reaction, if AGO is known at the desired temperature. The standard free-energy equations presented in this paper were calculated from the fundamental thermodynamic values of enthalpy of formation at 298°K (AH°,), standard entropy at 298°K (So298), heat capacity as a function of temperature (Cp), and enthalpies of transition, fusion, vaporization, and sublimation for the various constituents. Where possible the data reported in the recent "Selected Values of Chemical Thermodynamic Properties," published by the Bureau of Standards," were used. A large number of data came from the publications

Jan 1, 1951

By J. B. Warriner

Stripping is the name given to the process of removing clay, rock, or other cover from deposits of coal or ore. In this paper it is intended to cover the methods used in carrying on this operation in the anthracite coal regions of Pennsylvania. In doing this, attention will be chiefly devoted to those methods wherein practice in different sections of the region differs, or is susceptible to change or improvement, though it is intended to give as complete data as possible concerning all stages of the operation. The data from which this paper has been prepared have been collected and submitted by a committee† representing the larger users of stripping methods, of which committee the writer has acted as chairman. Data and assistance have also been obtained from various mining men, engineers, contractors and manufacturers of stripping equipment, to all of whom our appreciation is due. Early History and Statistics The earliest mining operation on a commercial scale in the anthracite region was a stripping operation. This was the famous Quarry mine at Summit Hill, where this method was used only because no other method of mining a deposit of the nature found there seemed feasible to the early operators. A description of this stripping from a report published in 1821 is as follows: "The coal mine at present worked by the company lies on the top of a mountain, and appears to extend over some hundred acres of land covered by about 12 ft,. of loose black dirt resembling moist gunpowder, which can be removed by cattle with scrapers, and thrown into the valley below so as never to impede the work. The thickness of the coal is not known, but a shaft has been sunk in it 35 ft. without penetrating through. More than an acre of mine has been uncovered and presents a huge rock of coal, which is easily quarried without blasting."

Jan 1, 1918

By Frank Harris

THE strength of hard drawn copper wire is a question of considerable importance to both manufacturer and consumer. Unlike steel and alloy wires, in which strength is governed by both chemical and physical considerations, the high conductivity required for copper wire in the electrical industry generally precludes the possibility of obtaining tensile strength through the use of alloys. Consequently, this strength is largely a matter of the physical structure, and all factors known to affect this structure, such as rolling temperature, die contours, lubricants, drawing speeds, etc., are matters of prime importance. The experiments described here have been carried out during the past year at the Baltimore plant of the American Smelting & Refining Co., in connection with a general investigation of some of the questions mentioned above, with the object of studying the physical structure of hard drawn copper, wire and the influence of certain factors on that structure. The work has been of an exploratory nature, rather than comprehensive, but it was thought that the results might prove of sufficient general interest to warrant their publication. The bulk of the hard drawn copper wire used in places where strength is an important factor is manufactured to strict specification, based usually in the United States on that of the American Society for Testing Materials (B-1-23). This specification calls for almost as high a value of tensile strength; consistent with elongation, as it is possible practically to obtain, and only physically perfect material can be relied on to meet such a specification. Obvious defects, such as laminations produced through fins in the original rods or brittleness due to overdrawing, are usually recognized and need only passing reference. Laminations can be detected by twisting and untwisting the wire several times; they will show up on the surface in the form of fins. Fig. 1 shows a very bad example of this defect. The wire may be perfectly smooth before twisting but when such laminations are present they will readily show up under this treatment. This trouble is caused by similar defects in the original rod produced by overfills in rolling. Fig. 2 shows the cross-section of the rod from which the wire in Fig.1 was drawn.

Jan 1, 1928

By R. E. Delavault, H. V. Warren

In normal soils there are usually 10 to 50 parts of copper in every million parts of .soil. Only 0.2 to .5 pct of this copper can be found by any simple cold chemical attack. Now, with rubeanic mid reagent paper, a prospector or field geologist can detect as little us 4 ppm of readily available copper ill soil. This degree, of sensiticity is enough to determine the presence. of copper anamalous an as and, ecentually, to discouer copper mineralization. Circumstances determine whether it is better to make analyses in the field or in a permanent laboratory. The rubeanic acid test described in this article has been designed primarily for field use: it is simple and virtually foolproof, and it requires a minimum of field kit." It is sensitive, easily de- • Ed. Note: Persons Interested in purchasing kits suitable for rubeanic acid prospecting can obtain information by writing Eldrico Geophysical Sales Ltd., 633 Hornby Street. Vancouver 1, B.C. The University of British Columbia does not produce these kits for sale and has no financial interest in their production tecting 4 ppm of readily extractable copper in a soil. This is by no means a quantitative test, but it is accurate enough to provide a valuable indicator of copper anomalous areas for both prospectors and field geologists. The easiest method for detecting metal deposits that do not produce visible float or stains is to make a simple chemical test for the metal in overlying soil, or in the silt of a stream that may have picked up metal farther upstream. In Brief: Testing for copper may be done easily by shaking a soil sample with strong acetic solution in a small test tube and pouring the mud into a small filter, the tip of which rests upon a strip of reagent paper impregnated with rubeanic acid (di-thio-oxamide). When copper is present—and only when it is—a blue spot develops. The more copper, the darker the spot. If the copper content is merely the small amount present everywhere, there is a pale blue or hardly visible spot; if it is abnormally high, the spot will be dark. There are, of course, intermediate cases where the experienced geochemist cannot tell offhand whether a medium-strength spot represents rich agricultural soil, weak copper mineralization, or distant rich copper mineralization. Reagents and material are inexpensive; the test may be readily done on the spot with a simple kit easy to pack and handle. Anyone interested in general problems of soil sampling as applied to prospecting may refer to an article recently presented to the AIME. In exploration work it is the contrast between the metal content of anomalous and background areas that is important; absolute values become of greater interest when an anomalous area is being investigated in detail. With specific reference to copper, it has been the authors' experience that the amounts of metal extracted from anomalous and normal soils with buffer solutions of decreasing pH show better contrast if an acid reagent is used. This contrast tends to increase with increasing acidity until 3 to 4 pH is reached. Using a short cold attack on unheated soil, it has been found that further increases in acidity do not produce better results, and only increase the hazards involved in carrying strong acids. An acidity of about pH 4 is satisfactory for direct determination of copper by dithizone. But dithizone itself introduces some problems: it must be made up fresh at frequent intervals, and with some soils, notably those with much ferric iron, oxidation mag take place before all the copper has reacted with the dithizone. Rubeanic acid keeps its strength unimpaired for long periods, is unaffected by oxidation, and is practically specific for copper at pH 4. Consequently it seems an ideal reagent to use in prospecting for copper. History and Background: Rubeanic acid (systematic name: dithio-oxamide (SC-NH2) has long been known as a spot test reagent for some heavy metals with which it gives a number of compounds. Only copper and some metals of the platinum family are believed capable of providing any ru-beanate compounds under conditions of moderate

Jan 1, 1959

By Norman B. Pilling

The technical difficulties hampering the metallographic analysis of silicon steels are chiefly the result of the extreme corrodibility of these alloys. The addition of silicon to iron in increasing quantities, up to about 6 per cent., rapidly increases the susceptibility of the alloy to chemical attack, not only in acid solution, but in water. This renders the preparation of metallographic sections very difficult, because of a non-selective attack upon the finely polished surface by the water used as a lubricant in polishing. This water attack masks the true structural details revealed by suitable etching reagents. It is thus necessary to use alcohol as a polishing lubricant in the last stages of preparation and to avoid all etching reagents having an aqueous base. A specific reagent for the identification of iron carbide in ferrous alloys, and the one hitherto used almost' exclusively by metallurgists, is an alkaline aqueous solution of sodium picrate, which stains this constituent selectively. Its application to silicon steels has not proved successful, as its distinctive selective action is more or less completely hidden by the general attack of the aqueous solvent on the silico-ferrite, greatly accentuated by the fact that this reagent must be used at its boiling temperature (105' C.). Thus, a powerful metallographic aid to the study of the higher silicon alloys, such as transformer steels, is lost. A new reagent has been developed for the purpose of overcoming this difficulty. It is with some hesitation that the list of etching reagents, already overburdened, is increased, but the properties of this new reagent are advantageous in several ways and a definite field for it may be found in the metallography of ferrous alloys. The reagent consists of a dilute solution of nitric acid and methyl alcohol in nitrobenzol. It is a great advantage to secure an anhydrous solution, as a tendency toward acidic etching has been traced to small amounts of water. A convenient method of preparation is to make an anhydrous stock solution of nitric acid in methyl alcohol in the proportion 20 per cent. acid by weight (12.5 per cent. by volume). The alcohol can

Jan 1, 1924

By Klaus Schwerdtfeger

The rules of solution of oxygen from H2O-H2-He gas and of nitrogen from N2-H2 gas in shallow melts of liquid iron were measured at 1610o and 1600o C, respectiuely. Concentration profiles were detemined in the liquid iron. Tire rate data indicate that the solution process is controlled by diffusion in the iron melt. The diffusivities for oxygen and nitrogen in liquid iron, as calculated from the present data, are DFe-o = (12 ± 3) < 10-5 sq cm per sec and DFe-N = 11 ± 2) X 10-5 sq cm per sec at the temperatures employed. AN attempt was made by Shurygin and Kryukl to measure the diffusivity of oxygen in liquid iron. In their experiments a silica disc was rotated in liquid iron containing oxygen, and the rate of formation of liquid iron silicate was measured. Assuming that the rate of dissolution of silica is controlled by diffusion of oxygen in the iron, the oxygen diffusivity was computed from the rate data giving Dfe-0 = 6.1 X 5 sq cm per sec at 1600°C. Although this value seems to be of the right order of magnitude, there is no proof of the correctness of the assumptions involved in the interpretation of these rate data. The oxygen concentration in the iron at the iron-iron silicate interface was taken to be that in equilibrium with the silica-saturated silicate melt. That is, it was assumed that no concentration gradient existed in the liquid silicate. This is a questionable assumption, unless it is proved that the thickness of the silicate layer is very much smaller than that of the diffusion boundary layer in the iron. Furthermore, Shurygin et al.1 used the Levich equation2 to interpret their rate data. This equation was derived for mass transfer between a solid disc and a single-phase liquid. The hydrodynamic and diffusion boundary layers in the iron stirred by a disc, via coupling of the silicate melt, may be appreciably different from those predicted by Levich&apos;s derivations. In the present work the diffusivities of oxygen and nitrogen in liquid iron were measured at 1610" and 1600oC, respectively. EXPERIMENTAL METHOD Iron melts contained in high-purity gas-tight alumina crucibles were reacted with H2O-H2-He gas for the determination of the oxygen diffusivity and with N2-H2 gas for the determination of nitrogen diffusivity. At the end of the reaction period, the samples were quenched in a cold H2-He gas stream at the top of the furnace. Oxygen or nitrogen contents in the iron were determined by chemical analysis. Two different types of diffusion experiments were perforxed. To determine concentration profiles, a few rate measurements were made using 4-cm-deep melts. The solidified samples were sliced into discs and each disc was analyzed for oxygen or nitrogen. In another series of experiments, oxygen or nitrogen was diffused into shallow melts (about 0.5 to 1 cm in depth) and the total sample was analyzed to obtain an average concentration of the diffusate. In most experiments, 4- to 5-mm-ID alumina crucibles were used. Some experiments were also made in smaller (3 mm) and larger (7 mm) diam crucibles. This variation in diameter caused no difference in the reaction rate, within the limits of experimental uncertainty. To promote the establishment of a stable density profile in the melt, all the samples were suspended in the lower end of the hot zone so that the top of the melt was hotter by a few degrees. Molybdenum wire resistance heating was used. The reaction tube of the furnace was a gas-tight recrystal-lized alumina tube. In most experiments the furnace was heated by an ac power supply. To check the possibility of inductive stirring, some experiments were carried out in a dc operated furnace, with essentially the same results. The temperature of the furnace was controlled automatically in the usual manner. The temperature was measured with a Pt/Pt-10 pet Rh thermocouple and is estimated to be accurate within ±5°C. The iron used was prepared by melting and vacuum-carbon deoxidizing electrolytic "Plastiron" in a zir-conia crucible. The main impurities are: Si 0.004 pct P, S <0.002 pct Cr 0.005 pct N 0.001 pct Zr 0.002 pct O 0.003 pct Mn 0.004 pct C 0.002 pct The gas composition was controlled by constant pressure head capillary flowmeters. Oxygen was removed from the gas mixture by passing it through columns of platinized asbestos (450°C) and anhydrone. Selected H2O contents were obtained by passing the purified gas through oxalic acid dihydrate-anhydrous oxalic acid mixtures held at constant temperature in a water bath. Water vapor pressure data for the oxalic acid dihydrate-anhydrous oxalic acid equilibrium were taken from the 1iterature.3 The flow rate used was about 1.5 liters per min. The whole system was checked for tightness at regular intervals.

Jan 1, 1968

By AIME AIME

This section contains announcements of general interest to the members of the Institute, but not always of sufficient permanent value to warrant republication in the volumes of the Transactions.

Sep 1, 1906

By A. D. Rich

THE term "bleaching clay" or "bleaching earth," as used in the oil industries, refers to clays that in their natural state, or after chemical or physical activation, have the capacity for adsorbing coloring matter from oil. There are three common types of bleaching clays: fuller&apos;s earth, activated clays, and activated bauxite. Fuller&apos;s earth, or naturally active clay, is prepared from bentonites that possess natural activity. It is not activated commercially; in fact, earths of this type ordinarily do not respond satisfactorily to acid activation. Fuller&apos;s earth is prepared in pulverized as well as granular form for use in the contacting and percolation processes, respectively. Acid-activated clays also are of bentonitic origin. The basic raw clay, however, is of a type that has a very low natural activity but is highly activable by treatment with mineral acid. Commercial acid-activated clays generally possess several times the decolorizing power (bleaching efficiency) of the best quality of fuller&apos;s earth. The former are prepared commercially only in the pulverized grade because of the difficulties in obtaining a satisfactory granular product, and hence are used only in the contact process. Activated bauxite is made by heat-treating bauxite ore, which in its natural state has very little natural activity. The commercial product is prepared in granular form for use in the percolation process on petroleum oils. For the most part, bleaching clay is used commercially in the decolorization of animal, vegetable and petroleum oils, fats and waxes. It is applied in two ways: (1) by the percolation method and (2) by the contacting method. Percolation refers to the passage of oil through a bed of granular clay whereas contacting refers to direct agitation of oil and pulverized clay followed by removal of the clay from the oil by filtration. In either case, the decolorizing effect is obtained by inti-

Jan 1, 1949

By G. P. de Forest, G. O. Hiers

The object of the experiments reported in this paper is to determine the eutectic composition of copper and tin and to determine the location of the part of the liquidus line immediately above the eutectic composition in copper. Three methods were used in the investigation: (1) the method of dissolving copper in a bath of molten tin at constant temperature, with the idea that when the bath was saturated with copper its copper content, by analysis, together with the temperature at which the saturation took place would locate a point on the liquidus line; (2) the method of the differential cooling curves, and (3) the method of microscopic examination. This paper is principally concerned with the results of the last two methods mentioned. The results of the first method, that of dissolving copper in molten tin, did not agree with the results of Miller,&apos; by the same method, nor with the results of other investigators by other methods, nor yet with the results of the cooling-curve experiments and microscopic examination reported here. Solution of Copper in Molten Tin To determine the amount of copper that would be dissolved by molten tin at a given constant temperature the apparatus shown in Fig. 1 was used. It consists of a cast-iron pot a, 6 in. deep and 8 in. dia., well cleaned inside and dressed with graphite. This pot, which holds 15 lb. of tin, g, rests on a hot plate b with resistance winding c. The thermocouple d leads to a Wilson-Maeulen temperature regulator for maintaining the temperahre at the heating coils at a fixed temperature to within ±5°C. There is a shallow bath of solder e on the top of the hot plate to improve the thermal contact between the plate and the pot. An insulating jacket f of asbestos prevents the irregular radiation of heat from the apparatus. The copper stirrer h slowly rotates in, and is dissolved by the bath of molten tin g. This bath is protected from excessive oxidation by a layer of charcoal j. The stirrer h is fixed to the lower end of the iron tube k, which is so mounted that it can be driven by a motor with reducing gear. The temperature of the bath is indicated

Jan 1, 1930