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By John Chipman, Helen Towers

DEVELOPMENT of a simple radioactive tracer technique for measurement of the diffusion coefficient of calcium ion in liquid slag has already been reported. The investigation was of a preliminary nature designed to explore the possibilities of using radioactive isotopes and to establish a method, and no great accuracy was claimed for the results. It was shown, however, that Ca15 could be used successfully, and the values obtained for the diffusion coefficient appeared to be of the right order of magnitude. However, it was considered that a better technique could be devised for carrying out the diffusion. The experiments were, therefore, continued to find a more accurate method, to check the calcium results, and to extend the investigation to include measurements of the diffusion coefficient of silicon in the same slag. There were two flaws in the original technique. Convection was the cause of too many failures, and the interface between the two slags in the diffusion cell was curved rather than plane, probably due to a surface tension effect caused by the addition of the tracer Ca45 in the form of chloride. Two methods of overcoming these defects were tried. Since it was planned to study diffusion of the short-lived isotope Si"' also, the development of methods was restricted to those which gave promise of being reasonably rapid. Method 1—The principle was identical to that previously used with respect to the diffusion conditions, but there were three differences in technique. Temperature control was more rigid, the tracer was added to the slag as Ca45O rather than the chloride and, finally, an effort was made to translate to high temperatures the elegant method developed by Cohen and BruinV or bringing together the two liquid layers and beginning the diffusion. A master slag was melted in graphite, ground to a fine powder, and analyzed (38.5 pct Ca0-20.9 pct Al2O3-40.5 pct SiO2). The tracer was received as Ca45C12 in an aqueous solution of CaC12 + HC1. From this, calcium oxalate was precipitated, ignited to calcium oxide, and added as such to the slag to give an activity of approximately 5 µc per g. The mixture was then melted into the form of a cylinder 3/16 in. diam and about 1 in. long. A solution identical to the tracer solution without Ca45 was given exactly the same treatment. The resulting Ca40O was mixed with that slag which was to form the tracer-free half of the diffusion cell, and this was likewise melted into a cylinder of the same size. Slag cylinders, two with and two without Ca15, were set in graphite blocks as shown in Fig. 1, and the crucible was lowered into position in the fur-

Jan 1, 1958

By J. S. Marsh

The student of steelmaking is all too well acquainted with the fact that in many instances he must deal with data that in graphical representation exhibit the property most desirable in bird shot. This is scarcely mystifying, since the effort to establish one variable as a function of another is usually hampered by the simultaneous operativeness of two or three other factors that may be important. A large part of arriving at relationships that have the pleasing self-consistency of, say, precise measurements of thermal expansion, consists of determining what factors must be held constant-—an even larger part usually consists of collecting data for which those factors have been so maintained. It is not intended to imply that functional relationships in the physical chemistry of steelmaking are hopelessly obscure; on the contrary, it is merely necessary to be undisturbed by marked deviation of some points from a curve that otherwise makes sense. A reaction mechanism suggested by such a curve may call attention to hitherto unsuspected factors operative in the origin of the deviating points, and thus permit another step to be taken in the direction of fuller understanding. It is proposed, therefore, to suggest several empirical relationships. Even though the approach is not always rigorous, deviations caused by simplifying assumptions appear to be too small to obscure a provisional It has been appreciated for some time that the carbon-oxygen reaction in liquid steel is highly important. For example, Körber et al.,' in introducing a summary of their extensive work on steelmaking reactions, said: "... the far-reaching and truly dominating action of carbon upon the metallurgical reactions will be especially stressed ..." In "Basic Open Hearth Steelmaking"2 (hereafter BOHS, for simplicity), it is accepted repeatedly that the various slag-metal interactions are nearly always controlled by the carbon-oxygen reaction. Before further discussion of this reaction, however, it will be worth while to consider briefly the carbon-oxygen equilibrium. In BOHS (p. 483) it is stated that: When liquid iron is brought into contact with gases containing carbon monoxide it absorhs carbon and oxygen. Conversely the carbon and oxygen in the metal unite to form carbon monoxide which is evolved from the bath during the open-hearth boil or while rimming ingots are solidifying. . . . When the equilibrium pressure is one atmosphere the equilibrium-constant equation simplifies, on the assumption that the activity of each element is equal to its percentage, to a constant which has been so much used that it has acquired a special symbol m. where m = %C X %O

Jan 1, 1945

IN CHAPTER I it was shown that the approximate market value of the copper produced at the twelve big Porphyry mines from 1905 to 1931, inclusive, was $2,821,300,000. This represented the refined metal ready for shipment to the consumer. In addition, at least $50,000,000 worth of gold and silver had been produced, more than $30,000,000 coming from the Utah mine alone. Consequently, the revenues totaled about $2,871,300,000, as shown in Table 58. Society paid this sum for a given quantity of metal that it wanted for industrial use. Where did the money go? Who were the direct beneficiaries of the creation of this new wealth? These questions this chapter will answer in a general way. Because some necessary data are not available, an exact tabulation in detail can not be made, but Table 58 is believed to reflect with reasonable accuracy the disposition made of the aggregate income from the twelve operations. The word "operations" is used advisedly because the complexity of corporate relations precludes the possibility of picking out companies, as could be done if each enterprise were an independent entity such as Miami, for example. Some explanation of the table and some elaboration of the items under "Outgo" is desirable. In the first place, it is assumed that the sum of surplus current assets existing in various treasuries at the end of 1931 was substantially equivalent to the “new” money that actually was put into the enterprises as a group. Less than $20,000,000 in new capital was realized from securities sold by the Utah Copper Co., the remaining funds coming from earnings. In respect to some of the others, such as Chuquicamata, Inspiration, and Andes, the amount of new money was much greater. However, of the two items-total new capital invested and total current surpluses-the former

Jan 1, 1933

By Lewis A. Smith

Chromium is one of the new metals, but considerable research has been required to determine an approximate record of its production from 1827 until the present. Its use in the form of pure metal is not extensive; of the chromite mined, about one-half is required for making ferrochro-mium, about two-fifths goes directly into refractories and the remainder is absorbed chiefly by the chemical trades. The industries that demand chromite for such uses are mainly in countries that produce little chromite, while the important chromite-producing countries are not generally consumers. The international flow of chromite is therefore of interest, as well as the political and commercial control of resources of the metal. World Production The first mining of chromite is said to have occurred as early as 1820, at the Roros deposit in Norway, but the first well-established output came from the Reed mine, in Maryland, about 1827. Thereafter the United States led the world in chromite production until 1860, when Turkey took the lead. Russia in turn became the chief producer from 1897 to 1902, inclusive. From 1903 to 1909, New Caledonia held first place, but alternated with Southern Rhodesia from 1910 to 1917, inclusive. In 1918, 1919 and 1920-1921, the United States, India and New Caledonia led, respectively. In 1922 Southern Rhodesia assumed first place and has since continued to be the world's foremost producer by a large margin. Fig. 1 illustrates the production of the leading countries from 1890 to 1929, inclusive. Fig. 2 shows the world production of chromite from 1890 to 1929, inclusive, in long tons and Table 2 gives the production by countries for the same period. The total world production for the 103 years, 1827 to 1929, ipclusive, is estimated at about 7,100,000 long tons, distributed as shown in Table 1. World Trade in 1928 In reviewing the figures for the flow of chromite in 1928, it is evident that the six countries that produce most consume little chromite and

Jan 1, 1931

By P. E. Fitzgerald, Dana G. Hefley

An apparatus has been developed which permits selective acidizing of producing formations and determination of the relative permeability of a formation by fluid injection. This apparatus, known as the "Electric Pilot," is an electrical fluid-interface locator, the electrical circuit of which is completed when the elec-tcodes in the well are in contact with a conductive fluid, but is not completed when immersed in a nonconductive fluid. Results are given for a number of typical acidizing applications in which the interface locator was used to control the acid. Description of the method used in making a permeability survey and the data obtained are also included. Introduction Early in the development of the acidizing industry it was recognized that one of the most important problems to be solved in the chemical treatment of any well was the determination of what part of the exposed section in the well should be treated and the selection of the technique that would insure treatment of the desired section. One of the first techniques adopted for assisting in proper placement of the acid, which is still widely used, is the method of confining the acid to the producing section by means of a column of oil, which is known as the Carr1 method of treatment, named for its inventor. In the Carr method it is not possible to selectively acidize a specific horizon in a multiple pay zone, so many improvements and modifications of the basic Carr technique were devised to accomplish this result. In order to overcome the possibility of the acid entering an undesirable section at the bottom of the well, organic gel plugs2 were introduced into the bottom of the well, which served to halt the entrance of the treating solution into these zones.3 These chemical gels later liquefied because of bacterial action and were removed from the well with the produced fluid. In fields where a gas cap existed, as in the Goldsmith field of Ector County, Texas) it was imperative that a treating technique be evolved that would confine the acid to the oil-producing zone below the gas cap. By so doing the oil-productive capacity of the wells could be improved without greatly increasing the gas production and this would lower the gas-oil ratio of the well. ~h, technique employed4 to achieve this effect utilized two pumps, one for pumping the chemicals down the tubing, the other to simultaneously force oil down the annular space to confine the acid to the oil pay, thus preventing the chemicals from entering the upper gas-bearing zones. Experience has indicated that gas wells and certain types of oil wells respond better to ''stage treating.'' This technique utilizes the introduction of a certain volume of acid and then allows the well to ''clean up99 before introduction of the next and usually successively larger stages. Where such methods are employed steps must be taken to keep a disproportionate share of the acid from entering the most permeable and previously treated Zones. A special tool

Jan 1, 1944

By R. H. Card

The geophysicist is interested greatly in the resistivities of different formations or parts of the earth's crust; sometimes he is interested in a single figure in the nature of an average, or what may be called the effective resistivity, of all the formations or parts of the crust at a given location to a certain depth. Conversely, the engineer whose work is concerned with the coordination of power and communication lines in such a manner as to avoid electrical interference between these two types of facilities is concerned very much with this effective resistivity; to a lesser extent he is interested in the resistivities of individual formations. In connection with his work the coordination engineer often estimates the effective resistivity of the earth from measurements of the mutual impedances of lines; in other instances he derives from measurements of a different type the resistivities of different layers of the crust and synthesizes these to obtain an estimate of the effective resistivity. In connection with problems concerning the coordination of power and telephone lines, measurements from which earth resistivities can be estimated have been made at many points in the United States by the American Telephone and Telegraph Co. and its associated companies, in cooperation with various power companies and with railroad companies having electrified sections of line. Other such measurements have been made by the Joint Subcommittee on Development and Research of the Edison Electric Institute and the Bell Telephone System. A study has been made of the correlation of these data with the ages and types of materials of the strata of the earth's crust at each of the test locations. The purpose of this study has been primarily to provide information to assist in predicting the order of magnitude of effective resistivities to be used in the preliminary consideration of problems concerned with the coordination of power and communication lines. To make the results of such a study most useful, it is essential that the geological data to be secured when such a prediction is wanted be readily obtainable. Data on the ages of strata and the types of materials composing geological structures can usually be obtained, therefore particu-

Jan 1, 1940

By H. Buttner, F. H. Udin, J. Wulff

GRAIN boundaries, the interface between adjacent crystals differing only in respective orientation, have been the object of much experimental and moderate theoretical attention for many years. The earlier experimental work was primarily concerned with the effect that grain boundaries have on the physical behavior of metals, while the basic nature of the boundaries themselves drew only secondary attention. A complete turnabout has been witnessed in more recent years, however, as researchers are now undertaking investigations bearing as directly as possible on the character and physical properties of the grain boundary. Quite comprehensive reviews of the past literature on the subject of grain boundaries have been reported on numerous occasions by various authors, and together these references represent a thorough coverage.'-? It becomes evident in these reviews and other papers"" that the properties of grain boundaries can be explained by regarding a grain boundary as a crystalline region of transition between two unmatched grains. Studies show that grain boundaries have a definite interfacial energy. By measuring the geometry about a point where three interfaces meet in equilibrium, the energy of any two boundaries can be measured with respect to the third. If the absolute interfacial energy of one boundary is known, the absolute energy of the other two boundaries can be calculated. This apparently holds true for any system of phases and interfaces.""25 Most studies have been carried out on solid-solid or liquid-solid systems, or systems of both. However, if about the point of intersection one phase is vapor and the other two are disoriented grains, then two interfaces are surfaces, and one is a grain boundary. Investigations leading to relative grain boundary energy for this particular system have been made by Fullman,23 Greenough and King," and Bailey and Watkins." Herring" treats the system mathematically and arrives at an equation, which appears as Eq. 1, in a form consistent with the reference angles indicated in Fig. 1, ( d?1 ?n = x sina + cosa ( ------- 2 ?2 Sinß da + C0Sß (d?2/d As the system of interfaces comes to equilibrium, a groove of angle appears at the intersection of the grain boundary with the surface, an effect first observed by Rosenhain and Humfrey." Eq. 1 is essentially a summation of the vertical components in Fig. 1 set equal to zero, where ?1 and ?2 are surface tension vectors lying along the side of the groove at point 0 in the groove root. The differential vectors represent the forces tending to rotate the surface into a position that will expose a crystal cleavage surface of lowest energy. Chalmers, King, and Shuttleworth- simplify Eq. 1 by assuming the differential vectors equal to zero, ?1 = ?2= ?Surface and arrive at the following equation: ?B = 2?s cos [2] Greenough and King24 use Eq. 2 for determining the grain boundary energy of silver using prepared bi-crystals of known orientation. Bailey and Watkins25 have done the same for copper, as did Chalmers and others on lead. These authors report the grain boundary values as ratios relative to the surface energy. In the above work, the orientation of grains forming the grain boundary in all cases was controlled so

Jan 1, 1954

By S. W. Churchill

A digital computer was used to obtain an exact numerical solution for the transient behavior of the insulation and earth adjacent to an isothermal, submerged flat surface for a single set of parametric values. Comparison of the computed results with analytical solutions for limiting conditions revealed that a complete and general solution for all parametric values could be constructed from these limiting solutions. Complete and general solutions for insulated spheres and cylinders can also be constructed from limiting solutions. The procedure is illustrated in part for an insulated spherical tank. The heat flow was found to fall rapidly to a pseudo-steady state; after some time, it then decreased slowly to zero for a flat plate and cylinder, and to a low steady-state rate for a sphere. The accumulative heat flow during the initial falling-rate period may be a significant fraction of the heat flow during the entire first year. INTRODUCTION Underground storage of liquefied natural gas and liquefied petroleum gas has received considerable recent attention. The rate of heat flow from the earth to the storage cavity and the resulting temperature field in the earth are important factors in the technical and economic evaluation of such storage facilities. The objective of this paper is to indicate how complete solutions can be developed for the transient flux and temperature field for various geometrical configurations. The representative properties and dimensions, and the resulting parameters utilized in the illustrative results, are indicated in Table 1. The results presented herein are for dry earth. The effect of the latent heat of solidification of water in the soiI will be described in a subsequent paper. The temperature field in the insulation and earth is determined by energy balances, boundary conditions and initial conditions. The physical problem can be described mathematically with virtually no idealizations insofar as physical properties are known. It appears possible to solve the equations by numerical integration on a high-speed digital computer for any geometrical configuration and conditions. For complex situations, however, the computations are expensive and the results are highly specific. Analytical solutions have been developed for a few simple but important geometrical configurations and conditions, including one-dimensional heat transfer from (or to) earth at an initially uniform temperature to (or from) flat plates, spheres and circular cylinders. The solution for an insulated flat plate has also been derived but is in the form of a slowly converging series involving taklated functions. It was planned to use a computing machine to evaluate this series for a number of representative conditions. However, upon examination of the results of preliminary computations it was discovered that a complete, general and accurate solution could be developed by interpolation between several much simpler solutions for limiting conditions. This technique then was used to develop a a complete solution for an insulated sphere. The equations presented herein are derived in Carslaw and Jaegerl and other books on applied mathematics, or they are simple extensions of these previous results. Hence, all derivations are omitted. Emphasis is instead placed on the results and their

By Robert Parker

Measurements of the latent heat of transformation from a to 0 titanium were made using a pulse-heating technique. Rapid heating was accomplished electrically by discharging a low-inductance capci-tor hank through a thin-strip specimen. Both high-purity titanium and titanium containing 2700 ppm of 0 were studied. An electrical-resistivity technique and a plot of energy input us temperature rise were used to monitor the phase change. It was concluded that: 1) the latent heat of transformation is 800 i 48 cal per mole; 2) phase change occurred in less than 200 sec; and 3) the percentage phase change that occurs is linearly a function of the energy available for phase change. In addition, this experiment provides a simple and inexpensive method for determining specific heat of electrical conductors over large temperature ranges. The chief advantages of this technique over past pulse-heating experiments are: 1) static measurements of capacitor-bank voltage capacitance and specimen resistance can be made quickly and accurately to determine the energy supplied to the specimen; 2) the specimen is heated so rapidly (10 µ sec) that there is no appreciable heat loss during the heating. THE purpose of this paper is to illustrate the use of the capacitor bank as a tool for basic experimental investigations and to determine the rapid phase-change kinetics of titanium. The capacitor provides a number of unique properties: 1) rapid heating rates in the order of l09oC per sec can be obtained; heating rates as slow as l04oC per sec are available by merely adding a given amount of inductance to the circuit; 2) the energy input can be precisely determined and can be varied from several joules to millions of joules, depending on the bank capacitance and voltage; 3) the specimen can be heated uniformly through the thickness and length or non-uniformly, as desired; 4) the apparatus is simple and inexpensive and can be easily altered; 5) the form of the specimen can be wires, sheets, foils, rods, and cylinders; 6) there is great precision in the timing of events; 7) this technique may be readily used in conjunction with rapid cooling.

Jan 1, 1965

By R. B. Tippin, J. S. Browning

Inasmuch as the higher grade potash deposits are rapidly being depleted, it is important that economic beneficiation techniques be developed for recovering potassium compounds from lower grade sylvite ores and deposits containing clay materials. The Federal Bureau of Mines has conducted research to develop processes for heavy liquid concentration of potash ores, This method of concentration is discussed, and results of tests made on potash ores from New Mexico are presented. The tests demonstrated the technical feasibility of producing near commercial-grade potash concentrates, with a high recovery of the contained sylvite. The concentration of minerals based on their differences in specific gravity dates back to the very beginning of mineral dressing, and the use of heavy liquids in the laboratory to achieve optimum mineral separations has been utilized for many years. With the advent of froth flotation and its success, the incentive to develop new processes has remained relatively dormant. However, flotation refinements in the nonmetallic ores have not progressed as rapidly as in metallic (sulfide) ores because of the complexity of the deposits and the chemical similarities of the minerals.

Jan 1, 1967

By C. E. Nelson

THE purpose of this discussion is to outline briefly the practices commonly followed in this country for the melting and refining of magnesium and its alloys. The processes used for the various forms of primary magnesium, as far as there are differences in the physical shape or behavior, will be discussed. The refining of general fine scrap or secondary magnesium was presented in an earlier paper.1 Inasmuch as the use of fluxes is an essential part of all the melting and refining processes, the principal aim of this paper will be to deal with these in sufficient detail to point out their unique characteristics, in order to make their use more effective. TYPES OF MELTING PRACTICE All melting and refining processes for magnesium and its alloys require the use of fluxes. These fluxes have a magnesium chloride base and other halide salts or oxides are added to give a density or behavior exactly suited to the particular melting practice. The successful handling of magnesium depends upon the proper use of the correct fluxes. There are four general methods of melting, summarized in the following paragraphs and treated in more detail in the section on Melting and Refining. Open-pot Method The open-pot method makes use of No. 230 flux.* The flux provides protection during melting and a molten pool of flux into which the solid magnesium melts. It is stirred through the molten metal bath and agglomerates oxide or similar foreign bodies; then on quiet standing separates away, leaving the refined metal ball floating in an encircling layer of molten flux. It forms only a thin fluid film over the surface of the molten metal, which may be parted for hand-ladling processes and tends to cover the metal again after the ladle is removed. A very light dusting of the pot surface with fresh flux immediately after the ladle is removed is usually desirable. The open-pot method is used generally in the following processes: (I) alloying and secondary smelting in the production of ingot, (2) in sand foundries for premelting and to a smaller extent for the production of small castings requiring hand ladling, (3) in permanent-mold founding for premelting and also direct ladling to castings, (4) for continuous methods of preparing metal in the production of billets or ingots from which wrought products are fabricated, (5) in general scrap recovery. Crucible Process The crucible process makes use of No. 310 flux, which has the property of being thinly fluid at the start, to provide protec-

Jan 1, 1944

By Joseph Hartshorne

This plant is situated in the borough of Pottstown, on the banks of the Schuylkill river, between the Philadelphia and Reading Railroad and the Schuylkill Division of the Pennsylvania Railroad, on a plot of about 125 acres, most of which is reserved for future extensions. About 45 acres are to be used for houses, 40 of which have already been built. The accompanying plan will give a clear idea of the general arrangement of the works. Beginning at the lower or eastern end, the first building is the basic-cinder grinding-plant. At present, it consists of a 2000 mm. Jenisch ball-mill (Kugelfallmühle) similar to those used so extensively for grinding basic cinder in Europe. It was built by Herman LÖhnert, of Bromberg. The mill is very simple in design, and efficient in execution. About 13 horse-power is required to run it, and the average output is 20,000 pounds in 10 hours. The best work we have done is 29,000 pounds in 10 hours, with perfectly dry cinder. From 95 to 98 per cent. of the product will pass through a sieve with 100 meshes to the inch, while from 70 to 75 per cent. will pass through a 150-mesh sieve. The mill has been in service since last March, part of the time on double-turn, and the renewals and repairs have been very slight. The product of the plant is sold as a fertilizer. It runs from 18 to 24 per cent. in phosphoric acid, about 14 of which is reverted. The merits of this fertilizer were explained by Mr. W. H. Morris, at the Baltimore meeting of February, 1892 (Trans., xxi., 232), and by Mr. W. B. Phillips, at the Birmingham meeting of 1888 (Trans., xvii., 84). The results obtained by its use in Europe, where over 600,000 tons were used last year, are well known. Near the cinder-grinding plant will be situated the new machineshop, which is now being erected. The next buildings contain the brick-making plant and ovens.

Jan 1, 1893

By R. DiBella, H. Biloni, G. F. Bolling

A study of the detailed relationship between solidification substructure and microsegregation in dilute tin alloys has been continued. New observations reveal that depressions form at the solid-liquid interface not only as an initial form of segregation but throughout the range of increasing constitutional supercooling. In order to show the importance of this node formation it proves convenient to make two simplifications. Although substructure changes continuously as constitutional- supercooling increases,&apos; the following discrete stages may be used for discussion: 1) the planar solid-liquid interface; 2) ordered nodes, or depressions at the interface;&apos; 3) two-dimensional or elongated cells;3 4) regular or hexagonal cells;4 5) distorted cells, or hexagonal cells with branches;4 6) dendrites. It is also convenient to ignore observations made near grain boundaries which interact with the cellular substructure.2-4 And, it should be clearly pointed out that all singular depressions at the solid-liquid interface will be called nodes. Heretofore, the term "node" has been used without clear justification to describe both the truly isolated depression and the junction of cell walls appearing in a later stage of segregation. This usage is continued because it seems proved by the observations. Standard systematic growth of tin crystals was undertaken over a broad range of constitutional supercooling using various added solutes. Except for one or two chance observations, this research failed to reveal any appreciable range of growth conditions over which a disordered array of isolated nodes exists. Even though &apos;some finite range of random instability must exist, it is now concluded that stage one passes very rapidly to stage two. Next, after confirming that stage two passes to stage three by the elongation of isolated nodes: a reexamina-tion of stages three, four, and five followed. Standard metallography showed that pockets of higher solute concentration (for ko < 1) became more numerous in cell walls the more severe the growth conditions. These high-concentration regions must arise from depressions; however, in stage three their segregation is not distinguishable from the segregation of the nodes which join cell walls together. It seems, therefore, that the presence of nodes is causal in the formation of new cell walls, and that the mechanism by which stage three passes to stage four is initiated by nodes. If a similar reasoning is followed, the separation of stage four from stage five appears to be just a convenience that has arisen from the decanted interface observations made in the past. The present observations again show that more severe growth conditions relate directly to an increase in the number of nodes in the hexagonal cell walls. These nodes apparently serve as the origin for lines of segregation extending within the body of a cell, and can thus be assumed to represent the earliest form of branching,* as shown here in Fig. 1. The examination of stage six involved decanted-interface structures as in Fig. 2, which are similar to those considered by Rutter and Chalmers,5 Plaskett and winegard,6 and Hellawell and Herbert,7 and where distinct protrusions are each surrounded by a depressed boundary. The corresponding microsegregation behind the interface, but not far enough behind to allow a smearing of the segregation because of diffusion,4 is shown in Fig. 3. Both the shape of the decanted interface and the segregation pattern behind it

Jan 1, 1968

By W. N. Lacey, C. G. Yundt, B. H. Sage, J. S. Billheimer

As a part of a general investigation of the separation of bitumen from hydrocarbon mixtures a study was made of a restricted quaternary system composed of methane, decane, tetralin, and bitumen. The work was limited to a pressure of 8000 psi, a temperature of 220 °F, and to a fixed relative proportion of decane, tetralin, and bitumen. The measurements permitted the determination of the distribution of these components in each of the fluid phases. It was not possible to distinguish a second liquid phase in the course of these measurements. Gas-liquid equilibrium "constants" of each of the components were found to vary markedly with the composition of the system while temperature and pressure remained fixed. INTRODUCTION The separation of bitumen frorn naturally occurring hydrocarbon mixtures has been of importance for a number of years in the production of petroleum, especially in the California area. The deposition of this material from crude oils was noted in earlier studies of the solubility of natural gas in crude oil.¹,²,3 Studies of the separation of bitumen from crude oils from the Greeley and Santa Fe Springs fields were carried out."." The behavior of these systems appeared complex and studies of two restricted ternary systems involving mixtures of n-pentane, tetralin, and bitumen,&apos; and of decane, tetralin; and hitumen, confirmed this belief. Reviews of the literature pertaining to the separation of bitumen from naturally occuring and refined hydrocarbons are available." The important effect of methane in the separation of bitu- men from naturally occurring hydrocarbon mixtures was apparent from the earlier studies and for that reason it appeared desirable to investigate a restricted quarternary system involving mixtures of methane. decane, tetralin, and bitumen; data concerning the behavior of mixtures of decane. tetralin. and bitumen having already been obtained.V his study was restricted to a pressure of 8000 psi," a temperatue of 220° F, and fixed relative proportions of bitumen, decane. and tetralin. This composite constituent, hereinafter designated as the less volatile constituent, was made up of 0.0455 weight fraction bitumen. 0.0909 weight fraction decane, and 0.8636 weight fraction tetralin. The experimental method involved bringing together mixtures of methane and the less volatile constituent in varying proportions in a constant volume container at the pressure and temperature indicated above. The composition of each of the phases was determined and from this the extent of the separation of bitumen was established. MATERIALS The bitumen used in this investigation was obtained from the same stocks employed in earlier studies. The crude material from the North Coles Levee field was stored in the laboratory] in a closed drum for a period of five years. Several samples from this stock were subjected to refining operations which were described earlier,&apos; and every effort was made to follow the same procedure in all cases. It was necessary to prepare supplies of bitumen for this investigation at two rather widely different times. These materials have been identified as samples 1 and 2. The composition of the crude bitumen after it was washed with n-pentane at room temperature

Jan 1, 1949

By A. W. Hesse

Ventilation of all types of coal mines is fundamentally the same, in that sufficient air must be provided to properly dilute and remove dangerous and obnoxious gases and leave the oxygen content of the air not under 1 9 per cent in all places where men and animals must work. Perhaps animals should not be mentioned, as the speed of mechanical loading leaves livestock behind and outmoded. Since this paper has to do with the influence of mechanical loading equipment on ventilation, the problems will be confined to the splits and the coal-producing places of the mine. The removal of coal dust from the air, or its rapid transmission to the return air courses; the possible increase in the liberation of gases by the multiplication of cuts in the coal made during one shift or multiple shifts; and the additional electrical equipment at the faces, are the factors that cause the added importance to good ventilation in the permissible equipment area of gassy bituminous coal mines. Ventilation tor Mechanical Loading in Gassy Mines In gassy mines, the air currents must be maintained across the faces in such a way as to prevent short cuts to the returns and leaving pockets in which accumulation of gas might occur. To do this, two or more doors are required on almost every entry containing a track to the face, so located that in no event will a trip of cars block open the doors and permit the air to bypass some place or places on the air-approach side. This method frequently requires the use of unusual lengths of duplex cables to reach the mechanical equipment at the faces, particularly where the distances between parallel working places are 100 ft., as at the Nemacolin mine. Fig. I shows a pillar section being worked with mechanical loaders. This layout requires carrying the air in on the right and releasing it on the left, because the track clearance is on the right side and the line brattice is built on this side from the last crosscut to the face. Thus, the air travels to the face with greater velocity and gives more assurance of sweeping out the gas that might be exuding from the crevices of the coal. All working places, in driving through solid coal, are thus treated alike. They are all potentially gassy and must be swept clear of whatever may contaminate the air. Once the air starts into the working section, it is not released until it does a good job. Of course the volume of air must be large enough not only to dilute the gases but to carry away explosive fumes and fine coal dust quickly. Mechanical loading entails cutting and drilling of the coal during the same working period as the loading when two-shift and three-shift operations are employed, and all three processes create finely pulverized coal, which in itself is hazardous if not controlled by some means. If the ventilation is inadequate and gas accumulates, and a spark from defective electrical

Jan 1, 1942

By Hans Conrad, W. D. Robertson

FORMAL theories of yielding and flow have been developed to describe thermally activated plastic flow in metal crystals.&apos;-" hey are all based on Becker&apos;s&apos; original idea that thermal fluctuations aid the applied stress in overcoming internal barriers to flow and lead to the following relation. where j is the strain rate; C is a constant which includes a frequency factor, the entropy, the number of flow units, and the amount of strain associated with each successful fluctuation; E(T) is the activation energy associated with flow, and is a decreasing function of the applied stress, 7; k is Boltzmann&apos;s constant; and T is the temperature in OK. The various theories differ mainly in the model chosen and in the nature of the relationship between the applied stress and the activation energy. Beckerl and Orowan&apos; suggest a relationship of the form E a(Ti — t)2, where .ri represents the stress required for flow without the aid of thermal fluctuations; Kauzmann,3 Cottrel1,5 and Seeger6,7 suggest E a(t — t) ; Fisher8 suggests E while Cottrell and Bilby4 suggest a more complex relationship between E and 7. Additional data are needed to test these various theories., esweciallv- in view of Dorn&apos;s9 ork. which indicates that the activation energy for creep is independent of the stress and strain. The present paper presents the stress-strain data derived from incremental loading of magnesium single crystals in tension and direct shear, in the temperature range of 78" to 364°K. Incremental loading was employed in order that the creep component of the strain could be determined. Stress-strain curves of aluminum10-13 and copper" single crvstals. derived from incremental loading tests, have been found to be in agreement with those obtained by the more conventional constant strain rate or loading rate tests. Two types of tests were conducted in the present investigation: 1) tests in which the temperature was maintained constant throughout the entire

Jan 1, 1958

By C. D. Dolman

Since the outbreak of the war we have discovered in the united States minerals of which there was no general knowledge, and which compared very favorably with anything that could be found in any foreign country. One of these was magnesite, or the carbonate of magnesium as it occurs in nature. This mineral crystallizes in the rhombohedra1 form, has a specific gravity of 3.00, molecular weight of 84.4, molecular volume of 28.1, and a hardness of 3.5 to 4.5.1 Had it not been for the development of the California deposits of this mineral and the discovery of immense new deposits in Stevens County, Wash., the production of steel during the war would have been more seriously handicapped than it was. Now that the war is over, we face the possibility of competition with the cheap Austro-Hungarian magnesite; and while that may not be so cheap as it was before the war, adequate protection should be given the producers in this country to insure the full development of our own resources. The consumption of magnesite in the United States in 1913, the year preceding the war, was 172,591 tons of calcined and 22,872 tons of crude magnesite. Less than 3 per cent. of this amount was produced at home. At the present time, practically all of the magnesite used in the United States is produced at home. Expensive plants have been constructed, extensive exploration work done, and production pushed to the utmost to supply the necessary requirements of the war. Thus a considerable industry has been built up within our borders. Some magnesite has been imported from Canada and Mexico, but the Canadian ore was of an inferior grade and could not be used satisfactorily. During the year 1918, production decreased in both the United States and Canada; the production in the United States was 225,000 tons in 1918 as against 315,000 in 1917, and in Canada 39,365 tons in 1918 as against 58,090 in 1917. This decrease was mainly due to over-production during 1917, the domestic demand being only 300,000 tons. The material produced and sold in the United States must contain, in the crude form, not more than 3.5 per cent. silica and 2 per cent. lime;

Jan 1, 1920

By W. Seymour

Uranium was cold rolled to a reduction in thickness of 90 pct and the preferred orientation of the grains was determined from X-ray intensity data. Complete pole figures for a large number of atom planes were plotted, and the preferred orientation was found to be duplex (102) [0101 + (012) [021]. These preferred orientations are compared with those reported for many of the hexagonal-close-packed metals. THE preferred orientation of a highly reduced cold-rolled uranium strip was determined in order to obtain additional experimental data which would be useful in further understanding the deformation mechanisms of uranium. The preferred orientations reported herein are not in agreement with those theoretically predicted by Calnan and Clews&apos; for cold-rolled uranium sheets, and differ somewhat from those reported from experiments by Fisher, and Burke and Turkalo. Such variations might be accounted for by differences in the fabrication temperature and the reductions. Experimental Procedure The uranium used in this investigation had been hot rolled to 0.060 in. at 575°C from 0.393 in., and from a 0.060 to 0.020 in. thick sheet at 275°C. From this point the sheet was cold reduced 90 pct to 0.002 in. at room temperature. Three specimens were used to obtain complete pole-figure data. The first was a 1/2 in. square section illuminated by the X-ray beam on the rolling surface. The other two were l/2 in. square longitudinal and transverse sections each made as follows: Approximately 200 1/2 in. square sections of the foil were piled one on top of the other, so that the rolling direction for each piece was kept coincident. A 1/2 in. square by 1/8 in. thick steel section was placed on the top and bottom of a pile and the entire assembly was then bolted tightly together through a 1/8 in. diam hole drilled down through the center. Each pile was then surface-ground from the two proper sides to sections 1/2 in. square by 3/16 in. thick. These specimens were then polished flat and electro-polished to remove 0.005 in. of the surfaces to be examined. It can be shown that uranium is so opaque to a Cu Ka X-ray beam that only a small percentage would be transmitted by one micron of uranium. Therefore, a method of measuring the X-ray intensities diffracted from specimen surfaces was used. The specimens were mounted in a modified Schulz reflection holder&apos; which automatically changed the position of the specimen at a constant rate. The holder, in turn, was mounted on a General Electric XRD-3 Spectro-Goniometer and an automatic record made of the diffracted X-ray intensity vs specimen position. While a specimen moved automatically through 10" inclination, at a rate of l° per min, it simultaneously rotated 360" about a normal to the illuminated surface. (The inclination and rotation angles are referred to as F and a, respectively.) The data were then plotted along the resulting spiral path on a stereographic projection, Fig. 1. Because of defocusing effects on the diffracted beam which occur when diffracting surfaces are in-

Jan 1, 1955

By Paul Pietrokowsky

THE formation of intermediate phases in the solid state reaction of titanium with silicon, germanium. and tin (of subgroup 4B in the periodic table) was the subject of a recent paper.&apos; Further investigation of the system Ti-Sn revealed the presence of a new compound on the titanium-rich side of this phase diagram. Metallographic evidence indicated that this new phase was situated very close to 75 atomic pct Ti. The present work is concerned with the crystal structure of the intermediate phase Ti3Sn. Iodide-process titanium metal, furnished by the New Jersey Zinc Co., was used in this investigation. The metallic tin was received in powder form from Charles Hardy Inc., New York; its purity was 99.80 pct. The titanium rod was machined into small cups 1 cm in diam and about 1.5 cm in height. The tin powder was compacted, melted, and then placed in the titanium cups and alloyed by electric arc melting in a helium atmosphere. The alloys, weighing approximately 8 g, were sealed in evacuated quartz tubes and homogenized at 1030°C for 5 days. This isothermal heat treatment was terminated by a water quench from the soaking temperature. Filings of the alloyed pellets were sealed in evacuated quartz bulbs and quenched from 1030°C into liquid argon. A 14.32 cm Debye Scherrer X-ray camera was used for the powder diffraction study. The copper radiation was filtered. X-ray diffraction data for the compound Ti3Sn are given in Table I. The data were indexed on the basis of a hexagonal lattice. Good agreement between observed and calculated values of the square of the reciprocal interplanar spacings was obtained with the following expression: (1/d)2 = 0.03810 (h2 + hk + k2) + 0.04410 (l2) Unit cell parameters were calculated by the method of least squares from the reflections (20.3), (22.2), (40.1), and (42.1); ao = 5.916 & 0.004A, co = 4.764 ± 0.004A, and co/ao = 0.805. The relatively small size of the unit cell allowed the unambiguous indexing of most of the reflections from planes of large spacing. An inspection of the assigned indices (Table I) reveals the absence of (hk.l) reflections when 1 2n. A systematic absence of this type leads to the space group C 6/mmc or one of its subgroups. Assuming, for a first approximation, a linear increase in the density of titanium with the addition of tin, it follows that there are two stoichiometric molecules of Ti3Sn per unit cell. The density calculated from X-ray measurements is 5.194 g cm-&apos;. At this point it became clear that Ti3Sn might be isomorphous with Mg3Cd. The 6 Ti and 2 Sn atoms were placed in the following positions of space group D4 6h, C 6/mmc: 6Tiin (h): X 2X 1/4; 22;; 1/4;Xx 1/4;x2x3/4; 2x x 3/4; x x 4; with x = 516 2 Sn in (c): 1/3 2/3 1/4; 2/3 1/3 3/4.

Jan 1, 1953

By E. A. Gulbransen, W. S. Wysong, K. Andrew

INTRODUCTION THE reaction of carbon in solid solution in a metal with the surface oxide film on many metals may be inferred from thermodynamic calculations for high vacua and high temperature conditions. Holm1 has recently shown that oxide films may be removed from ferrous materials by heating in a vacuum at high temperatures and that carbon is the essential element in the reaction. Considerable work has been described in the literature on the decarburization reaction. Several general references may be noted.2,3,4 However, the nature of the mechanism involved in the decarburization is not well understood. Our interest in this reaction resulted from many attempts to degas and to reduce by pure and dry hydrogen the surface oxides 0n strips of various types of chrome-nickel alloys. Some of the early experiments on the behavior of 13 pct chrome-iron in vacua of the order of 5 X 106 mm and at a temperature of 600°C have been reported.5 These experiments showed a slow reaction with the residual oxygen or water vapor in the system and no reaction with hydrogen. This is in accord with thermodynamic data which would lead to the prediction that it is extremely difficult to maintain a hydrogen atmosphere at 600°C pure enough to reduce Cr203 formed on the surface. The crystal structure of the superficial oxide film formed on 13 pct chrome iron and Nichrome V has been investigated in the thin film range by Gulbransen, Phelps and Hickman,6 and shown to be Cr203. It was surprising to us to note that when a specimen of Nichrome V containing approximately 80 pct nickel and 20 pct chromium was heated to 850°C in a high vacuum, the specimen&apos; lost weight. The rate of weight loss was very temperature sensitive. A study of this reaction in vacua and in a hydrogen atmosphere is the subject of this communication. TYPE REACTIONS Let us consider the various reactions which may occur when a metal is heated in vacua, in a hydrogen atmosphere, or in an oxygen atmosphere. The number and kind of reactions will depend upon the chemical nature, of the metal, its alloying constituents and the location of the alloying constituents. The metals used in this study are chrome-nickel alloys of the heater type. They consist essentially of chromium, nickel and iron, small amounts of carbon, silicon and manganese and traces of zirconium, calcium, aluminum and magnesium. The trace elements are added to improve the lifetime and other characteristics of the alloy when used as a heater. Seven of the more important reactions with which we are going to be concerned here are as follows: [I. Metal • (gas) ;--* metal + gas - degassing of the metal 2. xM(s) + y ½ 02(g) tom- M.0„ (s) – oxidation]

Jan 1, 1948