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By M. King Hubbert

In 1856 Henry Darcy described in an appendix to his book, Les Fontaines Publiques de la Ville de Dijon, a series of experiments on the downward flow of water through filter sands, whereby it was established that the rate of flow is given by the equation: q= - K(h2- h2)/I1 in which q is the volume of water crossing unit area in unit time, I is the thickness of the sand, h1 and h2 the heights above a reference level of the water in manometers terminated above and below the sand, respectively, and K a factor of proportionality. This relationship, appropriately, soon became known as Darcy's law. Subsequently many separate attempts have been made to give Darcy's empirical expression a more general physical fornzulation, with the result that .so many mutually inconsistent expressions of what is purported to he Darcy's law have appeared in published literature that sight has often been lost of Darcy's own work and of its significance. In the present paper, therefore, it shall be our purpose to reinform ourselves upon what Darcy himself did, and then to determine the meaning of his results when expressed explicitly in terms of the pertinent physical variables involved. This will be done first by the empirical method used by Darcy himself, and then by direct derivation from the Navier-Stokes equation of motion of viscous fluids. We find in this manner that: q = (N4(p/p)[g - (l/p) gradPI = WE, is a physical expression for Darcy's law, which is valid for liquids generally, and for gases at pressures higher than about 20 atmospheres. Here N is a shape factor and d a characteristic length of the pore structure of the solid, p and IL are the density and viscosity of the fluid, a = (Nd2)(pip) is the volume conductivity of the system, and E = [g - (l/p) grad p] is the impelling force per unit mass acting upon the fluid. It is found also that Darcy's law is valid only for flow velocities such that the inertial forces are negligible as compared with those arising from viscosity. In general, three-dimensional space there exist two superposed physical fields: a field of force of charucteristic vector E, and a field of flow of vector q. The force field is more general than the flow field since it has values in all space capable of being occupied by the fluid. So long as the fluid density is constant or is a function of the pressure only, curl E = 0, E = - grad F where F = gz + dp/p The field of flow, independently of the force field, must satisfy the conservation of mom, leading to the equation of continuity div pq = — f ap/at , where f is the porosity, und t is the time. For steady rnotion ap/at = 0. and div pq = 0 .

Jan 1, 1957

By Lester W. Strock

METALLURGISTS handling lead and zinc ores have long been familiar with the spectrograph as a routine analytical tool, as its earliest regular use by American industry was in controlling impurities of zinc metal and its alloys. This application has been extended to other metal industries on an extensive scale, accompanied by refinements of procedure to such an extent that a large part of some metals produced, especially magnesium, aluminum and steel, are checked only by spectrographic methods for conformity to specifications. The spectrographic analysis of ores and other poorly conducting powdered solids presents difficulties not encountered with metallic samples, which can be arced or sparked as self-electrodes or can be readily dissolved, so that their solutions can be analyzed, as in the American Society for Testing Materials standard methods for zinc and zinc-base alloys. Spectra of powdered solid samples can be prepared by using carbon electrodes provided with a crater of suitable size, into which the sample is packed. Ore samples and many other powdered solid materials usually analyzed in the chemical and metallurgical laboratory are more complex and varied in composition than samples of metals produced in large tonnages. More preliminary work therefore is usually necessary in devising a spectrographic method for analyzing a given type of powdered sample than for analyzing metal samples, in order to use that method with confidence. The knowledge that the standard samples and unknowns produce equivalent line intensities at equal concentration is the fundamental basis of any quantitative spectrographic method. On the other hand, powdered samples have an advantage over metals in that any desired number of chemical compounds can be mixed dry in any desired ratio to produce a synthetic standard. Experience has shown, however, that spectra of elements in finely divided compounds introduced into a standard in preparing a synthetic ore sample do not always behave in the electric arc in a manner that produces spectral line intensities similar to those observed at the same concentration in a natural mineral. In ore samples minor elements frequently are contained in the crystal lattice of larger particles of an abundant ore mineral. Their dissociation and volatilization from the sample into the arc then proceeds differently in the standard and sample, with resultant differences in intensity. During the past 10 years I have devised and applied several quantitative spectrographic methods for determining various elements in rocks and minerals in connection with studies on their geochemistry,1 but the incentive has gradually changed since the summer of 1940 to the specific practical problem of searching for domestic sources of rare and strategic metals. The

Jan 1, 1945

By J. E. Pollock, W. R. Hicks, E. Camp

In the oil-refining industry, steel comprises by far the greatest proportion of the materials used in construction work, but with an enormous number of alloy steels and nonferrous alloys available, and a greater knowledge of their properties and corrosion resistance, a substitution first in the "hot spots" and then in locations of moderately severe corrosive conditions will be made as the greater expense can be justified. In new construction work, advantage is taken of the experience already gained and appropriate materials used, whether for high temperatures and pressures demanding additional strength or for corrosive conditions. The locations, however, where equipment in operation constantly requires replacement will soon become evident, as will the necessity for replacement in more resistant materials, if considerable down-time is to be avoided. In what direction and how far to go in the matter of alloys then becomes a question of the highest importance. Obviously, any replacement with more costly material must be justified economically by the promise of longer life, thereby saving both material and installation costs besides the reduction of loss of production. Where the equipment is overcapacity and a regular schedule of cleaning periods is in force, the last item frequently must be ruled out and justification made on the basis of the first two only. Installation of material that will outlast the remainder of the equipment and have no recovery value must also be avoided; this is particularly important in temporary construction or in old equipment that will soon become obsolete. Test Methods Either one of two methods or a combination of both, in the absence of reliable data in similar services, may be adopted to determine to what extent replacement with other, and perhaps more expensive, materials is justified. A unit may be constructed incorporating different metals or alloys so that comparative service may be obtained under the same service conditions; this has been applied in many instances, such as condenser and tank construction, but the opportunities for inspection may be few and

Jan 1, 1935

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

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

Jan 1, 1943

By C. L. Mantell

Although so common and well known a metal, tin is really a less abundant element than many of those less familiar and usually ranked with the scarce or rare elements, such as cerium, yttrium, lithium, beryllium, titanium, zirconium and vanadium. The color of tin is white, with a slightly bluish tinge. When it is compared with nickel, the latter metal is brown. When placed alongside of tin, chromium is definitely blue. Tin is whiter than silver or zinc. Exceedingly thin films of tin show various shades of brown by transmitted light. The metal has a brilliant luster, and when mirror-polished, has high light reflectivity. The luster depends to a large extent upon the pouring temperature at which the metal is cast. If the temperature be too high, iridescent colors may show on the surface. These are the result of oxide film formation. If the pouring temperature be too low, the surface is dull. Small amounts of foreign metals, such as lead, arsenic, antimony and iron, decrease the luster of tin and impart a yellowish tinge to the metal. The structure is decidedly crystalline. The cast metal is a mass of crystals. When a bar of tin is bent, it emits a characteristic creaking sound. This is called the "cry" of tin, resulting from the grinding of the crystals one against the other during the bending of the metal. Tin metal may lose its crystalline structure by cold working, but grain growth occurs rapidly under the influence of heat. Metal which has been cast at a low temperature may become amorphous as the result of mechanical work. If such material be heated to temperatures well below the melting point, say at 110° C. for a half hour or for a few minutes at 150" C. recrystallization occurs. If the surface of tinned plate, tin foil, or tin meta1 in cast form be etched with hydrochloric acid containing a little free chlorine, attack occurs at the intererystalline faces. The surface shows patterns resembling the frost flowers on window panes in winter. The etched appearance is called moire metallique. Fine dendritic surface crystals of tin may be obtained by casting the metal on a surface of polished steel. In commercial tin plate, the intercrystalline boundaries are shown by fine grooves or channels, .which result from the method

Jan 1, 1929

By Earl W. Palmer, Cyril Stanley Smith

StKip of any of the metals used for deep drawing operations occasionally yields cups that are defective because of a rim that varies in height around the cup in a wave-like manner. Some such defects are traceable to tools or other press factors, but when the protuberances formed (usually four in number on brass and other copper alloys) are symmetrically disposed with respect to the rolling direction of the strip, they are invariably attributable to the metal. The effect is known as "earing" and the protuberances are called "ears." Other terms frequently heard are "tips," "scallops," and "corners." It is recognized that the effect is most commonly a result of a directional crystal structure produced by rolling and annealing operations in the manufacture of the metal strip. Numerous papers dealing with various aspects of the earing effect have appeared in the literature, those listed in the references1 being especially interesting and valuable. An investigation of the factors influencing earing of brass cups has been in progress in the laboratories of the American Brass Co. for several years, and it was thought desirable to make some of the results generally available in summarized form. The present paper discusses many factors that do and do not contribute to ear formation. In addition, a section is devoted to methods of minimizing the earing tendency of brass sheet by proper selection of the cold-rolling and annealing schedule by which it is produced. In the space available, it is impossible to quote detailed experimental procedures and numerical results. However, the authors make no statement that they do not believe to be properly substantiated, either by experimental evidence obtained under laboratory conditions or by experience in the actual production of deep-drawing brass in the brass mill. Mechanism of Ear Formation It must be clearly understood that the formation on cups of symmetrical ears, four or more in number, is attributable solely to the strip metal, and results from the strip having different deformation characteristics in different directions. The tools used in the drawing process, or the type and completeness of lubrication of the strip, have nothing to do with the problem of ears, although they do, of course, greatly affect the "drawing quality" of the strip and the general appearance of the cup. A single tip may be drawn up on the rim of a cup because of misalignment of the tools, or because the gauge of metal varies from side to side of the strip. The two-ear form that sometimes appears is also traceable to gauge variations. However, the four-ear and six-ear symmetrical forms that we are concerned with here are caused by factors inherent in the structure of the metal itself.

Jan 1, 1942

By David R. Mitchell

This paper is limited primarily to a description of dry coal-cleaning processes in which air currents are used to effectuate a separation between coal and refuse. Processes depending mainly on differences in the coefficient of friction, resilience and shape are not described unless the use of air is necessary for the proper functioning of the process. The air cleaning of coal is of primary importance to the coal industry of the United States. From figures presented in the 1941 edition Mechannual, it is estimated that at least 12 million tons of bituminous coal was cleaned in the United States during 1940 by machines using air as the separating medium. One of the current problems confronting the coal-preparation engineer is the dry cleaning of small sizes and slacks. Progress in machine development for the cleaning of small sizes has been slow in recent years in the United States of America; it has been much more rapid in Britain and on the European continent. This paper does not attempt an exhaustive survey of all these developments, and only machines and processes that have found considerable commercial application are cited. Further, no critical analysis has been made of the theory involved in the separation of coal from refuse by processes using air as the separating medium other than that necessary for an understanding of particular machine designs and applications. The possibility of using air for the separation of coal from refuse was recognized early by mining men and many attempts were made to develop commercial machines. The ingenuity of the early experimenters is to be marveled at in view of their lack of knowledge of the theoretical principles involved. As in other arts, practice has largely preceded theory. Yet, science and practice play a game of leap frog, now one ahead, then the other; the careful experimenmenter governs his efforts along practical lines by adapting his experiments to the limits prescribed by scientific laws. By first studying developments and the theory involved, it is not only possible to adapt processes to new uses but also to reduce materially operating cost and to build larger units without costly failures. Although many inventors have applied for patents for separating minerals by the use of air currents, the literature in regard to coal is meager. Berrisford2 describes briefly some of the early attempts to clean coal without the use of water. Several of the examples cited by him are reproduced herein. Fig. I shows a machine used for grinding and; izing, in which rollers running in a pan with a perforated bottom and fan opening on the side crushed the coal, which was then carried by the air currents to a settling chamber. The heaviest particles dropped out first and the light ones farthest away, as shown. In the year 1864, a machine was made that could be used as a sizer or to separate dirt from coal with a sized feed (Fig. 2).

Jan 1, 1942

By A. C. Fieldner, Lester L. Hirst, Henry H. Storch

Experimental work on liquefaction of coal was taken up by the Bureau of Mines in 1936 when it became evident that a prudent policy from the national point of view should include preparation for the time when gradual exhaustion of petroleum resources would require supplementing the growing demand for motor fuel with gasoline and diesel oil from coal. At that time (1936) certain foreign nations that had no home sources of petroleum, especially Germany, England, and Japan, were conducting active research and at least two of them were producing liquid fuel from coal on a commercial scale. Germany was reported to have an annual producing capacity of 800,000 metric tons of gasoline per year, and England had just put into operation the Billingham plant of Imperial Chemical Industries for the hydrogehation of bituminous coal and tar by the Bergius-I.G. process. The annual capacity of this plant was about 150,000 long tons of gasoline per annum (3500 bbl. per day). With these developments taking place in foreign countries, it seemed important to undertake a long-range program of fundamental research in this country to establish a sound groundwork for the evaluation of foreign work on synthetic liquid fuels and at the same time to obtain data on the oil yields and operating difficulties using various kinds of American coals and lignite to the hydrogenation process. The results of such research would be useful in determining the yields and quality of liquid products obtainable from various coals so that American industry would be in position to select the most suitable coals and make rapid progress in establishing this new industry when the commercial need should arise. It was hoped, also, that progress in a better understanding of the chemistry of coal hydrogenation would reduce the cost of the process materially. To carry out this program, a small continuous unit capable of hydrogenating 100 Ib. of coal in 24 hr. was installed at the Central Experiment Station of the Bureau of Mines at Pittsburgh, Pa. Small steel autoclaves or bombs of 0.3 gal. (1.2 liters) capacity also were used for batch-hydro-genation experiments in the study of the chemical fundamentals of the process. Much valuable assistance was obtained in planning the experimental program and designing the equipment from the Fuel Research Station of Great Britain and the Fuel Laboratories of the Mines Department of Canada, where such investigations had been in progress for several years. Equipment and General Procedure of Research The industrial liquefaction of coal by the Bergius-I.G. hydrogenation process as practiced at Billingham, England, from

Jan 1, 1944

By Robert B. Sosman

The chance that a Howe Memorial Lecturer will be able to refer back to a personal contact with the distinguished metallurgist for whom this lectureship is named grows steadily I I did not have the pleasure of his personal acquaintance, but I did receive from him in 1916, quite unexpectedly, a letter commenting On a paper that I had recently published27 On "Types of Prismatic Structure in Igneous Rocks." The paper was written for geologists and petrologists, but it had an application, naturally, to the crystallization of iron and steel in a mold. The letter impressed me at the time, and still does, with the breadth of of Howe's interests and his perseverance in keeping up with the progress of any branch of knowledge that had metallurgical connotations. Scope of the Lecture During several years preceding the date mentioned I had worked in collaboration with Arthur L. Day and E. T. Allen8 at the Geophysical Laboratory, Carnegie Institution of Washington, on the temperature scale as defined by the nitrogen thermometer at high temperatures. Later (1928-1947) I had the opportunity of helping to apply this experience to the pyro-metric problems of the steel industry. Because of the range of its temperatures, the multiplicity of the methods used, and the variety of its purposes, pyrometry in the open-hearth process has always offered a fertile field for both research and development. I am therefore devoting an hour to the subject of temperatures in the basic open-hearth furnace, the furnace that makes most of our steel in the united States. I would direct your attention particularly to the choice of the first two words in the title of the Lecture. One sometimes hears or reads of the ((temperature of such-and-such a furnace," as if it were a single, measurable, characteristic quantity. I need hardly emphasize to any one who has ever operated a furnace or a kiln that " temperature of the furnace " is a meaningless phrase. Even if we confine our attention to the space enclosed by the roof, walls, and hearth of an open-hearth furnace, it is doubtful whether any such space has ever been so uniform in temperature that the phrase would have a meaning. In any furnace, there are many different temperatures, capable of being measured at many different places, and actually being measured for several different purposes. These pyrometric purposes, methods, and results, if given in detail, would expand this lecture into a book on the basic open-hearth process. I must therefore confine myself to a statement of the range of temperatures as they have been observed in various parts of the furnace, indicating in a general way why they are measured, and mentioning the methods that are available without attempting to describe these

Jan 1, 1949

By E. B. Hughes, F. G. Norris

Oxidation is characteristic of all processes for making steel from pig iron. This thought has been aptly expressed by H. W. Graham13 in the recent Howe Memorial Lecture, "The process of steel-making consists of using iron oxide to reduce the carbon content of the pig iron to the desired level." Direct oxidation refers to the reaction that results from introducing oxygen either alone or mixed with other gases directly into the steel bath. In working a heat, oxygen in some form is added to the steel to remove the undesirable constituents as oxides. There are two general methods of supplying this oxygen to the open hearth bath. The method in which the oxygen is added as a compound such as Con or iron ore is designated an indirect method because the steel bath must first decompose the compound to attain oxygen in a usable form. The other method in which oxygen is added to the bath in the elemental or gaseous form, more or less diluted by other gases such as nitrogen, is a direct method because no decomposition is necessary before the oxygen reacts with iron to form FeO which is dissolved in the bath in a usable form. Bubble formation (at least of a macroscopic size) presents no problem in case of direct oxidation because the reacting agent (oxygen) is in the form of bubbles when entering the metal. Regardless of whether oxygen is intro- duced into the bath directly or indirectly, several reactions proceed concurrently. In the presence of the bath of molten iron, FeO is formed either by oxidation of iron by oxygen or reduction of oxides by iron. This FeO dissolved in the molten iron is the source of oxygen for the oxidation of manganese, carbon, silicon, and phosphorus if these are present. The oxidation of carbon from steel is the controlling steelmaking reaction. The introduction of oxygen into the bath, its reaction in the elimination of impurities, and its control by the use of de-oxidizing additions have been subjects of importance since steel was first made by the bessemer process. Direct oxidation is, in a sense, an application of the bessemer principle to the open hearth process. Graham13 states: "The use of oxygen or air jets introduced into the metal bath is essentially an effort to approach in the open hearth the turbulence, rapid interface reaction, and high production rate per hour that exists in the bessemer process." The general subject, "Oxygen in Steel-making," was given new life by the studies of Herty and associates starting about1925. The current interest in elemental oxygen is intimately related to the large scale production of oxygen developed during the war period. Some of the first applications were made during the early summer of 1946 at the Steel Co. of Canada using oxygen with the fuel. Such a use is of considerable interest and importance in contributing to faster heats but is not the subject of the present discussion which deals entirely with the introduction of elemental oxygen directly into the open hearth bath.

Jan 1, 1949

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

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

Jan 1, 1943

By Bernard Kopelman

The particle size of tungsten metal powder used to make tungsten wire for use in radio tubes and incandescent lamps must be closely controlled if the highly desirable feature of nonsagging is to be achieved. Our knowledge of factors affecting the particle size of tungsten powder has been limited by lack of any extensive literature on the subject. There are no publications in the English language discussing this problem in any but the most general terms. In this paper the published experimental information on this subject is reviewed. Based on the published data and some experimental data obtained by the author, a general theory of factors affecting the particle size of tungsten metal powder obtained by reduction of the oxides in hydrogen is offered. The various forms of the tungsten oxides and tungsten metal used in the experiments described were those prepared by commercial processes, so that the experimental results obtained on a laboratory scale would be more directly applicable to actual commercial reduction conditions. The effects of time of reduction, temperature. and concentration of water vapor in the hydrogen were observed by counting microscopically the particle distribution obtained. Such a method is very time-consuming, but the data obtained by this method are more reliable and more fundamental than those obtained by any of the several instruments available for measurement of particle size. Review of the Literature Until the year 1912, tungsten powder was prepared commercially by reducing tungstic oxide in the presence of carbon or one of its compounds (such as glycerin or ethylene glycol), usually by firing the mixture in a closed fire-clay crucible. The resultant powder contained about 95 per cent tungsten.' When reduction of tungsten oxides by H² was introduced Commercially,²,³ several investigators became concerned with the equilibria between tungsten metal and its several oxides in an atmosphere of hydrogen and water vapor.4-l3 While these many investigations were in fair agreement on the equilibria WO³ + H2 = WO2 + H2O and WO2 + 2H2 = W + 2H2O there arose considerable controversy as to the chemical composition of the oxide between WO³ and WO², because of very poor agreement on the equilibrium constant of this intermediate oxide reduction reaction. The controversy on this intermediate oxide has been in progress for more than 100 years. Thus Malguti,14 in 1835, decided it was WO2.56 In 1857, Riche15 proposed the formula W³O8. Usler,16 in 1865, confirmed the existence of WsO8 and further proposed W1O1l. In 1897, Desil7 agreed upon W²O8 but also found W5O14.

Jan 1, 1947

By J. O. Lewis

The operation of gas-condensate fields is comparatively new and involves physical principles with which the industry was not prcviously familiar. It has been necessary to devise methods for testing gas-condensate wells and to correlate laboratory and field data. In this paper new methods are advanced for interpreting well G.P.M.† tests whereby dilution by dry gas can be estimated and information supplied on revaporization of condensates by dry gas. Inaccuracies in well test data are discussed. Changes in flow rates can cause changes in the G.P.M. of the effluent and it may take some time for a well to become stabilized after an important change in flow rate. Retrograde tests as usually conducted cannot be directly compared with field G.P.M. data, because the retrograde tests usually include solution gas in the condensates, which are reported On the cumulative basis whereas field data (G.P.M.) usually report pentaneS PlUS on a rate or instantaneous basis. Introduction Though long known to physicists, the phenomena Of retrograde condensation became known to the oil and gas industry Only in recent years, when deeper drilling disclosed that the behavior of vapors under changing pressures was different in high-pressure reservoirs than under the low-pressure operations with which the industry was familiar. These deep, high-pressure reservoirs in which condensation and vaporization behaved inversely to the accustomed manner became known as "gas-distillate," or preferably "gas-condensate" fields. Partly to prevent precipitation and retention of liquids in the reservoir, but still more to prevent the waste of residue gas, the operation known as "recycling," or preferably "cycling," was instituted, in which the residue gas is reinjected into the reservoir, thus maintaining pressure and driving the wet gas to the producing wells. For lack of field experience to serve as a guide, the industry had to assume that theory and laboratory experiments could accurately forecast retrograde behaviors in operating these gas-condensate fields, but it is obvious that these assumptions should be checked at the first opportunities against actual field experience. To make such checks, it is necessary to accumulate a large quantity of reliable field data, but experience has shown that it is difficult to obtain reliable field data and that the laboratory data as usually presented are not in directly comparable form. The problems of correlation involve the complex phase behavior on the one hand, and a knowledge of field data and a visualization of underground conditions on the other hand. This paper is an approach from field experience, The purposes of this article are to discuss the sources of uncertainty in the data and to present methods of analyzing, interpreting and correlating laboratory and field data. Data mostly from lower Gulf Coast fields are presented, from which some conclusions can be derived, but better data from more sources than those available to the writer will be required before satisfactory answers to many questions can be obtained. This paper is presented to stimulate the analysis and publication of data from other fields, the reexamination of field and laboratory methods, and the taking of more complete and reliable field tests. For these purposes, the writer presents some speculations that otherwise would not be appropriate.

Jan 1, 1947

By Kurt Stock

The grades of spelter demanded by the consuming industries were not definitely established until the American Society for Testing Materials undertook to fix specifications, based on the varying percentages of the common impurities (lead, iron, and cadmium) as follows: Total, Not Leap, Iron, Cadmium, Over. Per Per Cent. Per Cent. Per Cent. Cent. A. High grade.................. 0.07 0.03 0.05 0.10 B. Intermediate................ 0.20 0.03 0.50 0.50 C. Brass special................ 0.75 0.04 0.75 1.20 D. Prime western............... 1.50 0.08 The question which grade was the best for certain purposes and why was left unanswered. The conservatism of the zinc-smelting industry and the unwillingness of the spelter-consuming industries to engage in research work prevented the full benefits being obtained that such standardization promised. The custom smelters, producing spelter in pigs or plates, found it impossible to adhere closely to the established limits on account of the variety of ores treated; and the smelters with long-established and known brands, or those manufacturing their metal into marketable products, like sheet zinc, did not have to abide by the newly established grades based on chemical percentages. Smelters engaged in the smelting of custom ores had occasional complaints about the quality of their metal, as some of the consumers, especially brassmakers and some galvanizers, used the rigid standards of the A. S. T. M. as a basis for obtaining redress from zinc smelters whenever some of their work was faulty. Indirectly, much good resulted from such complaints; for while the brassmakers and galvanizers, on the whole, did not know what was wrong, the metallurgists in charge of zinc smelters were induced to abandon their conservatism and study the influence of impurities in spelter from the point of view of the consumer. For some of us, spelter gradually ceased to be considered merely spelter; it

Jan 1, 1925

By David R. Mitchell

This paper is limited primarily to a description of dry coal-cleaning processes in which air currents are used to effectuate a separation between coal and refuse. Processes depending mainly on differences in the coefficient of friction, resilience and shape are not described unless the use of air is necessary for the proper functioning of the process. The air cleaning of coal is of primary importance to the coal industry of the United States. From figures presented in the 1941 edition Mechannual, it is estimated that at least 12 million tons of bituminous coal was cleaned in the United States during 1940 by machines using air as the separating medium. One of the current problems confronting the coal-preparation engineer is the dry cleaning of small sizes and slacks. Progress in machine development for the cleaning of small sizes has been slow in recent years in the United States of America; it has been much more rapid in Britain and on the European continent. This paper does not attempt an exhaustive survey of all these developments, and only machines and processes that have found considerable commercial application are cited. Further, no critical analysis has been made of the theory involved in the separation of coal from refuse by processes using air as the separating medium other than that necessary for an understanding of particular machine designs and applications. The possibility of using air for the separation of coal from refuse was recognized early by mining men and many attempts were made to develop commercial machines. The ingenuity of the early experimenters is to be marveled at in view of their lack of knowledge of the theoretical principles involved. As in other arts, practice has largely preceded theory. Yet, science and practice play a game of leap frog, now one ahead, then the other; the careful experimenmenter governs his efforts along practical lines by adapting his experiments to the limits prescribed by scientific laws. By first studying developments and the theory involved, it is not only possible to adapt processes to new uses but also to reduce materially operating cost and to build larger units without costly failures. Although many inventors have applied for patents for separating minerals by the use of air currents, the literature in regard to coal is meager. Berrisford2 describes briefly some of the early attempts to clean coal without the use of water. Several of the examples cited by him are reproduced herein. Fig. I shows a machine used for grinding and; izing, in which rollers running in a pan with a perforated bottom and fan opening on the side crushed the coal, which was then carried by the air currents to a settling chamber. The heaviest particles dropped out first and the light ones farthest away, as shown. In the year 1864, a machine was made that could be used as a sizer or to separate dirt from coal with a sized feed (Fig. 2).

Jan 1, 1942

By Lester L. Hirst, Henry H. Storch, A. C. Fieldner

Experimental work on liquefaction of coal was taken up by the Bureau of Mines in 1936 when it became evident that a prudent policy from the national point of view should include preparation for the time when gradual exhaustion of petroleum resources would require supplementing the growing demand for motor fuel with gasoline and diesel oil from coal. At that time (1936) certain foreign nations that had no home sources of petroleum, especially Germany, England, and Japan, were conducting active research and at least two of them were producing liquid fuel from coal on a commercial scale. Germany was reported to have an annual producing capacity of 800,000 metric tons of gasoline per year, and England had just put into operation the Billingham plant of Imperial Chemical Industries for the hydrogehation of bituminous coal and tar by the Bergius-I.G. process. The annual capacity of this plant was about 150,000 long tons of gasoline per annum (3500 bbl. per day). With these developments taking place in foreign countries, it seemed important to undertake a long-range program of fundamental research in this country to establish a sound groundwork for the evaluation of foreign work on synthetic liquid fuels and at the same time to obtain data on the oil yields and operating difficulties using various kinds of American coals and lignite to the hydrogenation process. The results of such research would be useful in determining the yields and quality of liquid products obtainable from various coals so that American industry would be in position to select the most suitable coals and make rapid progress in establishing this new industry when the commercial need should arise. It was hoped, also, that progress in a better understanding of the chemistry of coal hydrogenation would reduce the cost of the process materially. To carry out this program, a small continuous unit capable of hydrogenating 100 Ib. of coal in 24 hr. was installed at the Central Experiment Station of the Bureau of Mines at Pittsburgh, Pa. Small steel autoclaves or bombs of 0.3 gal. (1.2 liters) capacity also were used for batch-hydro-genation experiments in the study of the chemical fundamentals of the process. Much valuable assistance was obtained in planning the experimental program and designing the equipment from the Fuel Research Station of Great Britain and the Fuel Laboratories of the Mines Department of Canada, where such investigations had been in progress for several years. Equipment and General Procedure of Research The industrial liquefaction of coal by the Bergius-I.G. hydrogenation process as practiced at Billingham, England, from

Jan 1, 1944

By K. A. Johnson, F. H. Ellinger, C. C. Land

The Pu-In phase diagram has been determined by thevmal, filtvation, micrographic, and X-ray diffraction methods. This alloy system is characterized by 1) limited solubility of indium (-2 at. pet) in 6 and e plutonium, 2) one eutectic, and 3) fizte intermediate phases. Of the latter, PuIn and PuIn3 melt con-gruently, and Pu31n, Pu31n5, and the high-temperatuve 7 solid solution are formed peritectically. The n phase decomposes eutectoidally into Pu3In and PuIn at 865°C. Although the 6 phase can readily be retained to room temperature, it is not thermo-dynamically stable below 300°C. The Pu-In system has been investigated at Los Alamos as part of a study of the alloys of plutonium with the group 111-B elements. Constitutional studies of the Pu-A1 and Pu-Ga systems have been reported earlier.'9' To date, published information on the constitution of Pu-In alloys covers only the identification of the intermediate phases Pu3In and PuIn3.3,4 EXPERIMENTAL The alloys were prepared from five different lots of plutonium and three different lots of indium. The principal impurities in the plutonium differed from lot to lot within the following limits (in ppm): iron, 30 to 80; nickel, 30 to 60; aluminum, 15 to 30; silicon, 20 to 145: thorium, 50 to 300; carbon, 75 to 335; and oxygen, 20 to 135. Spectroanalysis of the indium showed that two of the lots were 99.9 wt pct pure, and the third was 99.98 wt pct pure. The alloys, in the form of about 5-g buttons, were prepared by arc melting in conventional equipment. The components for each alloy were weighed to the nearest 0.1 mg. In most instances the weight losses during melting were negligible; therefore confirmatory chemical analyses were usually not made. A few results are given in Table I. Density measurements of the arc-cast buttons were made by the liquid displacement of bromoben-zene. Heat treating was done in muffle furnaces controlled to +2°C. The alloy buttons were wrapped in tantalum foil before being enclosed in evacuated clear silica capsules. As a precaution against breakage, each capsule was in turn placed in a silica tube closed with a refractory wool plug prior to being charged into the furnace. For a moderately fast quench of the alloys, the outer protection tubes containing the capsules were plunged into cold water. Differential thermal analyses (DTA) in racuo were performed at heating and cooling rates of about 1.5°C per min. Tantalum crucibles having inverted thermocouple wells were used for most of the analyses. It was found micrographically, however, that the liquid alloys containing more than about 35 at. pct In reacted with the tantalum, resulting in contamination of the surface of the alloy. A search for a more satisfactory crucible material was not successful: tungsten and yttria behaved comparably to tantalum; thoria, vitrified magnesia, and vitrified alumina severely contaminated the alloys. So as to minimize the contamination by the crucible mater-

Jan 1, 1965

By D. C. Hilty, W. Crafts

A qualitative pseudoternary solidification diagram for the Fe-S-O system modified by manganese is proposed and supported by experimental derivation of an isothermal section at 1475°C and substantially 1 pct Mn in the solid-metal phase. The solubility of oxygen in liquid iron containing 1 pct Mn and sulphur contents up to 0.9 pct has been measured at 1600°C and found to increase as the sulphur content exceeds 0.15 pct. AS has been pointed out previously,' all oxide and sulphide inclusions in steel, excluding mechanically entrained matter, result from modifications of the basic Fe-S-O system. Therefore, one method of attack on the problem of the mechanism of deoxida-tion and inclusion formation is to examine the influence of deoxidizers on the Fe-S-O liquidus diagram. This approach has been adopted in work on the subject being carried out at the Metals Research Laboratories of the Electro Metallurgical Co. and has resulted in the postulation of types of solidification diagrams for the Fe-S-O system modified with common deoxidizers. This method has been of considerable assistance in interpretation of the factors affecting the formation of inclusions.' For the most part, however, these diagrams have been highly speculative. They were constructed primarily by inference from the pertinent binary and ternary systems and from the appearance of inclusions produced by specific deoxidizers. Moreover, since the systems contain four or more components, simplifying assumptions and qualifications were necessary in order to permit their representation as modifications of the Fe-S-O diagram. Consequently, experimental confirmation of the type of construction employed for these diagrams is desirable, and the present paper is concerned with such evidence. The addition of manganese to the Fe-S-O system was selected for initial investigation. Manganese is an important component of practically all steel and is, therefore, of fundamental interest. Because of its great affinity for sulphur, manganese has a more profound effect on the sulphide side of the Fe-S-O diagram than any of the other common deoxidizing eletments. In addition, more quantitative information pertaining to the contiguous binary and ternary systems involving iron, manganese, sulphur, and oxygen is available than for the other deoxidizers. Fe(Mn)-S-O Solidification Diagram Many of the side diagrams of interest in connection with this system are known. The Fe-Mn binary has been well established by several investigators;% the Fe-O system has been clarified by Darken and Gurry;' and FeO-MnO diagrams have been published by Herty,5 Andrew, Maddocks, and Howat,6 and by Hay, Howat, and White.7 The Mn-O diagram does not appear to have been derived experimentally, but the portion of 'it that is of interest can be visualized easily from a consideration of the melting points of Mn and MnO and the fact that a broad miscibility gap must exist between them. The ternary Fe-Mn-O diagram has been discussed by Benedicks and Löfquist,8 Wentrup,9 and by Körber and Oelsen.10 Experimental study of the Fe-Mn-O system has been carried out by Körber and Oelsen and to a lesser degree by Chipman, Gero, and Winkler,11 Hilty and Crafts," and others. On the basis of published information, then, an outline of the Fe-Mn-O liquidus diagram can be constructed as illustrated by Fig. 1. In this, as in all succeeding diagrams, transformations such as the ?-? reaction in iron have been ignored for purposes of simplification. The arrows denote falling temperature. The distinguishing feature of this diagram is the broad region of liquid immiscibility extending

Jan 1, 1955

By B. C. Allen

Surface free energy and surface self-diffusion of solid molybdenum were studied in the temperature range 1600" to 2400°C using pressure-sintered bi-crystals. Comparison of groove angles formed in various surfaces perpendicular to the grain boundary indicate a maximum of 1 pct variation in surface free energy with crystallographic mientation. This anisotropy tends to decrease with increasing temperature. The surface diffusion of the bicrystals is equivalent to that of sheet with a mild (100) Preferred orientation. Anomalously low values found for bi-crystals with surface orientations of (OOl), (012), and (011) are rationalized in terms of anisotropy in surface free energy. THE effect of crystallographic orientation on surface free energy1,' and surface self-diffusion3,4 has been primarily studied in fcc metals. The object of this work was to study the effect of orientation on surface diffusion and surface free energy of bcc molybdenum using pressure-sintered bicrystals. EXPERIMENTAL WORK Materials and Crystal Preparation. Arc-melted molybdenum rod was obtained commercially and electron beam zone refined at 50 cm per hr at 10- 5 torr to form single crystals about 8 cm long and 0.65 cm diam. Three crystals were prepared with axial orientations about 1 deg from [001.], [011], and. [111]. To reduce the carbon content, the crystals were annealed 2 hr in 1.4 atm flowing wet hydrogen at 2050°C. Then the oxygen content was reduced by annealing for 2 hr in -30°C dewpoint hydrogen at 2020°C. The resulting impurity analysis is given in Table I. Bicrystal Preparation. The single crystal rods were cut into transverse slices with a thin silicon carbide abrasive wheel to produce specimens about 0.6 cm long. They were mounted in epoxy and surrounded by stainless steel washers. Cutting in half was done longitudinally at various angles to known crystallographic planes containing the cylinder axis according to Fig. 1. To reduce surface deformation resulting from the cutoff wheel and thus reduce parasitic grain boundary formation on subsequent annealing, about 0.003 cm was manually ground off each cut surface with 600 grit paper. Care was taken to keep the surface flat. After removal from the mounts, one half was generally ro-tated 180 deg with respect to the other to give a po- tential symmetrical tilt grain boundary between the two halves. In the other cases when low misorienta-tion angles were desired, the crystals were not rotated. On the basis of symmetry, sufficient bicrystals were prepared to cover the entire range of misorientations for symmetrical tilt boundaries. The misorientations, +, ranged from 0 to 45, 0 to 90, and 0 to 60 deg for [001], [011], and [111] bicrystals, respectively. One [Ill] twist bicrystal was prepared from 2 single crystal discs rotated 17 deg relative to each other. Each specimen consisted of two pieces which were placed in a cylindrical tantalum can. Sharp edges were rounded and the fit was made as snug as possible to reduce subsequent deformation during bonding. The assembly and crystals generally were vicuum outgassed at 900" or 1700°C and then electron beam welded in the can at l x 10-4 torr. After being leak checked, the samples were placed in an autoclave and hydrostatically gas-pressure bonded5 in four batches under helium at 10,000 to 18,000 psi at 1650°C for 3 hr. Satisfactory bonds were obtained in many cases, and most of the crystals bonded after two exposures. The results did not appear to be affected by the various pressures used, preannealing conditions, crystal orientation, or time-pressure-temperature route taken to the final bonding condition. After bonding, the tantalum cans were selectively removed in cold concentrated HF. Measurements indicated overall deformation was under 1 pct. The bicrystals were metallographically ground and polished flat and perpendicular to the axis. Examination showed the boundaries were straight and almost free of parasitic grains caused by extraneous local deformation. Annealing. In preparation for thermal grooving, the bicrystals were cleaned and annealed by outgassing at 10-5 torr at 1900°C and heating at 2300°C under 1 atm 99.996 Ar for 0.5 hr. The crystals were held in a closed 4-deck box made of molybdenum sheet, and were heated in a Ta-1OW resistance furnace. The ar-

Jan 1, 1970

By Robert B. Sosman

The chance that a Howe Memorial Lecturer will be able to refer back to a personal contact with the distinguished metallurgist for whom this lectureship is named grows steadily I I did not have the pleasure of his personal acquaintance, but I did receive from him in 1916, quite unexpectedly, a letter commenting On a paper that I had recently published27 On "Types of Prismatic Structure in Igneous Rocks." The paper was written for geologists and petrologists, but it had an application, naturally, to the crystallization of iron and steel in a mold. The letter impressed me at the time, and still does, with the breadth of of Howe's interests and his perseverance in keeping up with the progress of any branch of knowledge that had metallurgical connotations. Scope of the Lecture During several years preceding the date mentioned I had worked in collaboration with Arthur L. Day and E. T. Allen8 at the Geophysical Laboratory, Carnegie Institution of Washington, on the temperature scale as defined by the nitrogen thermometer at high temperatures. Later (1928-1947) I had the opportunity of helping to apply this experience to the pyro-metric problems of the steel industry. Because of the range of its temperatures, the multiplicity of the methods used, and the variety of its purposes, pyrometry in the open-hearth process has always offered a fertile field for both research and development. I am therefore devoting an hour to the subject of temperatures in the basic open-hearth furnace, the furnace that makes most of our steel in the united States. I would direct your attention particularly to the choice of the first two words in the title of the Lecture. One sometimes hears or reads of the ((temperature of such-and-such a furnace," as if it were a single, measurable, characteristic quantity. I need hardly emphasize to any one who has ever operated a furnace or a kiln that " temperature of the furnace " is a meaningless phrase. Even if we confine our attention to the space enclosed by the roof, walls, and hearth of an open-hearth furnace, it is doubtful whether any such space has ever been so uniform in temperature that the phrase would have a meaning. In any furnace, there are many different temperatures, capable of being measured at many different places, and actually being measured for several different purposes. These pyrometric purposes, methods, and results, if given in detail, would expand this lecture into a book on the basic open-hearth process. I must therefore confine myself to a statement of the range of temperatures as they have been observed in various parts of the furnace, indicating in a general way why they are measured, and mentioning the methods that are available without attempting to describe these

Jan 1, 1949