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By J. G. Savins

Certain types of macromolecules added to water and salt solutions flowing in turbulent motion can reduce the pressure gradient. Alternatively, the volumetric capacity of a pipe for these fluids is increased by the presence of these materials. Examples presented show that the drag reduction can become significant. Thus, the presence of 0.28 per cent of a gum derivative in a solution of sodium chloride flowing at 200 gal/min in a 1.89-in. pipe yields a pressure drop which is 0.44 of the single-phase drop measured under the same conditions of turbulent flow; the addition of 0.1 per cent of a vinyl derivative to a I-in. water line yields a throughput capacity which is 1.78 of the single-phase capacity at the same pressure drop. It is further shown that these phenomena are distinctly different from previous observations with other classes of non-Newtonian systems. There a simple lowering of friction factors below the levels predicted from the resistance laws for Newtonian fluids is associated with a suppression of turbulent motion. A rational physical explanation for drag reduction is advanced. Briefly, the proposed mechanism is a storage by the molecular elastic elements of the macromolecules in solution of the kinetic energy of the turbulent motion. INTRODUCTION This study was inspired by a recent review of some paradoxical drag reduction phenomena in turbulent pipe f1ow.I Under very moderate conditions of turbulent flow, the pressure gradient necessary to pump solutions containing certain specific kinds of polymers, fibers and metallic soaps may become appreciably lower than that required* to pump the solvent, i.e., water or a low-viscosity hydrocarbon, under identical flow rates in the same conduit. As shown by our review, this phenomenon of drag reduction in turbulent duct flow was first noted during the second world war, apparently arising in connection with the development of flame warfare weapons. Since that time several papers illustrating this phenomenon have appeared: Toms, Oldroyd,3 Agoston et al., Bundrant and Matthews, Robertson and Mason,6 Ousterhout and Hall,7 Daily and Bugliarello~ Lummus, Anderson, and Fox. 9 That there are practical applications for techniques which increase discharge or decrease the pressure necessary to transport a liquid through a pipeline is illustrated in the patents which have issued which take advantage of this peculiar phenomenon, e.g., Mysels,l0 Dever, Harbour, and Seifert.11 One also finds fragmentary evidence of this effect in the data pertaining to a few of the polymeric solutions studied by Shaver12 and Dodge.13 However, these investigators were concerned with the development of friction factor vs Reynolds number correlations for a variety of non-Newtonian solutions and suspensions, rather than in a study of drag reduction-. A similar kind of drag reduction effect has been observed in gases. Sproull, for example, reports that adding dust to air flowing in turbulent motion through a pipe results in a lowering of the pressure gradient at identical flow rates. There are also military applications for reducing the drag on hydrodynamic vehicles. For example, the possibility of injecting a rheologically complex fluid into the boundary layers of bodies to reduce the skin friction has been investigated by Fabulal5 and Granville.16 Along somewhat different lines are the drag reduction studies of Kramer.17118 He has shown that skin friction can be reduced by covering the surface of a vehicle with a flexible skin. The effect is apparently due to the boundary layer being stabilized by the presence of the skin. Drag reduction by means of coexisting gas and liquid boundary layers, e.g., film boiling and continuous gas injection, has been proposed by Bradfield, Barkdoll, and Byrne,19 Cess and Sparrow,20'21 Sparrow, Jonsson, and Eckert.22 Here the skin friction occurs between a vapor and a surface rather than between a liquid and a surface. There are several references in the literature to friction-factor correlations for non-Newtonian solutions and suspensions: Shaver and Merri11,23 Dodge and Metzner, Clapp,25 and Thomas.26

Jan 1, 1965

By Charles E. Nelson

THIS paper will 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 jar 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 and will be discussed briefly.1 Inasmuch as the use of fluxes is an essential part of all the melting and refining processes, this paper will deal with these in sufficient detail to point out their unique characteristics, in order to make their use more effective. The outline of this discussion will closely follow that of an earlier paper,2 with such changes and additions as seem necessary to bring it up to date. 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, which provides protection during melting and a molten pool of flux into which the solid magnesium melts. The flux is stirred through the molten metal bath and agglomerates oxide or similar foreign bodies;, on quiet standing, it 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 desirable. The open-pot method is used generally in the following processes: (I) alloying and remelting in the production of ingot, (2) in sand foundries for premelting and to a smaller extent for the production of small castings, (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 protection and refining qualities, and then drys out or thickens after a time, leaving a protecting crust on the pot surface until the time of casting. At that time it can be readily skimmed off or held back, thus allowing the contents of the crucible to

Jan 1, 1946

By C. S. Sivil

To modern civilization the platinum metals are of inestimable value. Their distinctive properties, both physical and chemical, render them indispensable in an age in which the processes of the laboratory are becoming an essential part of the daily life of the world. Generally, their function, though vital to particular processes, is not spectacular, and so remains unknown to all except the operators. Early Methods of Manufacture The properties of platinum were recognized as of prime importance for scientific work at a very early date, probably between 1750 and 1760. The difficulty of making articles from it seemed almost insurmountable, because no means of attaining the temperature necessary to melt it were known at that time. It is true that solid platinum could be obtained by fusing the metal with a more volatile metal such as arsenic, which was subsequently driven off by baking, but such a method, at its best, would give only a very brittle product, which was totally unsuitable for the purposes for which it was intended. Little, if any, progress could be made until it was discovered that platinum sponge, heated to white heat and hammered in an iron or clay mold, would metallize and retain the shape of the mold. This was a process that could not be wholly satisfactory but from it developed the method of pressing the sponge in a mold and forging it at white heat into wire or sheet. At present a somewhat similar process must be used for fabricating articles of tungsten, molybdenum and other metals of high fusing point, as with these metals we face today the same problems that the scientists of the eighteenth century encountered with platinum, but possibly the next significant advance in the metallurgy of these metals will be the devising of means to melt and cast them. TO some extent this method of preparing platinum has survived, particularly in Europe. There are one or two objections to it, but they are not serious, as they can be surmounted with proper precautions. In the first place, the material is spongy and its millions of cavities contain entrapped air. Unless this is removed by thorough forging above 1000" C. the resultant sheet shows blisters. To give such a thorough forging,

Jan 1, 1931

By L. Burris, G. A. Bennett, P. A. Nelson

Staznless steels ave rrzuch less seuel-ely attacketl by zinc lapov than by molten zinc systems. To determine the applicubility of stainless steels fov equipment items which would be exposed only to zinc vapor, the corvosion resistance of several stainless steels to zinc vapor was investigated in 500-hr- exposuves at 900° C. Two austenilic stainless steels, Types 304 and 3-17, suffered severe intergranular attack. Loss of nickel from these steels and micro-probe crnalyses indicated the probable formation of low-melting zinc-rich phases. Good vesistance to attack by zinc vapor, as determined by metallo-9-rpaphic excr)rtination and physical testing, Loas exhibited by Type 405 stainless steel, a jevvitic steel. Type 440C stainless steel, a tnartensitic steel, although suffering considevable loss in weight, was not structurally weakened. At Argonne National Laboratory liquid zinc and zinc-rich alloys are being employed as solvent media in pyrometallurgical processes under development for recovering and purifying discharged reactor-fuel materials.' Because of the high solubility of most metals in liquid zinc,' there are few metals which can serve as container materials for liquid zinc at temperatures much above the melting point. The poor corrosion resistance of the common metals and alloys to molten zinc has been discussed by Eldred.3 DeKany, Lavendel, and Burris4 tested some of the less-common alloys of the nonrefractory metals and found that they also have poor resistance to attack by liquid zinc and Zn-Mg solutions. Of the metallic materials, only some of the refractory metals such as tantalum, tungsten, and molybdenum and their alloys have shown resistance to attack by liquid zinc.4-7 In the process-development work at Argonne National Laboratory, tantalum and tungsten vessels have been used to hold liquid-zinc alloys. These vessels are housed in stainless-steel equipment, principally to permit maintenance of an inert atmosphere and operation at various pressures. In this experimental work, it has often been observed that Type 304 stainless steel suffers little attack by zinc vapor at temperatures up to about 800 °C. In contrast, severe attack occurs in areas where zinc condenses as a liquid. The extent of attack by zinc vapor on several stainless steels was investigated because there are possible useful applications of stainless steel for equipment items which would be exposed only to attack by zinc vapor. These applications include, for example, housings around processing equipment as indicated above and vapor lines leading from zinc stillpots or retorts to condensers. EXPERIMENTAL EQUIPMENT AND PROCEDURE The experimental procedure consisted in exposing stainless-steel test coupons to static zinc vapor for 500 hr at a temperature of about 900°C. The apparatus, shown in Fig. 1, consisted of a 12-in.-long closed tantalum tube jacketed in Type 304 stainless steel to prevent oxidation of the tantalum. A Zn-10 wtpct Mg* alloy charge of 293 g in the bottom of the

Jan 1, 1965

By Robert L. Taylor, Richard E. Goodman

A complete rational analysis for design of excavation slopes and loaded rock masses is a desirable but perhaps unattainable goal. Irregular external and internal boundary conditions, poor understanding of failure criteria for large masses of rock, capricious material properties, and the importance of indeterminate forces and inaccessible and virtually unsampleable rock defects emphasize the importance of experience in this aspect of rock engineering. The experience must be correlated with geological factors. In certain regions the accumulation of such experience through the observation of existing rock slopes in various formations constitutes an important aspect of studies for design of rock excavations. In former times an accepted method of rock construction consisted of trials and adjustments. This approach is not often compatible with present methods of contract management. With the development of improved instruments and warning devices such as inclinometers, piezometers, relays, stress meters, and rock noise detectors, modified trial procedures of rock construction may reappear in specific applications. In spite of the great advances made, development of methods to predict the performance of rock slopes, abutments, and foundations deserves vigorous effort. Two distinct approaches may be taken. The rock mass in question may be considered a continuum and the stresses and strains throughout the region of influence of the work may be calculated. Or, the rock mass may be described as a discontinuum whose stability calculation involves the statics and kinematics of accumulations of rigid blocks. The prototype must lie in the range between these contrasting models. As yet, however, there is little reconciliation between the two methods

Jan 1, 1967

By J.B. Pullen

The United Verde mine is in the north central part of Arizona, on the northeasterly slope of the Black Hills, near the town of Jerome. Ore was first discovered in the district about 1875, and the first mining claims were located by M. A. Ruff-ner and associates in 1877. In 1888 the late Scnator William A. Clark secured control of the property and under his ownership it developed into one of the country's most important copper producers. The property was sold to the Phelps Dodge Corporation in 1935, and since then has been under this Corporation's management. Except for shutdowns caused by general world-market conditions, production has been continuous from 1890 to date. Geology The mineralized zone ranges in area from approximately 12 acres to less than 5 acres. All mineralization occurs in the pre--Cam-brian intrusives. The first intrusion, according to geologic records, was the quartz porphyry, which later was intruded by augite diorite. Following the diorite intrusion through a series of intrusions of lesser magnitude, a pipelike mass of massive sulphide, quartz and rock was formed. The diorite forms the hanging wall of this mass, and the porphyry the footwall. Between the footwall and the sulphide a band of chlorite schist was formed, probably owing to metamorphic conditions. Commercial ore occurs along the contact of the schist and sulphide extending into the sulphide, sometimes entirely through the schist, and fingering out into the porphyry. The ore deposit was formed by replacement similar to deposits formed in limestone areas. Faulting and deformation occurred in pre-Cambrian times and again in the Tertiary period, removing approximately 2000 ft. from the top of the main United Verde ore body, forming the United Verde Extension ore body, the only other major ore body in the district. Major development work has shown that the sulphide mass extends to the 3300-it. level, and diamond drilling below this level has indicated that the mass might extend below the 3700-ft. level, but in a diminished quantity. While many copper minerals exist in the mine, the chief commercial mineral is chalcopyrite. Aplan and vertical section of the mineralized zone showing the principal geological eatures is shown in Figs. I and 2. General Description and Physical Condition or Mine After over 50 years of active production, ore still exists on almost every level of the mine. This condition is due to many causes —-mine fires, which broke out as early as 1894, caused the abandonment of certain areas; subsidence and ground movements retarded the cleaning up of others. Furthermore, in the early days there was such an abundance of ore that when mining became dificult it was a simple matter to replace the production by going to a deeper level. Several attempts were made to recover the ore in the fire zone, both by glory-holing

Jan 1, 1943

By J. B. Pullen

The United Verde mine is in the north central part of Arizona, on the northeasterly slope of the Black Hills, near the town of Jerome. Ore was first discovered in the district about 1875, and the first mining claims were located by M. A. Ruff-ner and associates in 1877. In 1888 the late Scnator William A. Clark secured control of the property and under his ownership it developed into one of the country's most important copper producers. The property was sold to the Phelps Dodge Corporation in 1935, and since then has been under this Corporation's management. Except for shutdowns caused by general world-market conditions, production has been continuous from 1890 to date. Geology The mineralized zone ranges in area from approximately 12 acres to less than 5 acres. All mineralization occurs in the pre--Cam-brian intrusives. The first intrusion, according to geologic records, was the quartz porphyry, which later was intruded by augite diorite. Following the diorite intrusion through a series of intrusions of lesser magnitude, a pipelike mass of massive sulphide, quartz and rock was formed. The diorite forms the hanging wall of this mass, and the porphyry the footwall. Between the footwall and the sulphide a band of chlorite schist was formed, probably owing to metamorphic conditions. Commercial ore occurs along the contact of the schist and sulphide extending into the sulphide, sometimes entirely through the schist, and fingering out into the porphyry. The ore deposit was formed by replacement similar to deposits formed in limestone areas. Faulting and deformation occurred in pre-Cambrian times and again in the Tertiary period, removing approximately 2000 ft. from the top of the main United Verde ore body, forming the United Verde Extension ore body, the only other major ore body in the district. Major development work has shown that the sulphide mass extends to the 3300-it. level, and diamond drilling below this level has indicated that the mass might extend below the 3700-ft. level, but in a diminished quantity. While many copper minerals exist in the mine, the chief commercial mineral is chalcopyrite. Aplan and vertical section of the mineralized zone showing the principal geological eatures is shown in Figs. I and 2. General Description and Physical Condition or Mine After over 50 years of active production, ore still exists on almost every level of the mine. This condition is due to many causes —-mine fires, which broke out as early as 1894, caused the abandonment of certain areas; subsidence and ground movements retarded the cleaning up of others. Furthermore, in the early days there was such an abundance of ore that when mining became dificult it was a simple matter to replace the production by going to a deeper level. Several attempts were made to recover the ore in the fire zone, both by glory-holing

Jan 1, 1943

By Ta M. Li

Recent start-up of the Pinto Valley mine and mill is expected to add to domestic copper mine capacity by some 62,500 tpy. Owned and operated by Cities Service Co.'s Miami Operations, the complex lies approximately 5% miles west of Miami, Ariz. The estimated $100- million project, the largest single construction project ever undertaken by Cities Service, includes the Pinto Valley open pit mine, a 40,000-tpd concentrator, and a 10-mile slurry pipeline that will transport a 28% copper concentrate slurry to a new filter plant located in Miami. Concentrate will be treated nearby at Inspiration Consolidated Copper Co.'s new smelter complex. The current pit design contains reserves of approximately 350 million tons of ore averaging 0.44% Cu. Based on an initial production target of 40,000 tpd ore and 60,000 tpd waste, mine life is estimated at 24 years. The current stripping ratio is 1.5: 1, requiring the ultimate removal of more than 500 million tons of waste and leach-grade material.

Jan 6, 1975

By Fred A. Anderson, George B. Wallace, Edward J. Slebir

As the reservoir rises behind an arch dam, it presses the arch into the canyon walls and valley floor. To compute the stresses, deflections, and arch reactions, it is necessary to know how much the rock deforms under the combined loads of gravity, temperature, and water. Under sustained loading for a period of time, the rock continues to deform or "creep" slightly, causing changes in the stresses and shape of the arch. Under reduced loading, the elastic arch tends to resume its unstrained position and it is important to know that the rock will follow it and maintain tight contact along the abutment. It is, therefore, important to know the "set" characteristic of the rock. Past attempts to define load-deformation properties of rock, including creep and set, have largely l been limited to laboratory test of intact cores and in-situ jacking test utilizing bearing plates 2 to 3 ft in diam. In both cases, a uniaxial load has been applied to a volume of rock too small to fully reflect the influence of cracks, joint systems, foliation, and other inherent weaknesses within the rock mass. This chapter describes a large radial jacking test which more nearly duplicates the action of an arch dam by penetrating the load deep into the rock mass, bringing into play more of the factors which contribute to prototype deformation. Results obtained from the large radial test are compared with those from smaller uniaxial test. DESCRIPTION OF RADIAL TEST The radial jacking test described in this chapter was performed in an adit off of an exploratory tunnel driven into a proposed dam abutment

Jan 1, 1972

By C. Perez-Rosales

A simplified method for evaluating specific surface of porous media is described. The theory takes as its point of departure a previous statistical method. Due to its simplicity, it is considered that the proposed method has certain advantages over methods currently used. By making some simplifications, the procedure for estimating specific surface is reduced to superposing, on an enlarged reproduction of a section of the sample to be analyzed, an evenly spaced grid and counting the number of intersections of the grid lines with the perimeter of pores. An indirect test of the theory is presented and the advantages of the method are discussed. INTRODUCTION The specific surface of a porous medium, defined as the surface area of the pores per unit bulk volume, is an important parameter with regard to flow of fluids through porous materials. In particular, it has long been recognized that specific surface is closely related to permeability. Since the internal surface of any porous material is extremely complex, the measurement of specific surface can only be accomplished by indirect means. It is considered that the best method' in current use for determining specific surface is the statistical method of Chalkley, Cornfield and Parka who originally applied it for estimating volume-surface ratios of morphologic components, such as cells or nuclei. This method will be outlined later. A method which has been used extensively in determining specific surface is based on the adsorption of a vapor by the internal surface of porous media. However, this method does not yield the surface pertinent to fluid flow, since it includes the tiny molecular interstices which do not influence the permeability of the porous material.' This method has been employed by Brooks and Purcell measure internal surface area of sedimentary rocks. The Kozeny equation, which relates the specific surface to the permeability of a porous medium, has found wide use in determination of specific surface. However, the KOzeny equation is not strictly correct. Large discrepancies have been found between theory and experiments.' Consequently. the specific surface estimated by this method is subject to serious uncertainties. Finally, there are other methods for specific surface measurements which are based upon a variety of physical and chemical properties: the heat conduction by a gas, ionic adsorption phenomena and direct chemical reactions of the surface with other substances. This paper describes a simplified statistical method for determining specific surface of porous materials. It is considered that, due to its simplicity, it has certain advantages over the methods presently used. For its validity, it is required that the porous structure of the material under study be of a spatially random nature. This is not a serious limitation since the naturally occurring porous media have this characteristic. THEORY The method proposed in this paper takes as its point of departure the interesting result obtained by Chalkley et al The method shows that if a line of length r is dropped repeatedly at random over a section of a porous medium, and counts are made of the number of times the two end points fall within pore areas (denoted by h for "hits") and the number of times the line intersects the perimeter of pores (denoted by c for "cuts"), then in a very large number of throws where S is the internal surface of the sample (surface of pores) and V, the volume of the pores (Fig. 1). Since the specific surface S, and the porosity 4 are given, respectively, by S. = Sl V, and 4 = V,l V,, where V, is the total volume of the sample, it follows from Eq. 1

By Raymond S. Weimer

Of the several characteristics of a coal that influence its suitability for use in a given piece of burning equipment, the clinkering and slagging characteristics of the ash of the coal are highly important. They determine the maximum rate at which the coal may be burned on a stoker or in pulverized form without difficulty from damage to metal parts, from erosion of refractory walls, or from stoppage of gas passages by accumulation on the tubes. They also determine the minimum rate at which a slag-tap furnace may be operated without difficulty in removal of the ash in fluid form. Need for a Better Criterion In common with other producers and users of coal, the Northern Illinois Coal Corporation has long used the available methods for the measurement of the clinkering characteristics of coal ash, chemical composition and fusion temperature of the ash, as criteria for the selection of coal that would suit the particular requirements of its customers. These two available criteria have greatly helped in the problem of selection but it is unnecessary to dwell upon the fact that they are not completely adequate for the purpose. The composition of the ash and its clinkering tendency vary widely over the company's mining area. In a certain period, some years ago, an unusual amount of severe clinkering of the ash of coal shipped made extremely acute the need for a better criterion of the clinkering that might be expected. It was also desirable that the criterion result from a reasonably rapid method, so that the clinkering characteristics of the coal would be known before shipment. Complaints on the severe clinkering of the ash came from only a fraction of the output of the mine but the occurrence of the clinkering seemed quite unpredictable. Attempts to relate the chemical composition of the ash and the fusion temperatures to the clinkering were unsuccessful. Coal from the area of the mine in which the fusion temperature of the ash was the lowest gave the least trouble from clinker-ing. Chemical analysis of the ash from that section giving the most trouble showed high contents of iron and low contents of silica, but frequently these were not greatly different from those of coals that gave little trouble from clinker. Aside from the clinkering difficulty, the coal was quite satisfactory. The ash content was normal and high rates of burning could be obtained, but again and again such severe clinkering would occur that the furnace would be shut down because of the accumulation of clinker. Examination of the clinker from the customers' plants showed that the clinkers that adhered to the grates and fouled the fuel beds were hard, flat, dense, and usually dark in color. Coal that was satisfactory gave clinkers that were softer, bulky rather than flat, of low density, and usually lighter in color.

Jan 1, 1944

By Raymond S. Weimer

Of the several characteristics of a coal that influence its suitability for use in a given piece of burning equipment, the clinkering and slagging characteristics of the ash of the coal are highly important. They determine the maximum rate at which the coal may be burned on a stoker or in pulverized form without difficulty from damage to metal parts, from erosion of refractory walls, or from stoppage of gas passages by accumulation on the tubes. They also determine the minimum rate at which a slag-tap furnace may be operated without difficulty in removal of the ash in fluid form. Need for a Better Criterion In common with other producers and users of coal, the Northern Illinois Coal Corporation has long used the available methods for the measurement of the clinkering characteristics of coal ash, chemical composition and fusion temperature of the ash, as criteria for the selection of coal that would suit the particular requirements of its customers. These two available criteria have greatly helped in the problem of selection but it is unnecessary to dwell upon the fact that they are not completely adequate for the purpose. The composition of the ash and its clinkering tendency vary widely over the company's mining area. In a certain period, some years ago, an unusual amount of severe clinkering of the ash of coal shipped made extremely acute the need for a better criterion of the clinkering that might be expected. It was also desirable that the criterion result from a reasonably rapid method, so that the clinkering characteristics of the coal would be known before shipment. Complaints on the severe clinkering of the ash came from only a fraction of the output of the mine but the occurrence of the clinkering seemed quite unpredictable. Attempts to relate the chemical composition of the ash and the fusion temperatures to the clinkering were unsuccessful. Coal from the area of the mine in which the fusion temperature of the ash was the lowest gave the least trouble from clinker-ing. Chemical analysis of the ash from that section giving the most trouble showed high contents of iron and low contents of silica, but frequently these were not greatly different from those of coals that gave little trouble from clinker. Aside from the clinkering difficulty, the coal was quite satisfactory. The ash content was normal and high rates of burning could be obtained, but again and again such severe clinkering would occur that the furnace would be shut down because of the accumulation of clinker. Examination of the clinker from the customers' plants showed that the clinkers that adhered to the grates and fouled the fuel beds were hard, flat, dense, and usually dark in color. Coal that was satisfactory gave clinkers that were softer, bulky rather than flat, of low density, and usually lighter in color.

Jan 1, 1944

By R. C. Buehl, J. P. Riott, E. P. Shoub

PILOT-PLANT tests have demonstrated that it is possible to produce low-sulphur sponge iron (0.03 to 0.05 per cent sulphur) as a continuous process in an internally fired rotary kiln from iron ore or mill scale; a solid carbonaceous reducing agent; and dolomite to control the sulphur content. The proportion of dolomite employed is small, so that it does not add materially to the cost of the sponge iron. The entire operation is carried out at temperatures well below the melting point of iron, so that the product is discharged in granular form. Compared with other methods for the production of sponge iron, the rotary-kiln method has the advantage of simplicity and low cost of equipment and; in addition, requires little labor for the operation of the process. The pilot-plant equipment used for this work was sufficiently large to demonstrate that the production of low-sulphur sponge iron in rotary kilns is feasible and that the costs are not excessive for applications in which sponge iron has distinct advantages over competing materials. This report constitutes a part of a program by the Bureau of Mines under a special Congressional appropriation for studying gaseous and solid fuel reduction of iron ores. Numerous articles on various phases of these investigations have appeared in Bureau of Mines publications or technical journals. Other articles are being prepared and will be published in the near future. The present program, which is under the supervision of Dr. R. S. Dean, Assistant Director of the Bureau of Mines, was initiated in .1942. However, a considerable portion of the work was a continuation of previous research performed by the Bureau. Previous investigators1-4 utilizing the rotary kiln for the production of sponge iron did not develop a suitable method for controlling the sulphur content. A review of the literature shows that the sulphur content in the product usually exceeded 0.2 -per cent unless reducing agents with very low sulphur contents were employed. This high sulphur value made the product generally undesirable for use as melting stock in electric or open-hearth furnaces. The production of sponge iron in an internally fired rotary kiln has been described in detail in Bureau of Mines Bulletin 2702; consequently, this article will be confined mostly to new features of the process-that is, means for controlling the sulphur content of the sponge iron. Suitable raw materials include iron ores or mill scale; coal or coke for reducing them, and sized dolomite (-20+100-mesh) as the sulphur-controlling agent. A mixture of the raw materials in granular form is fed into the elevated end of the kiln, which is fired axially from the lower or discharge end. In the reducing zone, which is approximately one third the length of the kiln measured from the dis-

Jan 1, 1946

The Institute is custodian of funds for support of numerous gold medals and prizes and has representatives on boards awarding still others. Details regarding the Institute Awards are given below. The Institute is represented on the boards of the John Fritz Medal, the Hoover Medal and the Washington Award, in connection with the three national societies of Civil, Mechanical and Electrical engineering; and, also, in the case of the Washington Award, with the Western Society of Engineers. The Institute is represented with these four societies on the committee in charge of the Alfred Noble Prize.

Jan 1, 1939

Jan 1, 1902

By B. L. Averbach

Recovery and primary recrystalliza-tion in cold worked metals are usually considered as two competing processes. Some of the effects which usually accompany recovery are: alleviation of stress corrosion tendencies, changes in thermal emf,1 damping capacity,2 electrical resistivity,2 and magnetic properties,3 and only minor changes in hardness or the related strength properties. During primary recrystalliza-tion new unstrained grains are formed at the expense of the strained matrix. These new grains eventually become visible metallographically, and nucle-ation and growth kinetics have been indicated for this process.4,5 Frequent attempts have been made to study the cold-working phenomenon by observations on the line broadening by X ray diffraction patterns. Relatively few measurements of line intensities have been made, although Brind-ley and his collaborators, 6,7,8 by means of film techniques, compared the intensities of cold worked Cu, Ni, and Rh patterns with those from chemically precipitated powders. These precipitated powders were presumed to be strain free, and it was found that the intensities for the cold-worked materials progressively decreased as the Bragg angle increased except for the first line, where there was an increase due to reduction in extinction. This was interpreted as a randomness in atomic position induced by cold work. Such randomness is similar to that caused by thermal agitation and has been described as "frozen heat" displacement of 0.08-0.10 A from the mean atomic position. In a recent study9 on the effect of cold work in metals on their powder pattern intensities, the changes in integrated intensity for heavily cold worked alpha brass were observed as a function of the annealing temperature. These measurements were made with a manually operated Geiger-counter spectrometer using CuKa radiation monochromated with a rock salt crystal. Intensity measurements were made with a scaling meter over small intervals of angle, and the equipment was so arranged that the diffracted and incident beams made equal angles with the specimen. Intensities could be compared directly by simply interchanging specimens, and comparisons from day to day were made with a standard whose line intensities did not change on aging. It was shown that a cold worked alpha brass standard was stable for at least a year. Table 1 indicates the results of the integrated intensity measurements on a 70 Cu-30 Zn brass. In the sample preparation, a brass plate was first cold rolled 50 pct and then filed, screened to —325 mesh, compacted into briquettes at a pressure of 60,000 psi and finally annealed for one hour at various temperatures up to 400°C. The briquetting pressure did not seem to influence the integrated intensities, and most of the cold work was introduced by the filing. Although this method of cold work is not quantitative, it was used to obtain random orientation (and thus uniform diffraction lines) in order to make accurate measurements of integrated intensity. Back reflection patterns were taken in each case to check the uniformity of the lines, and from the observed line broadening it was apparent that this type of plastic deformation was quite severe. Care was taken to traverse the entire background of the pattern and to assign to each peak the total intensity above this background. The bases of the diffraction lines were quite broad and spread out over several degrees, even for the narrow peaks. The theoretical intensities were calculated to include a temperature correction, a dispersion correction, and a Lorenz- polarization factor corrected for the crystal monochromated beam. In Table 1 it was necessary to match the calculated and observed values at only one point, and the rest of the experimental values were converted directly to this arbitrary scale. The integrated intensities in Table 1 are listed in arbitrary units, and the accuracy was sufficient to reproduce any of the measured line intensities to within + 1.5 units. It is evident that the percentage error on the strongest line (111) was quite low. The calculated values and the observed intensities for the cold worked material matched reasonably well. As the annealing temperature was raised, however, the intensity of the strongest reflections, particularly the (lll), decreased measurably. Since the background intensities of all of these patterns were identical, such behavior could be interpreted as a primary

Jan 1, 1950

By Woolsey Johnson

THE object of this paper is to, describe the several necessary characteristics of the zinc-retorting charge and to show how by certain improved methods; the large excess of coal, over that theoretically required, can be reduced, thereby effecting an increase in the smelting capacity of a retort plant as well as other economies. In the Southwestern zinc works a charge of roasted zinc ore with a side mixture of carbonates and silicates, analyzing on the average 50 per cent. Zn, is mixed with 55 or more per cent. of its weight of a mixture of coal and coke analyzing 60 to 70 per cent. fixed carbon. . The ore is of varying fineness and the coal and coke are usually crushed in a semi-moist condition through a 3/8 -in. screen. With ores of a slaggy nature, this coal proportion is increased, sometimes to as much as 100 per cent. of, the weight of the ore. With carbonate ores, or where anthracite screenings with higher carbon content are cheap enough, the percentage of reducing agent is cut to 45 per cent. or even somewhat lower. The average charge per retort for a monthly run of a plant on ore, as distinguished from retorts on blue-powder, ladle-skimmings and other between-products, runs from 60 to 66 lb., with a mean of 63 lb. for the Southwest with standard retorts of 8 ½ -in. inside diameter and 50 in. long inside, using roasted sulphide ores. Conditions will change these figures, but 40 lb. of ore per cubic foot of retort space is, I believe, an average in the better-operated plants. Since the rise in. the price of spelter, the tendency has been to overcharge. To remove the slag that is formed when retorts are overcharged, extra men are put on to "gum-chisel" the retorts to prevent "set" furnaces and "butchered, retorts." Taking the above conditions as premises, we find that from four to six times the amount of coal necessary for the reduction is used, as is evidenced by the fact that the residues analyze as high as 35 per cent, fixed carbon. There are good reasons why this excess of fixed carbon must be used and perhaps these can be best explained by a description of the metallurgical requisites of a zinc charge. We may enumerate these as follows: 1. High reducing power, especially at the end f the shift, to reduce any carbon dioxide to monoxide and bring about a good condensation

Jan 2, 1918

By Richard V. Hughes, Rudolf J. Pfister

The necessity for getting more water into sands of low permeability in any secondary-recovery water-flood operation in order to recover all the available oil always has been a major problem. In the early days of water-flooding the addition of soda ash and caustic soda to fresh input waters was recommended and tried without success in the Bradford field. The most frequent difficulty was sand plugging. The use of natural and artificial brines often has been suggested for water-flooding, in the belief that laboratory observations of decreasing fresh-water throughput rates in measuring water permeabilities of consolidated sand cores might be partially explained by swelling of clays. A review of available literature bearing on the subject and related laboratory experiments are presented herein, offering an explanation for failure in use of soda ash and caustic soda waters and supporting the recent concept that every water used for input purposes in the secondary recovery of oil should possess such physical and chemical characteristics as to keep the clay content of the producing sands in a permanently flocculated condition. Produced brines meet this requirement. Their use is recommended as a means of increasing intake rates of tight sands and oil recoveries, as a solution to brine-disposal problems, and as a means of conserving a natural resource. Introduction There is a general belief among those engaged in the secondary recovery of oil by water-flooding that one of the most important requirements for the success of any such project is an adequate supply of good, fresh water. Fresh waters have the advantages of being more easily stabilized than salt waters and of being usable about the lease for all purposes. The use of brines for water-flooding never has been given much consideration in the Pennsylvania Grade area. The use of brines in Mid-Continent operations has been considered largely as a substitute for fresh waters, which were economically unobtainable for many operations. Estimated recoveries for some water-drive fields indicate that less of the original oil in place will be left upon abandonment than with the above-average practices used in Pennsylvania Grade water-flood operations. Lower residual oil saturations than 25 pct of the pore space following the water-flooding of Third Bradford sand cores in the laboratory are unusual. In comparison, water-flushed sands surrounding any virgin oil pool are found to be practically devoid of oil. Such lower natural residual oil saturations may be the result of a time factor much longer than economic under artificial water-flood operations, but neither the producer of primary oil nor the producer of oil by secondary recovery can obtain maximum recoveries unless full advantage is taken of all natural forces and

Jan 1, 1947

By Richard V. Hughes, Rudolf J. Pfister

The necessity for getting more water into sands of low permeability in any secondary-recovery water-flood operation in order to recover all the available oil always has been a major problem. In the early days of water-flooding the addition of soda ash and caustic soda to fresh input waters was recommended and tried without success in the Bradford field. The most frequent difficulty was sand plugging. The use of natural and artificial brines often has been suggested for water-flooding, in the belief that laboratory observations of decreasing fresh-water throughput rates in measuring water permeabilities of consolidated sand cores might be partially explained by swelling of clays. A review of available literature bearing on the subject and related laboratory experiments are presented herein, offering an explanation for failure in use of soda ash and caustic soda waters and supporting the recent concept that every water used for input purposes in the secondary recovery of oil should possess such physical and chemical characteristics as to keep the clay content of the producing sands in a permanently flocculated condition. Produced brines meet this requirement. Their use is recommended as a means of increasing intake rates of tight sands and oil recoveries, as a solution to brine-disposal problems, and as a means of conserving a natural resource. Introduction There is a general belief among those engaged in the secondary recovery of oil by water-flooding that one of the most important requirements for the success of any such project is an adequate supply of good, fresh water. Fresh waters have the advantages of being more easily stabilized than salt waters and of being usable about the lease for all purposes. The use of brines for water-flooding never has been given much consideration in the Pennsylvania Grade area. The use of brines in Mid-Continent operations has been considered largely as a substitute for fresh waters, which were economically unobtainable for many operations. Estimated recoveries for some water-drive fields indicate that less of the original oil in place will be left upon abandonment than with the above-average practices used in Pennsylvania Grade water-flood operations. Lower residual oil saturations than 25 pct of the pore space following the water-flooding of Third Bradford sand cores in the laboratory are unusual. In comparison, water-flushed sands surrounding any virgin oil pool are found to be practically devoid of oil. Such lower natural residual oil saturations may be the result of a time factor much longer than economic under artificial water-flood operations, but neither the producer of primary oil nor the producer of oil by secondary recovery can obtain maximum recoveries unless full advantage is taken of all natural forces and

Jan 1, 1947

By Douglas Ashmead

In his paper Mr. Braley makes no mention of the bacteriological aspects of the problem. It is now quite well established that certain bacteria play a major role in formation of acid mine waters, and it is a simple matter in the laboratory to show that under sterile conditions the rate of acid production from a pyrites suspension is only about one quarter of that obtained from a similar suspension inoculated with drainage from a mine producing an acidic pit water. Under sterile conditions the oxidation is due to direct chemical action and, from the evidence just given and from much other evidence, this increase under nonsterile conditions is due to certain bacteria. Experiments recently completed, and shortly to be published, have shown that this bacteriological oxidation can be prevented by the maintenance of pH conditions above 4. It was found that to raise this pH above 4 at the beginning of the experiments was not sufficient but that, due to the continuing chemical oxidation, alkali had to be added daily to maintain the pH conditions above 4. The amount of alkali added, however, over a fixed period, was only about one quarter of the alkaline equivalent of the acid produced when pH conditions were not controlled over an equal period. The opinion expressed by Mr. Braley that sodium hydroxide has little or no effect on the rate of oxidation of pyrites is not substantiated by the above experiments. The writer does not claim that these results show a practical solution to the problems, especially in abandoned workings, but feels that the application of an alkaline coating, such as lime wash, to exposed accessible workings might be well worth trying. S. A. Braley (author's reply)—In 1919 Powell and Parrl suggested that bacteria, or some catalytic agent, hastened the oxidation of pyritic or marcastic sulfur in coal. Carpenter and Herndon (1933)' attributed the action of Thiobacillus thiooxidans. Colmer and Hinkle (1947)3 observed an organism similar to T. thiooxidans and another organism that oxidized iron. Leathen and Braley 9rst discovered this organism in 1947 in a sample of water from the overflow of the Bradenville mine (Westmoreland County, Pennsylvania). They characterized the organism in 1954" and gave it the name Ferrobacillus ferrooxidans. Although Temple and Colmer (1951)' had suggested the name Thiobacillus ferrooxidans, since they claimed it oxidized both ferrous iron and thiosulfate, we have found that pure cultures of the organism do not oxidize thiosulfate, hence the name F. ferrooxidans. In 1955 Ashmead7 isolated an organism, similar to the one called Thiobacillus ferrooxidans by Temple and Hinkle, from acid mine water in Scotland. It is probable that this organism was F. ferrooxidans. In 1954 Bryner, Beck, Davis, and Wilsonh reported microorganisms in effluents from copper mine refuse. These organisms appeared to be similar but were not in pure culture. In view of this history of bacterial investigation of acid mine water and our own ten years of experience, we do not agree with Mr. Ashmead that bacteria play a major role in acid formation. We do not find that any of these bacteria will directly oxidize pyritic material. They do, however, augment the chemical formation of sulfuric acid by atmospheric oxidation. In two papers in 1953% eathen, Braley, and McIntyre discuss the role of bacteria in acid formation and postulate the mechanism through which they operate. Mr. Ashmead in his discussion of my paper has assumed that this work was carried on in the presence of acid mine water in which bacteria would be present. This was not the case. Strictly sterile conditions were not maintained, but the organisms present in mine drainages were definitely absent in these experiments. We believe that we have demonstrated that alkalis do not inhibit the chemical oxidation of pyritic material. This is also indicated by Mr. Ashmead's discussion in which he says that alkali must be added daily due to the continuing chemical oxidation. It is interesting to note that Mr. Ashmead finds that maintenance of pH above 4.00 decreases the activity of the bacteria. We have found also that a decrease in pH below 2.8 also inhibits its activity. Table XIII of published data'" illustrates the decrease in activity with increased acidity, although pH values are not given. These values are in comparison with uninoculated controls and show the marked increase in acidity up to 22 weeks but a decline at 29 weeks, at which time the experiment was terminated. It is probable that after a longer period only chemical oxidation would have continued. From our studiesv we have postulated that the iron oxidizing bacterium (Ferrobacillus ferrooxidans) oxidizes the ferrous iron, resulting from chemical oxidation, to ferric iron. The ferric iron then aids the atmospheric oxidation of the sulfuritic material and is itself reduced to ferrous iron, which in turn acts as food for the autotrophic bacteria. Study of the physiologic properties of F. ferrooxidans shows that its preferred pH is about 3.00 and its activity decreases with variation in either direction. It is extremely inactive above pH 4.00 and below 2.5. This inactivity above 4.00 is indicated by Mr. Ashmead's observations. These properties of F. ferrooxidans then correlate perfectly with our hypothesis. Ferrous iron is oxidized very slowly by atmospheric oxygen in highly acid sohtion and since the bacteria become inactive, acid is formed only by atmospheric oxidation. At a pH of 4.00 or above iron is more readily oxidized by atmospheric oxygen, but the bacterial activity is decreased. However, with a pH above 4.00 the ferric iron is removed from the field of activity since its soluble sulfate hy-drolyzes and precipitates the iron as ferric hydroxide or a basic sulfate. As we have shown in the paper under discussion, the alkali does not inhibit the chemical oxidation, and thus the acid formation continues. This

Jan 1, 1957