Search Documents

Jan 1, 1891

By Irving A. Palmer

During the past 15 years in this country there have been few additions to the literature of lead smelting. After the consolidation of the principal smelting companies at the beginning of this period it became the policy of the larger company not to permit the publication of details in regard to many of its metallurgical processes. This led to similar action on the part of some of its competitors. The result, of course, was a decided decrease in the number of papers written upon the practical side of the subject. Even upon the theoretical side the contributions have been few. It would seem that the industry as a whole has suffered from this general unwillingness to exchange information. While it is true that a given company is entitled to the reward that may come from its own development of a new process, it is also true that a still greater reward might be the result of a free exchange of ideas with other plants. This principle has been recognized for a long time in other metallurgical industries, notably those engaged in the smelting of iron and the manufacture of steel. It is pleasing to note that the leading lead-smelting company has very recently decided to modify its policy of secrecy, and to permit the publication of papers covering some details of its metallurgical methods. The statement has been made that there has been but little progress in lead smelting during the period just referred to. This impression is due in part, no doubt, to the scarcity of papers written on the subject. 'There has been, it is true, some discussion of the new sintering processes, but with little reference to detail, and to the effect that blast roasting has had upon the industry as a whole. In spite of the prevailing belief, it may be said that lead smelting, in common with other metallurgical industries, has made steady and substantial progress. It is the purpose of the present paper to discuss briefly some features of the industry as it is now conducted, with special reference to the blast-furnace practice in the larger silver-lead smelting plants of the United States and Mexico.

Jan 1, 1915

By J. J. Gilman

Zinc monocrystals, when compressed nearly parallel to their basal planes (within 20), deform in a new way; and certain deformation markings, called "-bands," are typical of this new mode. Characteristics of these bands are described. Mechanical behavior of low angle zinc monocrystals was investigated in some detail. Recrystallization did not occur upon annealing of banded specimens that were free of deformation twins. -Bands do not seem to be the result of nonbasal slip, but rather, a result of a microbuckling mechanism. u-Bands differ qualitatively and quantitatively from ortho kink bands. A dislocation model, consistent with some of the features of u-bands, is described. THE plastic deformation of zinc monocrystals with slip planes (0001) nearly parallel to the stress axis was studied in this investigation. In a previous investigation, it was shown that some low angle zinc crystals (those with slip planes making angles of more than about 2.5+1° with the compression axis), deform by ortho kinking while others (those with slip planes making angles of less than 2.5+1° with the compression axis) deform in a new way.' This new mode of deformation will be described in some detail here. Some of its striking features are: 1—it operates only for compressive stresses, 2—its temperature dependence is anomalous, and 3—it exhibits a new type of "yield-point" behavior. The mode of deformation to be discussed is not new in the sense that no previous evidence of its existence had been reported. The markings that it creates on the cleavage surfaces of zinc crystals have been described by several investigators.'" However, this is the first time that it has been made to operate under controlled conditions so that its response to mechanical variables, temperature, and aging treatments could be investigated and its geometry completely described. Apparently. Jillson' as well as Holden3 and Pratt" believed that the small bands they observed were simply small versions of ortho kink bands. In fact, two of these authors3,6 "alled the markings "micro kink bands." In spite of the precedence, it is felt that this term is not entirely suitable because these bands do not have the same genesis as kink bands, and they are qualitatively different in structure. As will be indicated by later discussion, the bands seem to be related to the tensile deformation bands observed in aluminum. The present author has chosen to call the bands "micro deformation bands," or simply ",ubands," and the deformation process, ''p-banding." Experimental Methods Crystals were grown from 99.999+ pct Zn obtained from the New Jersey Zinc Co. The details of the technique are given elsewhere." It should suffice to say that the crystals were seeded for orientation control, and precision pyrex tubes were used for molding them. About 40 crystals were used, yielding some 130 specimens. Fig. 1 illustrates the typical form of the specimens and shows how the orientation angles are defined. The crystal specimens were usually 1 3/4 in. long and about 150 mil in diameter. The angle between the slip or cleavage plane (0001) and the specimen axis is designated by xo, while a is the angle between the maximum slope of the (0001) plane and the nearest close-packed direction [1210], vary ing from 0°to 30°. The crystals were cut into specimens with a jeweler's saw and the ends were squared by filing (specimens held in V-block). Crystals of this orientation are stiff toward bending, so this procedure introduced only deformation localized at the ends. Then the specimens were polished either chemically in 50 pct HNO³ or electrolytically in 20 pct chromic acid. The mechanical tests were made with an Instron testing machine. This machine weighs by means of electric strain gages on elastic bars and is quite stiff, since the full-load deflection of its load cells is at most 0.002 in. Most of the testing was done at a

Jan 1, 1956

By W. B. Finkeldey, C. H. Mathewson, C. S. Trewin

This paper was prepared upon request as a contribution to a symposium covering the manufacture, properties, and uses of the important non-ferraus metals. In approaching a subject as broad as this, there is a natural desire to build up a comprehensive and finished production which shall constitute a dependable source of information on all questions properly belonging to this branch of metal technology. There are, however, a number of circumstances, apart from the mere routine of labor and thought involved, which operate rather effectively against the possibility of completing such .an ambitious program at the present time. First of all, as far as any public record of results is concerned, the commercial rolling, drawing, and forming of zinc with relation to changes of structure and properties—and this we consider to constitute the clement~ of metal technology—might as well be an unpractised art. We have never seen a published photomicrograph showing the structural characteristics of either hard or soft sheet or strip, although the structure of castings has been frequently described, and other coarse-grained structures resulting from hard-hammering and annealing have been reproduced. Thus, an author in this field must proceed to his task without much assistance from the literature, and the outcome can represent only a personal estimate of principles, facts, or findings, and not a summary or survey of progress in the entire field as determined by varied experience, practice, and settled opinion.

Jan 1, 1921

By Shueling Woo, Charles S. Barrett, Robert F. Mehl

When one solid phase is generated from another, fixed and rational orientation relationships are observed to subsist between the parent and the new crystal. The principle has been proposed1 that the relationships obtaining between the same two phases are identical whatever the type of phase change involved, or whichever of the phases may act as parent. Many types of phase changes have been studied: allotropic transformations in pure metals, precipitation from solid solutions, eutectoid decompositions, peritectic reactions, the formation of oxide layers, and others2 Phase layers generated by diffusion of one metal into another constitute an additional type of reaction. This report provides new data on the orientation relationships occurring between phase layers formed by diffusion, in the Cu-Zn system,§ and furnishes further evidence in support of the principle. Materials and Methods The Cu-Zn system is especially suitable for these studies since the high vapor pres- sure of Zn provides an opportunity readily to create one phase poorer in Zn upon a parent phase richer in Zn by removing Zn by vaporization, or to reverse this process by adding Zn from Zn vapor; e.g., the beta phase can be found as a layer upon gamma by dezincing, or gamma can be found on beta by addition of Zn from Zn vapor. Since orientation relationships are to be sought, requiring crystals large enough for orientation determinations, it is convenient to prepare single crystals or large grains of the parent phase. The samples were prepared from oxygen-free high-conductivity copper and Horse Head zinc by melting under a borax flux in a graphite crucible. Large crystals of beta brass were grown by the strain-anneal method, in plates sectioned from the cast ingots, by the following procedure. Rockwell-hardness indents were made at I cm. intervals and with various loads, then the plates were annealed for 4 days at 700°C. in Nichrome boxes packed with beta-brass chips and graphite. Surface layers were removed by grinding and etching to a depth of about 1.0 mm., and individual grains were cut out. Crystals of alpha and gamma brass were prepared by freezing, by lowering a graphite crucible at speeds less than one inch per hour through a furnace held at a constant temperature above the melting point. Single crystals were cut out with a jeweler's saw, ground, polished and etched. Care was taken to remove cold-worked layers from the finished crystals

Jan 1, 1944

By Charles S. Barrett, Robert F. Mehl, Shueling Woo

When one solid phase is generated from another, fixed and rational orientation relationships are observed to subsist between the parent and the new crystal. The principle has been proposed1 that the relationships obtaining between the same two phases are identical whatever the type of phase change involved, or whichever of the phases may act as parent. Many types of phase changes have been studied: allotropic transformations in pure metals, precipitation from solid solutions, eutectoid decompositions, peritectic reactions, the formation of oxide layers, and others2 Phase layers generated by diffusion of one metal into another constitute an additional type of reaction. This report provides new data on the orientation relationships occurring between phase layers formed by diffusion, in the Cu-Zn system,§ and furnishes further evidence in support of the principle. Materials and Methods The Cu-Zn system is especially suitable for these studies since the high vapor pres- sure of Zn provides an opportunity readily to create one phase poorer in Zn upon a parent phase richer in Zn by removing Zn by vaporization, or to reverse this process by adding Zn from Zn vapor; e.g., the beta phase can be found as a layer upon gamma by dezincing, or gamma can be found on beta by addition of Zn from Zn vapor. Since orientation relationships are to be sought, requiring crystals large enough for orientation determinations, it is convenient to prepare single crystals or large grains of the parent phase. The samples were prepared from oxygen-free high-conductivity copper and Horse Head zinc by melting under a borax flux in a graphite crucible. Large crystals of beta brass were grown by the strain-anneal method, in plates sectioned from the cast ingots, by the following procedure. Rockwell-hardness indents were made at I cm. intervals and with various loads, then the plates were annealed for 4 days at 700°C. in Nichrome boxes packed with beta-brass chips and graphite. Surface layers were removed by grinding and etching to a depth of about 1.0 mm., and individual grains were cut out. Crystals of alpha and gamma brass were prepared by freezing, by lowering a graphite crucible at speeds less than one inch per hour through a furnace held at a constant temperature above the melting point. Single crystals were cut out with a jeweler's saw, ground, polished and etched. Care was taken to remove cold-worked layers from the finished crystals

Jan 1, 1944

By Charles S. Barrett, Robert F. Mehl, Shueling Woo

WHEN one solid phase is generated from another, fixed and rational orientation relationships are observed to subsist between the parent and the new crystal. The principle has been proposed' that the relationships obtaining between the same two phases are identical whatever the type of phase change involved, or whichever of the phases may act as parent. Many types of phase changes have been studied: allotropic transformations in pure metals, precipitation from solid solutions, eutectoid decompositions, peritectic reactions, the formation of oxide layers, and others.2 Phase layers generated by diffusion of one metal into another constitute an additional type of reaction. This report provides new data on the orientation relationships occurring between , phase layers formed by diffusion, in the Cu-Zn system, § and furnishes further evidence in support of the principle. MATERIALS AND METHODS The Cu-Zn system is especially suitable for these studies since the high vapor pressure of Zn provides an opportunity readily to create one phase poorer in Zn upon a parent phase richer in Zn by removing Zn by vaporization, or to reverse this process by adding Zn from Zn vapor; e.g., the beta phase can be found as a layer upon gamma by dezincing, or gamma can be found on beta by addition of Zn from Zn vapor. Since orientation relationships are to be sought, requiring crystals large enough for orientation determinations, it is convenient to prepare single crystals or large grains of the parent phase. The samples were prepared from oxygen-free high-conductivity copper and Horse Head zinc by melting under a borax flux in a graphite crucible. Large crystals of beta brass were grown by the strain-anneal method, in plates sectioned from the cast ingots, by the following procedure. Rockwell-hardness indents were made at I cm. intervals-and with various loads, then the plates were annealed for .4 days at 700°C. in Nichrome boxes packed with beta-brass chips and graphite. Surface layers were removed by grinding and etching to a depth of about 1.0 mm., and individual grains were cut out. Crystals of alpha and gamma brass were prepared by freezing, by lowering a graphite crucible at speeds less than one inch per hour through a furnace held at a constant temperature above the melting point. Single crystals were cut out with a jeweler's saw, ground, polished and etched. Care was taken to remove cold worked layers from the finished crystals

Jan 1, 1944

GENTLEMEN : Herewith are submitted reports for the calendar year 1933 of your Treasurer and the Chairmen of the following standing committees: Finance, Admissions, Membership, Papers and Publications, Library, and MINING AND METALLURGY. TO these reports you are referred for additional details of the year's activity. Finances.-Income for 1933 from all sources totaled $121,690 com- pared with $138,331 in 1932. Incidentally, this exceeded the income as estimated in the budget by $7,190; the largest item being a "surplus" of $3,316 over the budget expectancy as to member dues. As compared with 1932 the most important items of shrinkage in income were $9,000 from dues and initiation fees; $5,500 from the magazine, MINING AND METALLURGY; and $2,500 from sales of publications other than the magazine.

Jan 1, 1934

By P. G. Shewmon

A novel technique for determining the surface energy (?) and its derivative with respect to orientation, (?') is described. Essentially it involves the 'floating" of a wedge on the substrate, said wedge being made of a material which is not wet or only slightly wet by the substrate, i. e., as a greased needle "floats" on water. A thermodynamic analysis of a system in which the wedge is supported entirely by surface energy is given. If the original suyface is not at a cusp orientation, the surface tension is directly measurable from the groove angle formed. If the original surface is at a cusp orientation, there may or may not be a groove depending on the relative value of ?' and the weight of the wedge. Experiments primarily on copper and silver showed that sapphire, quartz and refractory metal wedges were wet while graphite wedges were not. The technique was demonstrated to work using graphite wedges, but the results obtained were not as eccurate as those obtained by other workers using the wire-creep experiments. It is concluded that the technique might prove most useful with non-metals where ?' is large and filament creep experiments would be quite difficult. If an absolute value of the surface free energy (?) of a metal is to be determined, the most reliable methods used to date measure an average over the various orientations exposed on a polycrystalline sample. For example, ? for silver, gold, and copper have been measured by determining the force required to just keep a thin wire,' or foil,' specimen from contracting under the influence of ?. Herring 3 has predicted and experiment confirms, that the sensitivity of this method is inversely proportional to the grain size.' Thus it cannot be used to measure ? for a particular orientation by using a foil single crystal or a very coarse-grained specimen. An accurate value if ? for tungsten averaged over a range of orientations has been determined using a field emission technique. The same techniques cannot or have not been used to measure ? for non-metallic solids, and as a result the values available are much less accurate.4 This Paper resents a means of making an absolute determination of ? for a particular surface orientation on any solid, as long as the given surface orientation does not break up into other orientations during an anneal. Experimentally ? is found to vary with orientation and at a few low index orientations it is found to have a cusped minimum, i.e., the derivative of ? with respect to the orientation of the surface changes discontinuously at the low index orientation, see Fig. 1. The slope of a plot of ? vs orientation (herein designated ?') is called the torque on the surface, since it tends to rotate the exposed surface toward the low index orientation, or if the surface is at the cusp orientation it opposes any force tending to rotate the surface out of the low index orientation. The ratio ?'/? has been determined for a few metals, but in cases where this ratio is high there is presently no means of determining either ?'/? or the absolute value of ?' for the orientations present on an annealed surface. The technique discussed herein also provides a means of determining an absolute value of ?' for those orientations which deviate only infinitesimally from a cusp orientation. It should work best on surfaces where ?'/? is large; that is, for cases where no other technique is available for measuring ?'. Aside from trying to learn more about surfaces through measuring ? and ?', the primary reason for wanting values of ? or ?' is to study adsorption. From measurements of the variation of ? for a particular orientation with the concentration of an impurity, one can obtain the number of impurity atoms adsorbed per unit area (Ti) on that orientation using the Gibbs adsorption equation.' where µi is the chemical potential of the adsorbed impurity. Thus, if absolute values of ? could be obtained for the free surface of a given surface orientation as a function of µi, ri could be determined for the given orientation. Furthermore, by equilibrating a grain boundary with the given surface at various values of ki, one could also determine ri for the grain boundary. Similarly Robertson 6 has pointed out that if y is taken to be a continuous function of and µi, then a2 ?/a @a µ2 = a2 ?/a pi a +. Thus, at all orientations away from cusps the following equation holds From a measurement of ?' vs ki, it is thus possible

Jan 1, 1963

THE illustration below shows the design of the face of the clock to be erected as a memorial to the American engineers who gave their lives overseas in the World War. It will be placed in the tower of the library at Louvain, which has been rebuilt through contributions from America. Large clocks seldom have figures on their faces, and each hour on this one will be marked by a gold star, the four faces containing 48 stars, one for each State of the Union. Contributions toward the memorial have been received from every one of the States, and from Alaska and Hawaii as well, but additional subscriptions are invited by the Com-mittee which is arranging for the memorial.

Jan 3, 1928

By Sidney Fischler

Large striation-free single crystals of bismuth have been grown from the melt by rapid freezing. Zone-refined bismuth, together with doping impurities if desired, is placed in a shallow flat-bottomed graphite boat and melted in air with a propane hand torch. The torch is then withdrawn in a manner which causes the melt to freeze direction-ally. Crystallization, which resuires only a few minutes, usually results in the formation of a single crystal even when a seed crystal is not used. Crys -tals of any desired orientation may be grown by using oriented seeds. Undoped crystals grown by this method have residual resistivity ratios greater than 200. THE growth of large single crystals of bismuth by either the Czochralski or horizontal zoning technique is not entirely satisfactory. Specifically, difficulties are encountered in producing single crystals of the required dimensions in all desired orientations, and striations caused by low-angle polysynthetic twins are frequently present in the crystals. In addition, both methods are time-consuming and require special apparatus of some complexity. A simpler method has now been developed for growing large striation-free bismuth single crystals of desired orientation in a short time. Fig. 1 shows a typical setup consisting of a rectangular graphite boat which contains zone-refined bismuth, a 1/8-in.-thick flat quartz plate which covers the entire inner bottom of the boat, and three additional quartz plates about 1/4 in. thick which are used to separate the bismuth from the graphite everywhere except at a small area at the left of the boat. The graphite boat is 1 in. high, and its sides and bottom are about 1/8 in. thick. The quartz plates should be smooth and clean. The graphite boat is heated from the right with a propane torch, as shown in Fig. 1, until the bismuth is completely melted. The melt has the shape of a triangle with a narrow neck at the apex farthest from the torch. The melt is frozen direc-tionally by gradually moving the torch toward the right, away from the boat. The bismuth in contact with the graphite, at the left end of the neck, freezes first. The freezing interface then moves down the neck into the main bulk of material, where it develops a convex shape ideal for the continuation of single-crystal growth. The interface continues to move through the melt until the entire bulk is solid. The entire procedure may be completed, in air, in a matter of minutes. The technique described almost always yields a single crystal whose basal plane is nearly perpendi,cular to the bottom of the graphite boat. In earlier experiments, in which the bottom of the melt was in direct contact with the graphite boat, single crystals were grown with basal planes parallel, perpendicular, or at some intermediate angle to the bottom of the boat. At times the orientation of the bulk of the material differed from the orientation of the material in the narrow neck. In these cases, a nucleation site initiated the growth of a differently oriented crystal, and the thermal conditions favored the new orientation over the initial one. The thermal conditions depend on a number of factors, including the heating technique, the placement, shape, and thickness of the quartz plates, the thickness of the walls and bottom of the graphite boat, and the quantity of bulk bismuth employed. All of these factors, plus the initial orientation and the presence and effectiveness of nucleation sites, will determine the orientation of the final large single-crystal slab. When a crystal of specific orientation is desired, an oriented section of a rapid-freeze crystal is shaped by spark cutting and grinding for use as a seed. To grow a doped crystal, the desired impurity is placed in the graphite boat together with the bismuth chunks and seed. Crystals doped with mercury, cadmium, lead, and selenium have been grown. The rate of freezing is so great that the distribution coefficient of any impurity approximates unity. On a gross scale, therefore, impurities should be more homogeneously distributed in rapid-freeze crystals than in Czochralski or zoned crystals. Because of the possibility of constitutional supercooling, however, it is quite possible that impurities are not homogeneously distributed on a microscopic scale in the rapid-freeze crystals. Generally the single crystal slabs which have been prepared are initially 5 to 7 mm thick. Thicker crystals may be obtained by using one of these slabs as a seed. The slab is placed in a graphite boat resting on a large aluminum block, either air- or

Jan 1, 1964

By O. J. Hassel, W. T. Maidens, J. H. Calbeck

The rotary gas fired reheating furnace used by the American Zinc Oxide Co. at Columbus, Ohio for Therotarygasfiredreheatingfurnacerefining lead-free zinc oxide is described. The outstanding features of this operation are that the color of the zinc oxide is greatly improved, sulphur is eliminated, and cadmium arethatrecovered without densifying the product to an objectionable degree. IN 1919 Leland S. Wemple obtained a patent for a process of reheating zinc oxide wherein the "coarsening of grain due to excessive heating was avoided." He taught in his specification that if solid carbonaceous material, such as lamp black, was added to the zinc oxide in proper amounts prior to reheating, objectionable sulphur compounds could be removed and the color would accordingly be improved and no objectionable densification would occur because of the relatively low temperature required. The situation that made this invention imperative was the newly opened zinc oxide plant of the American Zinc, Lead & Smelting Co. in Hills-boro, Ill. This was one of the early Western Type American Process zinc oxide operations. Characteristic of all of these early Western operations using Tri-State and Western ores was the great difficulty encountered in obtaining a product low enough in sulphur to compete with the Eastern Type American Process zinc oxides which were made from ores containing very low sulphur percentages. Wemple demonstrated that the refining process of his invention produced a superior color and although this was true and a most welcome feature, the primary purpose of the early refining operations at Hillsboro was to reduce substantially the high sulphur content of the crude zinc oxide. Although many and varied attempts had been made for refining zinc oxide none of the processes had a commercial history of any consequence until Wemple's invention became standard practice for the American Zinc, Lead & Smelting Co. in 1919 and their operations have been unique in that substantially all of their lead-free zinc oxide has been reheated since the first installation at Hillsboro. This process has become known in the industry as refining. The furnace developed by Wemple and continued in use by the company from 1919 until 1943 was unusual and merits some consideration by way of review in this paper. The furnace was essentially a double hearth coal-fired muffle furnace with a mechanical raking system consisting of a central shaft supporting six rabble arms in each muffle. The untreated or "crude" zinc oxide was fed onto the outer rim of the top muffle, moved to the center where it dropped to the lower muffle and progressed to the outer rim where it was discharged into an alloy screw conveyor. The retention in this furnace was extremely short, about 5 min, and the shallow zinc oxide bed on the hearths of the muffles was being continuously turned by the fast moving rabbles. Soft coal was burned on the grates below the lower muffle and the long yellow flame necessary to carry the heat around both muffles resulted in a very inefficient combustion of the fuel. The temperature of the top of the lower muffle seldom exceeded 65 °C although the oxide itself often reached 700°C before discharge. The capacity of this furnace was approximately 1/2 ton per hr. In our plant at Columbus it was necessary to keep four of these furnaces running in parallel to take care of the production because, as mentioned above, every pound of zinc oxide produced during these 24 yr passed through one of these refining furnaces. An essential part of this refining operation was the use of carbonaceous material admixed with the zinc oxide fed to the furnaces. Between 1 and 2 pct of a bran produced in the processing of cotton seed was added to all zinc oxide charged to the furnaces. The bran ignited on the top hearth and was still burning when the charge fell from the top hearth to the bottom hearth making a cascade of sparks. The rapid turning of the zinc oxide caused these particles of bran to flash on the hearths behind each rabble; but the combustion, of necessity, had to be complete by the time the charge reached the outer rim of the bottom hearth, otherwise the finished product would be contaminated with the charred particles of bran which would give the zinc oxide an unsatisfactory color. Although this operation was initiated to reduce objectionable sulphur percentages, as time went on new properties of the product were appreciated which made advisable continuing the refining process long after other methods of sulphur reduction became known in the industry. The particle size and particle size distribution, the absence of colloidal fines and perhaps a unique surface condition gave this product an outstanding performance when used in paints. The Wemple furnaces installed in Columbus in 1919 had to be rebuilt frequently and were extravagant in the use of fuel. The raking mechanism and the muffles required excessive maintenance expense and as the furnaces wore out the problem arose whether to continue along this line or to explore the possibilities of obtaining similar or better results in the simpler and more commonly used rotary furnace. To this end special research was initiated in 1941 on a small laboratory rotary

Jan 1, 1951

By Robert D. Pehlke, Robert G. Blossey

The solubility of nitrogen in liquid iron alloys containing chromium and nickel has been measured in the temperature range 1550° to 1700°C at nitrogen pressures to 1 ah. The solubility surface has been determined for the iron corner of the liquid metallic ternary to 21 pct Cr and 11 pct Ni. The nitrogen solubility increases markedly with increasing chromium concentration. The effect of nickel and the bilinear effect of chromium and nickel are less pronounced. The solubility data are presented, and interaction coefficients are determined from them. THE solubility of nitrogen has been determined in liquid Fe-Cr-Ni binary and ternary alloys. The work in this laboratory has been directed toward a relatively limited composition range, that is to 20 pct Cr and 10 pct Ni. Humbert and Elliott1 studied the entire ternary; but their investigation was, understandably, limited in this region. The region considered here is of the greatest commercial interest. Knowledge of the solubility in these alloys is important for accurate control of the nitrogen levels in various stainless alloys. Also, the solution behavior is of theoretical interest because of its deviations from ideal dilute solution rules at moderate chromium levels. The nitrogen solubility in the iron binaries has been reviewed extensively by Pehlke and Elliott,2 particularly with respect to the dilute solution interaction parameters. More recently, there has been some interest in accurate descriptions of solute interactions in non-dilute solutions. Most of the investigators have adopted a power series fit to accommodate any non-linearity of the data. The Taylor series expansion is adopted here, using Scimar's notation3 for the interaction coefficients. An alternate method, instead of requiring higher-order expansions, is to restrict the range of the composition variables. A planar solubility surface may be fitted to the data and its range of validity determined. If the axes of this region are displaced from the usual origin—the solvent pure iron—a change in standard state is required for the solution reaction. The standard state for nitrogen in iron is commonly taken as the hypothetical 1 wt pct solution of nitrogen in pure iron. However, for an alloy of appreciable solute concentration, e.g., 13 pct Cr or 18 pct Cr-8 pct Ni, it would be convenient to use that base composition as the solvent and redefine the solution reaction in terms of that particular solvent. A brief derivation follows, defining the free energy of solution in an alloy solvent. Following the treatment by Darken and Gurry,4 for a nitrogen pressure of 1 atm: N (pure component) = N (1 wt pct in solvent) [l] AG=RT ln100/ wt pct N in solvent Taking this reaction for an alloy solvent less the same reaction for a pure iron solvent the relation between nitrogen in pure iron and an alloy is: N (1 wt pct in Fe) = N (1 wt pct in alloy) [2] AG = RT[ln(wt pct N in Fe) - ln(wt pct N in alloy)] Adding ½ N2(g) to each side and subtracting N (1 wt pct in Fe) = ½N2(g), the total free energy for solution of nitrogen in an alloy, referred to nitrogen at infinite dilution, is given by: ½N2 (g) = N (wt pct in alloy) L3] AG°3 = -RT ln(wt pct N in alloy )PN =1 atm Interaction parameters have their usual meaning when ?G°/RT is differentiated with respect to the proper composition coordinate. If desired, the dilute alloy treatment may be utilized with the new reference composition as the solvent. This has. indeed, been done by Small and pehlke5 in their analysis of nitrogen solution in liquid 18-8 alloys. The Sieverts' technique was used for this investigation on an apparatus previously described.6 The materials used in this program were: Ferrovac-E iron, 99.95 pct, Crucible Steel Co.: chromium, 99.95 pct, Union Carbide Metals Co.; nickel, 99.9 pct, International Nickel Co. Recrystallized alumina crucibles were used with no evidence of crucible-melt reaction. RESULTS The locations of the ternary compositions investigated are shown in Fig. 1. The data of Turnock7 and small8 have been alluded to in other papers.5'6 There were no departures from Sieverts' law observed for

Jan 1, 1969

By CHARLES E. W.

I. LOCATION. THE Mojave mining district is situated in a group of small hills centering around Soledad peak, in the Mojave desert, Kern county, Cal. These hills are about 4.5 miles SSW. of Mojave, a railroad town at the junction of the Santa Fé and Southern Pacific railroads. The town of Mojave is about 50 miles north of Los Angeles, to which it is connected both by telegraph and by rail. The distance on the Southern Pacific railroad is 102 miles, covered in 3 hr. and 45 min. by express train. A sketch-map of this region is shown in Fig. 1. The Mojave district is relatively isolated. The only other mining towns in this section of California are Randsburg and Johannesburg, in a district (containing the well-known Yellow Aster mine) at the northern end of a low ridge of hills, which begins about 20 miles NE. of Mojave, runs nearly N. for 35 miles, and varies in width between 3 and 6 miles. As will be seen later, the origin and formation of these hills are not the same as those of Soledad peak. II. CLIMATE AND VEGETATION. The climate and vegetation of the Mojave district are typical of the arid regions of the southwestern United States. During the winter and spring there is some rainfall, and the tempera-ture is generally from 60° to 70° F. in the day-time. The rainfall in the spring is often very considerable for short spaces of time, and cloud-bursts are not infrequent. In summer there is continual sunshine, with temperatures, as a rule, exceeding 100° F. in the day-time, while 115° F. in the shade of a house is not at all unusual; but at night the temperature falls considerably. No rain falls during the summer. The vegetation

Jan 1, 1906

By D. L. Archer, W. W. Owens

Conventional waterflooding often is uneconomic in highly fractured reservoirs because of the gross bypassing of the reservoir oil by injected water. Imbibition and pressure pulse flooding have been used in at least one fractured reservoir in an attempt to achieve better oil recovery performance. This paper presents the results of laboratory flow tests conducted on large cores to evaluate the possible applicability of these methods (particularly pressure pulse flooding) to different types of reservoir systems. Test data were obtained on both water-wet and oil-wet systems, and on systems having two widely different levels of compressibility and flow capacity. Results indicate that pressure pulse recoveries from fractured reservoirs will likely not exceed 5 to 10 per cent pore space with maximum response achieved during the first pulse cycle. Improved recovery by this method is possible from both oil-wet and water-wet reservoirs. Comparable saturation distributions during imbibition and pressure pulse production suggest that an initial pressure pulse cycle to speed production response would not interfere with subsequent imbibition flooding in water-wet reservoirs. INTRODUCTION There is a steady increase in the number of fluid injection projects being initiated each year to improve oil and gas recovery over that obtained by primary production mechanisms. Experience gained in different geographical areas and with different recovery methods is teaching that reservoir anatomy is one of the more important factors controlling the success or failure of such projects. Fractured formations appear to be the rule rather than the exception, especially in carbonate reservoirs. Conventional methods of fluid injection, whether it is waterflooding, gas injection or miscible flooding, have limited applicability to highly fractured reservoirs because of the severe bypassing of reservoir fluids. The result is early breakthrough of the injected fluid and rapidly increasing ratios of injected to in-place fluid with an undesirable effect on return on investment. Thus, innovations to conventional methods must be developed if recovery from fractured reservoirs is to be optimized. One new method proposed for application to highly fractured reservoirs is pressure pulse waterflooding. Although pressure pulsing with gas has been suggested' and rested in at least one reservoir; the Sohio Oil Co. is generally credited with the development and testing of pressure pulsing in conjunction with waterflooding. Publications" of Sohio's waterflood operations in the Spra-berry Trend indicate that the idea for pressure pulse flooding evolved from a critical analysis of the disappointing early performance of their flood initiated in a portion of the trend in April, 1961. This flood was planned to take advtantage of imbibiltion and high pressure gradients across the reservoir matrix blocks (unfractured Mocks of the reservoir rock which are visualized to be generally surrounded 'by the fracture system) evaluated in pilot tests by the Atlantic Richfield Co.5 and Humble Oil & Refining Co.' However, the early recovery and pressure performance of this flood indicalted that high pressure gradients induced between the fracture system and the centers of the matrix blocks were forcing water into the periphery of the blocks and temporarily interfering with the counter-current flow of oil due to imbibition. Fill-up in the blocks was occurring with re-solution of the free gas phase as pressures climbed above the original reservoir bubble point. It appeared that cessation of water injection to permit the capillary forces to become dominant and that expansion of the rock and its contained fluids during pressure reduction might aid in expulsion of oil from the rock matrix into the fractures. Subsequent production performance. aflter cessation of injection, proved this hypotheslis correct. Thus, pressure pulse waterflooding was born. Pressure pulse flooding appears to have several advan'tages over imbibition type flooding in highly fractured reservoirs. First, all wells may be used for water injection which should hasten fill-up and achieve a more rapid increase in reservoir pressure. Second, because of increased injection pressures and rates, flooding gradients will force water into the reservoir matrix more rapidly than would be achieved by imbibition alone. Third, during the pressure depletion cycle of the flood, the compressibility of the system, which has been increased by resolution of the free gas phase, provides energy for the displacement of oil at a rate greater than would correspond to countercurrent flow during imbibition. Fourth, during depletion all wells may be put on production, thus contributing to higher oil withdrawal rates on a reservoir-wide basis. One possible disadvantage of pressure pulse flooding as compared to imbibition floodling, however, is that the outer periphery of each matrix block is flooded to a residual or near residual oil saturation during the Water lnjection stage. This zone of reduced permeability to oil m'ay offer greater restriction to the production of

Jan 1, 1967

By J. S. Marsh

OPPORTUNITY to pay tribute to the memory of Professor Henry Marion Howe is a strenuous assignment as well as an honor. Upon recalling Howe lecturers and lectures of the past 25 years, glancing over the list of those earlier, and rereading Howe's books, I arrive at several conclusions: 1—Many lecturers either worked under or knew Professor Howe. 2—It is virtually impossible to pick a subject on which Professor Howe did not touch. 3—There is precedent for a technical paper based upon pursuit of a single subject. 4—There have been listening lectures and reading lectures. There is solid comfort only in 2: the subject field is wide open. I did not know, nor even ever saw, Professor Howe, so can supply no fitting reminiscence. As a college student I was dimly aware that he counted among the giants. Fuller appreciation of his stature came with reading his books and papers, growing acquaintance with some of his associates, and the intrinsic dignity of the climax of the Annual Meeting, beginning at four o'clock of a Thursday afternoon in the auditorium of the Engineering Societies Building in New York. As for producing the technical paper sort of thing, it is my lot to have reached an age and assignment such that to do so would be to filch information from those who did the work and whose story is theirs to tell; for this I have no enthusiasm. As for the final conclusion, Professor Howe was one of the chosen few so highly expert at expository writing that he could produce a lecture or paper that reads as though it would also have listened well. One of his tricks was the free use of words not ordinarily part of the technical vocabulary, provided that such words were likely to communicate most precisely what he had in mind. How wonderful it would be for all who must read reports by the ton if ability at exposition could be taught with the effectiveness open, say to, differential calculus! Perhaps Professor Howe should be required college reading even if for no other reason than to prove that technical writing need be neither dull nor diffuse. My assignment is clearly still strenuous. Another point to consider is the fact that metallurgy is now so tremendously diversified that hope of finding a topic of universal appeal is negligible, even if one were competent enough to be permitted free choice. That which follows is, therefore, a compromise composed of necessity and of the obligation to attempt to avoid boring to slumber those of you who are not especially interested in the general subject chosen. The Iron and Steel Div. is now essentially a process metallurgy division, heavily concerned with the smelting of iron and the making of steel. The American Iron and Steel Inst. figure for present steel capacity of this country is 125,828,310 net tons; how this is divided among processes is indicated by the production totals for 1953, shown in Table I. The glamor girls and boys make the front page and so it is with steelmaking processes. If there is an Antarctic Daily Bugle, it undoubtedly has carried stories of revolutionary development, such as oxygen processes and vacuum melting, and stories of the incomparably rosy destiny of electric arc melting. All such certainly have their place and their future; meanwhile, it is the sturdy and old reliable open hearth that accounts for the bulk of production reported back on the financial page, and it is the old reliable that is most likely to continue to account for the bulk for some perfectly sound raw material, technologic, and economic reasons. This, plus the fact that next year marks a centennial (for it was in 1856 that Frederick and William Siemens conceived the regenerative open hearth), is reason enough to talk about open hearth furnaces, but is not the real one. The real reason is that in some years of association with open hearths, I have accumulated—in addition to a genuine liking and respect for them—certain odds and ends of fact and fancy that this lecture provides a unique chance

Jan 1, 1956

By Charles J. Moore

It seems a duty incumbent on the older members of the Institute to set forth in permanent form some of the results of their experience for the benefit of the younger members; this is the principal object of the present paper, which is the result of a recent examination requiring somewhat unusual geologic investigation. History. The London vein mas first discovered by float and occasional outcrops in the year 1873, four years before the great lead carbonate discoveries of Leadville, but the mine was not definitely located and opened until two years later, when the present locations, Mother, Paris, London, and Hard to Beat, were surveyed for patent. Since 1875 the London mine has been worked almost continuously until 1911, when the force was reduced to a few men only. In its early life the ore was assumed to be free-milling gold-quartz, although lead was a constituent of the vein throughout, and much useless expenditure was made in the erection and operation of a free-gold stamp-mill, with plates and tables for saving concentrates. The vein then opened was in the porphyry-limestone contact, a siliceous lead-ore, clearly most amenable to reduction by lead-smelter. The losses due to this process led in time to the close of the mill. For 20 years past, the mine has been worked under lease and the ore shipped to the lead-smelters in Denver or Salida. In January, 1912,I examined the mine to ascertain whether it was advisable to run a cross-cut tunnel some 4,200 ft. in length to intersect the main vein at a depth of 650 ft. below the present lowest workings. Finding a greatly-faulted zone, a close determination of the geological conditions became necessary to the solution of the problem.

Jan 1, 1914

By William P. Jones

THE consumption of sulphuric acid, one of the most important commodities in our modern industrial world, is often used as a barometer for industrial activity. The economics of acid manufacture are largely dependent upon the location of the place of consumption and the availability of raw materials in that locality. Sulphuric acid is made from SO,, oxygen from the air and water. Therefore the sulphur dioxide is the only raw material to be considered in an economic study. SO, can be obtained from almost any material containing inorganic sulphur, such as elemental sulphur, pyrites, coal, sour gas and oil, metallurgical gases, waste gases, or gypsum and anhydrite. Many tons of acid can also be reclaimed by the recovery and concentration of spent acids. The aim of this paper is to present a guide to the economic aspects to be considered when the installation of an acid plant is contemplated. It must be remembered that 1 ton of elemental sulphur produces 3 tons of sulphuric acid and that the shipping of sulphuric acid by tank car is very costly. The size of the plant must also be given careful consideration. For instance, operation of a plant producing 5 tons of acid per day might be warranted in Brazil or Pakistan, whereas economics usually favor buying quantities up to 50 tons per day for use within the United States. Elemental sulphur, when available at the low price of 1M4 per lb delivered at an acid plant, has always been the raw material most frequently used for sulphuric acid. All conditions favor its use at this price. The so-called sulphur shortage has been the subject of so many technical papers, magazine articles, and newspaper items during the past y6ar that it hardly seems necessary to mention it again, but a very brief review of the matter will serve as a foundation for the discussion that follows. There is no shortage of sulphur. Only a shortage of low-cost Frasch-mined brimstone exists today. Other more expensive sulphur-bearing materials are plentiful, both in the United States and abroad. The low cost of Frasch-mined brimstone has discouraged the development of higher cost sources. However, the approaching depletion of Gulf Coast dome deposits and the greatly increased demand for sulphur here and abroad have made it necessary for industry to prepare for conversion to utilize sulphur in other forms. For future planning this situation must be considered permanent and not temporary. This conclusion is based on the fact that although sulphur demand will continue to rise, the production of Frasch-mined sulphur probably will not increase greatly beyond its present level of about 5,000,000 long tons per year. The International Materials Conference in Washington estimates 1952 requirements of the free world at nearly 7 million long tons; and the Defense Production Administration has recently set a new goal for 8,400,000 long tons annual domestic production by 1955. The total sulphur equivalent produced in this country in 1950 was 6 million tons. What, then, are the alternatives for the manufacture of the vital chemical, sulphuric acid? Today about 85 pct of this country's sulphur, and nearly 50 pct of the world supply, comes from our Gulf Coast salt domes and is extracted from the earth by Frasch's hot water process. The Gulf Coast salt dome deposits have been the most important known natural deposits in the world, producing 90 million tons of sulphur during the past 50 years. However, at the present rate of extraction these deposits cannot be expected to last indefinitely. Pyrites Pyrites are, and have been for many years, the source of more than 50 pct of the world's sulphur requirements. The principal use, of course, is in the manufacture of sulphuric acid. The use of pyrites in the United States has diminished greatly because of the availability of low cost native sulphur, but pyrites have continued a major source of sulphur in many other countries. The most available pyrites for use in this country are in the form of lump pyritic ore and in mill tailings from flotation of other minerals such as lead, zinc, copper, gold, and silver. An important factor, when the use of pyrites for acid manufacture is being considered, is the disposal of calcine. A ton of sulphuric acid requires approximately ton of high-grade pyrite and results in 1/2 ton of calcine. If the calcine is a fairly pure oxide, free of harmful impurities, it can be used, after sintering, in an iron blast furnace burden. Its value might be as high as 15d per unit of Fe at the blast furnace; or possibly $10.00 per ton of sinter, if it assays 65 pct Fe. This might result in a credit of $4.00 per ton of acid if the sintering plant and blast furnace are both located adjacent to the acid plant. On the other hand, several factors must be considered before this credit can be realized, i.e., freight to blast furnace, availability of sintering facilities, methods of eliminating impurities, and the removal of valuable metal values. In some locations it would be most economical to dump the calcines.

Jan 1, 1953

By William P. Jones

THE consumption of sulphuric acid, one of the most important commodities in our modern industrial world, is often used as a barometer for industrial activity. The economics of acid manufacture are largely dependent upon the location of the place of consumption and the availability of raw materials in that locality. Sulphuric acid is made from SO2 oxygen from the air and water. Therefore the sulphur dioxide is the only raw material to be considered in an economic study. SO2 can be obtained from almost any material containing inorganic sulphur, such as elemental sulphur, pyrites, coal, sour gas and oil, metallurgical gases, waste gases, or gypsum and anhydrite. Many tons of acid can also be reclaimed by the recovery and concentration of spent acids. The aim of this paper is to present a guide to the economic aspects to be considered when the installation of an acid plant is contemplated. It must be remembered that 1 ton of elemental sulphur produces 3 tons of sulphuric acid and that the shipping of sulphuric acid by tank car is very costly. The size of the plant must also be given careful consideration. For instance, operation of a plant producing 5 tons of acid per day might be warranted in Brazil or Pakistan, whereas economics usually favor buying quantities up to 50 tons per day for use within the United States. Elemental sulphur, when available at the low price of 1 ½ ¢ per lb delivered at an acid plant, has always been the raw material most frequently used for sulphuric acid. All conditions favor its use at this price. The so-called sulphur shortage has been the subject of so many technical papers, magazine articles, and newspaper items during the past year that it hardly seems necessary to mention it again, but a very brief review of the matter will serve as a foundation for the discussion that follows. There is no shortage of sulphur. Only a shortage of low-cost Frasch-mined brimstone exists today. Other more expensive sulphur-bearing materials are plentiful, both in the United States and abroad. The low cost of Frasch-mined brimstone has discouraged the development of higher cost sources. However, the approaching depletion of Gulf Coast dome deposits and the greatly increased demand for sulphur here and abroad have made it necessary for industry to prepare for conversion to utilize sulphur in other forms. For future planning this situation must be considered permanent and not temporary. This conclusion is based on the fact that although sulphur demand will continue to rise, the production of Frasch-mined sulphur probably will not increase greatly beyond its present level of about 5,000,000 long tons per year. The International Materials Conference in Washington estimates 1952 requirements of the free world at nearly 7 ½ million long tons; and the Defense Production Administration has recently set a new goal for 8,400,000 long tons annual domestic production by 1955. The total sulphur equivalent produced in this country in 1950 was 6 million tons. What, then, are the alternatives for the manufacture of the vital chemical, sulphuric acid? Today about 85 pct of this country's sulphur, and nearly 50 pct of the world supply, comes from our Gulf Coast salt domes and is extracted from the earth by Frasch's hot water process. The Gulf Coast salt dome deposits have been the most important known natural deposits in the world, producing 90 million tons of sulphur during the past 50 years. However, at the present rate of extraction these deposits cannot be expected to last indefinitely. Pyrites Pyrites are, and have been for many years, the source of more than 50 pct of the world's sulphur requirements. The principal use, of course, is in the manufacture of sulphuric acid. The use of pyrites in the United States has diminished greatly because of the availability of low cost native sulphur, but pyrites have continued a major source of sulphur in many other countries. The most available pyrites for use in this country are in the form of lump pyritic ore and in mill tailings from flotation of other minerals such as lead, zinc, copper, gold, and silver. An important factor, when the use of pyrites for acid manufacture is being considered, is the disposal of calcine. A ton of sulphuric acid requires approximately ¾ ton of high-grade pyrite and results in ½ ton of calcine. If the calcine is a fairly pure oxide, free of harmful impurities, it can be used, after sintering, in an iron blast furnace burden. Its value might be as high as 15¢ per unit of Fe at the blast furnace; or possibly $10.00 per ton of sinter, if it assays 65 pct Fe. This might result in a credit of $4.00 per ton of acid if the sintering plant and blast furnace are both located adjacent to the acid plant. On the other hand, several factors must be considered before this credit can be realized, i.e., freight to blast furnace, availability of sintering facilities, methods of eliminating impurities, and the removal of valuable metal values. In some locations it would be most economical to dump the calcines.

Jan 1, 1952

By William P. Jones

THE consumption of sulphuric acid, one of the most important commodities in our modern industrial world, is often used as a barometer for industrial activity. The economics of acid manufacture are largely dependent upon the location of the place of consumption and the availability of raw materials in that locality. Sulphuric acid is made from SO,, oxygen from the air and water. Therefore the sulphur dioxide is the only raw material to be considered in an economic study. SO, can be obtained from almost any material containing inorganic sulphur, such as elemental sulphur, pyrites, coal, sour gas and oil, metallurgical gases, waste gases, or gypsum and anhydrite. Many tons of acid can also be reclaimed by the recovery and concentration of spent acids. The aim of this paper is to present a guide to the economic aspects to be considered when the installation of an acid plant is contemplated. It must be remembered that 1 ton of elemental sulphur produces 3 tons of sulphuric acid and that the shipping of sulphuric acid by tank car is very costly. The size of the plant must also be given careful consideration. For instance, operation of a plant producing 5 tons of acid per day might be warranted in Brazil or Pakistan, whereas economics usually favor buying quantities up to 50 tons per day for use within the United States. Elemental sulphur, when available at the low price of 1M4 per lb delivered at an acid plant, has always been the raw material most frequently used for sulphuric acid. All conditions favor its use at this price. The so-called sulphur shortage has been the subject of so many technical papers, magazine articles, and newspaper items during the past y6ar that it hardly seems necessary to mention it again, but a very brief review of the matter will serve as a foundation for the discussion that follows. There is no shortage of sulphur. Only a shortage of low-cost Frasch-mined brimstone exists today. Other more expensive sulphur-bearing materials are plentiful, both in the United States and abroad. The low cost of Frasch-mined brimstone has discouraged the development of higher cost sources. However, the approaching depletion of Gulf Coast dome deposits and the greatly increased demand for sulphur here and abroad have made it necessary for industry to prepare for conversion to utilize sulphur in other forms. For future planning this situation must be considered permanent and not temporary. This conclusion is based on the fact that although sulphur demand will continue to rise, the production of Frasch-mined sulphur probably will not increase greatly beyond its present level of about 5,000,000 long tons per year. The International Materials Conference in Washington estimates 1952 requirements of the free world at nearly 7 million long tons; and the Defense Production Administration has recently set a new goal for 8,400,000 long tons annual domestic production by 1955. The total sulphur equivalent produced in this country in 1950 was 6 million tons. What, then, are the alternatives for the manufacture of the vital chemical, sulphuric acid? Today about 85 pct of this country's sulphur, and nearly 50 pct of the world supply, comes from our Gulf Coast salt domes and is extracted from the earth by Frasch's hot water process. The Gulf Coast salt dome deposits have been the most important known natural deposits in the world, producing 90 million tons of sulphur during the past 50 years. However, at the present rate of extraction these deposits cannot be expected to last indefinitely. Pyrites Pyrites are, and have been for many years, the source of more than 50 pct of the world's sulphur requirements. The principal use, of course, is in the manufacture of sulphuric acid. The use of pyrites in the United States has diminished greatly because of the availability of low cost native sulphur, but pyrites have continued a major source of sulphur in many other countries. The most available pyrites for use in this country are in the form of lump pyritic ore and in mill tailings from flotation of other minerals such as lead, zinc, copper, gold, and silver. An important factor, when the use of pyrites for acid manufacture is being considered, is the disposal of calcine. A ton of sulphuric acid requires approximately ton of high-grade pyrite and results in 1/2 ton of calcine. If the calcine is a fairly pure oxide, free of harmful impurities, it can be used, after sintering, in an iron blast furnace burden. Its value might be as high as 15d per unit of Fe at the blast furnace; or possibly $10.00 per ton of sinter, if it assays 65 pct Fe. This might result in a credit of $4.00 per ton of acid if the sintering plant and blast furnace are both located adjacent to the acid plant. On the other hand, several factors must be considered before this credit can be realized, i.e., freight to blast furnace, availability of sintering facilities, methods of eliminating impurities, and the removal of valuable metal values. In some locations it would be most economical to dump the calcines.

Jan 1, 1953