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By G. W. King, A. Bogrow, L. F. Marek

The purpose of this paper is to present the data and some interpretation of the results of a laboratory study of the reduction of iron ore and the deposition of carbon from the reducing gas mixtures in such reductions. One major object of the study was to determine the effect of gas pressures on these chemical processes. Effort was made to approximate the conditions of temperature, gas composition, linear and mass gas velocities, pressure range, and extent of reduction prevailing in commercial blast furnaces. The results show that the reduction of Fe203 proceeds by two steps, largely consecutive under the conditions used herein: reduction of Fe203 to FeO, and reduction of FeO to Fe. Unless the gas has a CO!CO, ratio greater than 2.1 only the first step occurs under these conditions (850°C) but the following generalizations apply to either step or to the combination. The rate of reduction of relatively fine ore particles .at any time is proportional to the mass rate of supply of CO (provided some of it is thermodynamically available): the rate therefore is proportional to the linear velocity at constant pressure, or to the pressure at constant linear velocity. Thus, the rate of reduction may be increased without increase in linear velocity of the reducing gas by increasing the mass velocity of the gas and increasing the pressure correspondingly to avoid any increase in the linear velocity. The rate "constants"—i.e., the efficiency of conversion of the "available" CO supplied— is not actually constant but decreases as the reduction proceeds, and is a function only of the state of the ore; i.e., of the amount of reduction already accomplished and hence of the amount of CO passed. The particle size of ore used in nearly all the experiments was relatively small (8 to 14-mesh). The rate of reduction in run 16 with 3 to 8-mesh ore particles is within experimental error the same as with the finer ore. Although this would indicate an absence of effect due to particle size in this range of ore particles, it is desirable to have more data on other ore sizes and on ore of different densities before arriving at any generalizations on this point. Although it is possible to extend the analysis of these results to consideration of the more detailed kinetics and mechanism of iron oxide reduction, such extension is beyond the scope of the present paper. From the experiments on carbon deposition, it was evident that if carbon deposition is increased at all by the application of pressures up to 10 psi ga., such increase appears to be less than the experimental and analytical error. It appears safe to conclude that at top pressures on the order

Jan 1, 1948

By George A. Morrison

THE Columbia Chemical Division of the Pittsburgh Plate Glass Co. is at Barberton, Ohio, 35 miles south of Cleveland. For many years large tonnages of limestone have been brought to the Barberton plant from distant points. The stone is here burnt in vertical kilns, the resultant product then hydrated and the hydrated lime used in chemical processing. To eliminate the expense of these shipments, the company decided to investigate a limestone bed known to exist on company property at Barberton, where the stone is used. The bed lay at a depth of more than 2000 ft. and was known locally as the "Deep Lime." Chemical analyses of sludge from churn-drill holes made some years ago proved that the limestone was of sufficient purity to warrant diamond-drill exploration. Four diamond-drill holes were put down at well-spaced intervals, to represent fairly an area of four miles by one mile. Cores logged as to chemical and physical conditions were found to compare closely, and to corroborate the earlier evidence that the limestone was of superior quality for chemical use. A plant of 300 tons per hour was subsequently decided upon. SITE The yard at the chemical plant was already so congested that location of the projected mine within its area could not be considered. Eventually a site was selected 2 miles northwest of the plant, near the main line of the Erie Railroad. Here 412 acres were owned outright by the company and stone rights were obtained on 250 additional acres. This location required a transportation line of nearly 2 miles (8800 ft.), crossing two major highways, and to avoid interruption of deliveries to the plant, overpasses were planned. GEOLOGY The limestone in the immediate vicinity lies about 2200 ft. below the surface. Geologists* identify this stone as Delaware of Devonian age. It is overlain by 18 ft. of unconsolidated (sand and gravel), 100 ft. of water-bearing sandstone, and finally 2080 ft. of shale into which sandstone in thin layers is interbedded. The contact of shale and limestone is abrupt, flat-lying and very pronounced. Berea sandstone, often found at 520 ft., is absent, but Euclid sandstone was encountered, together with a seepage of oil and a small amount of methane gas. The limestone bed itself is 345 ft. thick, and overlies 200 ft. of gypsum. The lower part becomes dolomitic as it approaches the gypsum. A detailed study of the drill cores indicates that the upper 50 ft, are highest in lime and reasonably low in silica. The physical make-up shows several separating cherty layers. These occur at definite horizons and cause distinct partings, which become horizontal planes of

Jan 1, 1943

By E. C. Harder

In view of the gradually decreasing known reserves of high-grade manganese ore and the rapidly increasing consumption of iron-manganese alloys in the steel industry, it is well to turn our attention to the development of low-grade manganiferous ore deposits and to the utilization of these ores in steel manufacture. The dependence of this country on imported manganese ore and ferromanganese has been forcibly brought to the attention of steel makers during the last few years by the cessation of manganese-ore imports from Russia, the restriction of manganese-ore imports from India and of ferromanganese imports from Europe. Should the importation of manganese ore from Biazil cease, the steel industry of this country would face a serious situation. The present practice of steel making requires ferromanganese in large quantities and ferromanganese of the grade used at present can be produced only from high-grade manganese ores such as the United States appears to possess only in insignificant amounts. There are in the United States, however, large reserves of manganiferous iron ore which could probably be used extensively in the steel industry if certain changes in the practice of steel manufacture were made. Thus high-grade manganese ore could be conserved. Among the most important deposits of manganiferous iron ore in this couniry are those of the Cuyuna iron-ore district of Minnesota. It is probable that in case of restriction of foreign supplies, the users of manganese in the United States would have to rely to a large extent on the Cuyuna district to make up the shortage. Manganiferous iron ore was found in association with iron ore in the Cuyuna district in many of the early drilling operations and the possibility of its utilization was in the minds of various explorers in the dis-

Jan 1, 1918

By L. F. Marek, G. W. King, A. Bogrow

The purpose of this paper is to present the data and some interpretation of the results of a laboratory study of the reduction of iron ore and the deposition of carbon from the reducing gas mixtures in such reductions. One major object of the study was to determine the effect of gas pressures on these chemical processes. Effort was made to approximate the conditions of temperature, gas composition, linear and mass gas velocities, pressure range, and extent of reduction prevailing in commercial blast furnaces. The results show that the reduction of Fe203 proceeds by two steps, largely consecutive under the conditions used herein: reduction of Fe203 to FeO, and reduction of FeO to Fe. Unless the gas has a CO!CO, ratio greater than 2.1 only the first step occurs under these conditions (850°C) but the following generalizations apply to either step or to the combination. The rate of reduction of relatively fine ore particles .at any time is proportional to the mass rate of supply of CO (provided some of it is thermodynamically available): the rate therefore is proportional to the linear velocity at constant pressure, or to the pressure at constant linear velocity. Thus, the rate of reduction may be increased without increase in linear velocity of the reducing gas by increasing the mass velocity of the gas and increasing the pressure correspondingly to avoid any increase in the linear velocity. The rate "constants"—i.e., the efficiency of conversion of the "available" CO supplied— is not actually constant but decreases as the reduction proceeds, and is a function only of the state of the ore; i.e., of the amount of reduction already accomplished and hence of the amount of CO passed. The particle size of ore used in nearly all the experiments was relatively small (8 to 14-mesh). The rate of reduction in run 16 with 3 to 8-mesh ore particles is within experimental error the same as with the finer ore. Although this would indicate an absence of effect due to particle size in this range of ore particles, it is desirable to have more data on other ore sizes and on ore of different densities before arriving at any generalizations on this point. Although it is possible to extend the analysis of these results to consideration of the more detailed kinetics and mechanism of iron oxide reduction, such extension is beyond the scope of the present paper. From the experiments on carbon deposition, it was evident that if carbon deposition is increased at all by the application of pressures up to 10 psi ga., such increase appears to be less than the experimental and analytical error. It appears safe to conclude that at top pressures on the order

Jan 1, 1948

Experimentation which measures differences in pressure across the interfaces of immiscible fluids in the interstitial spaces of porous media may be termed "capillary pressure experimentation". In the literature of petroleum technology since 1941 there have appeared twelve papers popularizing capillary pressure concepts and developing applications of these concepts for the solution of problems of practical reservoir engineering importance, such as the determination of connate water, fluid distribution. in transition zones, reservoir rock textural properties, and oil recovery from petroleum reservoirs.' Although a review of the literature would be justified at this time in order to reconcile the conflicting viewpoints which are contained in the cited papers, the object of this note will be of more limited scope. It is believed that the recent paper of Muskat alls sufficient attention to many of the uncertainties which arise upon examination of the published literature. such that until satisfactory counter-proposals can be made it will serve our purpose only to mention some other like uncertainties. This will emphasize further the need confronting petroleum technologists to re. consider and reformulate the application possibilities of capillary pressure experimentation. In particular, I sug- gest that we examine the thesis that capillary pressure experimentation as above defined can lead to measurements reflecting the recovery of oil from petroleum reservoirs, as was proposed first" by Amyx and Yuster" and was first reduced to practice by the experimentation of Welge. In fact. I shall deal exclusively with the Welge papers since it is the principle one on this subject which has appeared to date. I shall attempt to show that the possibility of describing oil recovery features in terms of capillary pressure phenomena has not been established entirely. The Welge paper was a pioneering effort to evaluate this recovery application possibility. P. P. Reichertz' comments on the Welge paper state that non-wetting phase discontinuities are developed occasionally in the Welge experiment, and restate Muskat's argument that discontinuous fluid elements (partially saturating the interstices of porous media which are elsewhere saturated with some other immiscible phase or phases) are not subject to the requirements of hydrostatic equilibrium. It is the purpose of my comment to show that it is unnecessary to make Reichertz' postulation regarding non-wetting phase discontinuities (however valid) when it is desired to criticize welge's theoretical treatment of his problem. It can be shown that Welge's method of measuring values for ''capillary pressure" is invalid in many instances of application, such that his reported curves of capillary pressure Versus fluid saturation often have no physical meaning, even throughout the interval of fluid saturation where it might be otherwise suspected that no phase discontinuities occur. By considering established principles of capillary pressure experimentation it can be shown that the pressure difference experimentally observed between wetting and non-wetting fluid Phases which are contained in external reservoirs will reflect on the capillary pressure difference at the interfaces of contact between these phases only when the following conditions are satisfied: (a) There shall be a balance between the opposing forces of gravity and capillarity, as obtains under conditions of hydrostatic equilibrium when the positions of the interfaces of contact become fixed in pore spaces of certain geometry (b) The wetting and non-wetting fluids within the interstitial spaces shall everywhere be continuous with the external wetting phase reservoir and the external non-wetting phase reservoir, respectively. It will become apparent immediately that in any instance when a greater pressure is recorded in the external wetting phase reservoir than in the external non-wetting phase reservoir, one may establish either that static equilibrium has not been attained or that discontinuities in one or more of the fluids have been developed. This is because the pressure otherwiee is always ereatest in the non-wetting phase at each static interstitial interface of contact with the wetting phase. such that the externally measured pressure in the non-wetting phase likewise must be greatest if the above conditions are to be satisfied.

Jan 1, 1949

By Edwin F. Brush, John Chipman

Published data on the activity of carbon in binary and ternary austenite at 1000°C are reviewed. The composition variables are . The coefficient, Vj, has the value for substitutional elements but may be assigned a ualue -1 for silicon to effect a simplification on the mathematical treatment. The activity coefficient PC = is obtained from gas equilibrium data. For the ternary systems studied the Henrian activity coefficient is given by the expression: The principle advantage in cornparison with the analogous expression in terms of atom fractions is found in the fact that for most systems the final term and in many the last two terms are zero. Values of the interaction parameters are tabulated and the graphical comparison of the equation with experirt~ental data is sho,wn in several figures. The thermodynamic properties of the solid solution, austenite, are of considerable importance in the heat-treatment of alloy steels and in other aspects of ferrous metallurgy. Early studies embodied in the Fe-C diagram have been extended to include other binary and some ternary diagrams. Our best hope of obtaining a useful thermodynamic treatment of reactions in complex alloy steels will not be found in quaternary and quinternary phase diagrams but in determinations of activities and interaction relations among the several solute elements. The foundation for such a development was laid by smith' in his early studies of the activity of carbon in Fe-C alloys and his subsequent work on Fe-C-Si, Fe-C-Mn, Fe-C-Ni, and Fe-C-Co solid solutions.2"4 Other observers have also made noteworthy contributions and these will be discussed and correlated here in the light of a somewhat simplified mathematical treatment of solute interactions. Fe-C AT 1000°C In a recent review of the thermodynamic properties of binary Fe-C austenite it was shown that the simple mathematical treatment employed by smith' was capable of describing all the published results on this solution. The treatment utilizes the atom ratio, yc = nC/nF,, rather than the atom fraction. The activity of carbon is proportional to the equilibrium gas ratio, either measured on a scalk in which the activity of graphite is taken as unity or, alternatively, aC may be set equal to yc at infinite dilution. In either case the ratio aC/y = (PC, the activity coefficient. It was found that the experimental data of smith1 and those of Diin-wald and wagner; Bungardt, Preisendanz, and Lehn-ert,' and Scheil, Schmidt, and Wiinnings at temperatures of 800" to 1200° C as well as reliable data on the solubilities of graphite and cementite could be represented by the equation for which graphite is the standard state: The data on alloyed austenite have been obtained at 1000°C. For this temperature, the "Henrian" activity coefficient (which is unity at infinite dilution) is: FOr an interstitial solute such as carbon in austenite it has been shown by statistical mechanicsg that the activity in the infinitely dilute solution is proportional to the ratio of the number of lattice sites occupied by carbon to the number of yet unfilled lattice sites. A variable zz proportional to this ratio serves as a useful measure of concentration:" in which b is the number of lattice sites provided by each atom of solvent; in austenite b = 1. The Henrian activity approaches zz at infinite dilution and the ratio a is the activity coefficient. The effect of a change in concentration is then given by: It has been shown further that in some systems the derivative in Eq. [4] remains constant over a wide range of concentrations. In such a case second-order terms become negligible and the Henrian activity coefficients is:

Jan 1, 1969

By J. S. Bryner

INTRODUCTION IN the study of metallographic specimens in the electron microscope, there is need for a method of locating the same field in both the light microscope and the electron microscope. This need arises chiefly from the fact that in the electron microscope the magnification and degree of resolution are so much higher, and the field so much smaller than in the light microscope that it is often difficult, if not impossible, to identify positively what is being observed. The difficulty is increased by the fact that, because a transparent film replica of the metal surface must be used in the electron microscope, micro-constituents can be identified not by their color but only by their texture and contours. For these reasons it is desirable to obtain a series of photographs showing the same field in both microscopes in order that the appearance of common microstructures and micro-constituents in the electron microscope may be identified and catalogued for future reference. The need for a method of locating the same field in both microscopes arises also when it becomes desirable to enlarge in the electron microscope for more detailed study a particular interesting structure observed in the light microscope. Using the standard polystyrene-silica1,2 replica technique, in which the silica film replica is fished from the ethyl bromide on a 1/3 in. diam 200-mesh specimen screen, the possibilities of locating a particular area on the film in the electron microscope are rather remote. The desired structure may be obscured by the wires of the specimen screen or unrecognizable at the high magnification. A solution to the problem would be provided if a specially designed specimen screen, containing an opening which could be absolutely identified and quickly located in the electron microscope, could be fastened to the silica film replica in such a position that the desired field on the specimen would be located at the identifiable opening in the specimen screen. The design for such a specimen screen, a method for producing it, and a technique for fastening it to the silica film replica are described below. DESCRIPTION OF METHOD The Specimen Screen A simple design for a specimen screen containing an opening easy to identify and locate in the electron microscope is one with two lines of openings at right angles in the form of a cross. Such a screen is shown in Fig I. The opening at the center of the cross is identified easily and can be located quickly in the light microscope and in the objective image of the electron microscope. The specially designed specimen screens for this work were produced in quantity by electroforming. On both sides of a polished strip of copper 1 X 3 X 1/8 in., twenty patterns of the cross of openings were punched with a diamond point micro-hardness tester, using a load of magnitude

Jan 1, 1948

By D. J. Barrett, M. A. Sochocky

INTRODUCTION Summary of Factors Influencing Comminution Circuit Design The selection of an appropriate comminution circuit for a specific ore is one of the most important decisions in the design of a processing plant. The importance is related to the fact that the capital and operating costs for crushing and grinding plant generally represent, as is well known, the major portion of the plant costs. This chapter will, therefore, identify as many as possible of the factors which influence the selection of a comminution circuit. The number of factors which will have to be considered for any comminution project will depend, among other things, on the type of project. If, for example, the project is an entirely new mining development, then most, if not all, the factors identified will have to be analyzed. If the project is an expansion of a developed mining operation or if the new orebody is adjacent to a viable operation, then the existing operation will influence the choice of factors or design constraints which need to be considered. The existing infrastructure or supporting systems may be quite adequate to accommodate the requirements of any expansion or new development. Hence, those factors may not have to be considered. To cover, however, the widest spectrum of projects, the factors which have been identified in this chapter are those which will have to be considered for the most complex of projects, that of developing an entirely new mining operation. The range of factors is as broad as the range of different ore types. Thus, each development must be treated with individualized care. The most important step in the development is the analysis and understanding of the ore characteristics. The hardness of the ore, its abrasiveness, friability, moisture content, grade, mineralization including gangue mineralization, liberation size, chemistry, and other characteristics should be the first to be analyzed in the investigation. The next should be the determination of factors such as plant size, throughput, location, climate, accessibility, and availability of water. The selection of samples for initial bench scale work and bulk sampling (when needed) for further

Jan 1, 1982

By W. F. Kieschnick, and W. J. McGuire&apos, Eugene Harrison

This paper concerns the induction and extension of fractures into rock formations as involved in drilling, completing, and production stimulating operations on wells. Conclusions concerning formation breakdown are derived from (I) a review and extension of published analyses relating to mechanical theories of rock stress and the state of stress in the earth's crust and (2) a correlation of field data from fracturing operations. Conclusions concerning the mechanics of fracture extension, which indicate the relationship between fracture dimensions and rock properties, depth, and volume of injected fluid, are tentative and largely establish limits of relationships. These conclusions are derived from stress calculations, limited field data, and laboratory experimental studies. The experimental work involves the study of the stresses at the fracture boundaries and the geometry of pressurized fractures by means of photo-elastic modeling methods. Results of this investigation indicate that a large majority of pressure induced wellbore fractures are vertical, particularly in deeper wells; and variations in the pressures necessary to create and extend fractures can be explained largely on a basis of established rock properties. It is also shown that variations due to tectonic forces should usually be expected to be slight. Other results indicate that during that extension of fractures rather large fracture volumes are temporarily created by the parting of the formation. The purpose of this paper is to present the results of calculations and laboratory experiments concerning the mechanics of fracture induction and extension with a view to broadening existing knowledge relating to these phenomena. It is believed that continued progress in developing knowledge of this type is important to the further development of techniques for drilling and completing wells. When a wellbore is subjected to sufficiently high pressure, fracturing of the formation surrounding the well occurs. This phenomenon is a common cause of lost circulation during drilling operations, is a deliberately planned factor in most squeeze cementing operations, and is the controlling factor in many productivity stimulation operations. The exploitation of formation fracturing in recent years has been particularly impressive in sand-viscous fluid well stimulation treatments which were first introduced to the industry by the Stanolind research group1,2,3 several years ago. The borehole fracturing phenomenon has been analyzed mathematically by application of the principles defining the elastic and inelastic behavior of thick-walled cylinders of homogeneous, isotropic, and impermeable material.1,5,6 This basic argument is re-presented in this paper along with new considerations which strengthen it. In addition to these arguments relating to fracture induction some calculations and experimental results relating to the mechanics of fracture extension are presented. Since the nature of the pressure induced fracture at distances from the well is of great importance in considerations of well stimulation procedures there appears to be a need for an integrated approach which deals with the mechanics of fracture extension as well as with wellbore rupture.

Jan 1, 1955

By L. Ekstrom, J. P. Dismukes

The homogeneity and microstrcture of zone-leveled Ge-Si alloys haw been investigated by sellera1 physical techniques and by metallography as a function of growth rate in the range 3 x 10 1x10 cm-sec', and as a system of alloy composition throughout the system. The temperature gradient at the solid-liquid interface was about 50 deg-cm-' Cellular or dendritic structures char-acteristic of constitutional supercooling were ob-served except at very slow growth rates, which ranged from about 2 x 10 cm -sec for Ge 1 sio alloy to about 2 X 10'5 cm-sec'1 for Ge .sSio.s alloy. Using a simple model similiar to that employed for dilute solid the dependence upon compo-sition over the entire system of the critical growth rate for the onset of constiutional supercooling was calculated, and was .found to he in good agreement with the experimental results. THE recent discovery of the low thermal conductivity of Ge-Si alloys' at high temperatures has revealed that these alloys have high efficiencies for thermoelectric-power generation.', Therefore, a reliable method was needed for the preparation of homogeneous samples required for definitive measurements throughout this alloy system. Due to the low diffusion rates in the solid alloys, the segregated samples obtained by quenching a melt are not readily homogenized by annealing.475 However. isothermal solidification from a melt of constant composition can produce uniform material. Of the available semiconductor crystal-growth procedures, the zone-leveling technique6 applied to a complete solid-solution alloy system by Wang and Alexander' and by others provides a simple method of doing this. In the present work, the homogeneity and microstructure of zone-leveled alloys have been correlated with growth conditions, and the conditions for preparing homogeneous Ge-Si alloys have been established. This has provided insight into the solidification process of alloy semiconductors. EXPERIMENTAL PROCEDURE Sample Preparation. The Ge-Si alloy phase diagram4 shown in Fig. l(a) consists of a complete series of solid solutions. The zone-leveling technique used to prepare most of the samples consists of moving a zone of liquidus composition (C1) through charge material of the corresponding solidus composition (C,), as is illustrated in Figs. l(b) and l(c). To prepare the charge materials, high-purity germanium and silicon were pulverized in a steel hammer mill, cleaned magnetically, and melted together to make uniform chill castings. The zone leveling was carried out in a resistance-heated furnace similar to that of Mitrenin et al.' shown in Fig. 2. However, a few specimens of high silicon content were prepared by the Czochralski technique. The growth rate ranged from 3.5 x X6 to 1.2 X 10~3 cm-sec-'. Temperature gradients in the solid and in the melt were determined by recording the temperature as the molten zone passed over a Pt-Pt 13 pct Rh thermocouple contained in a small

Jan 1, 1965

By Henry Hibbard

Fox the purpose of this paper all steels will be divided into two divisions: effervescing and non-effervescing. This classification must be borne in mind as many statements true of one class are not true of the other. Effervescing steels are those that effervesce in the molds, evolving large volumes of gases, which, in escaping, throw up a spray of molten particles of steel and give the molten metal in the mold a rapid stirring or churning motion until it freezes, or, at least, becomes pasty. This effervescing is intended and proper. The non-effervescing steels, which are more or less completely killed, should not evolve any gas in the molds. Many years ago the writer proposed to call the two classes of steels evolution and solution steels, depending on whether the gases in the molds are evolved or kept in solution, but the present designations seen to be better. In America, at least, effervescing steels are in a class by themselves and include steels made for boiler, tank, and ship plates, steel pipe, soft steel wire, wire nails, soft machinery, and structural steels. These are all low-carbon steels with less than 0.40 per cent. carbon. Low-carbon steels that do not effervesce but are killed are also made; these are put into ingots and castings but they are outside the limits of this paper. Effervescing steel is cast into square or slab molds, either top or bottom poured. Most of the effervescing steel is made in the basic open-hearth furnace, though much is made by the acid Bessemer process and a little is made in the acid open-hearth. It is not made by the crucible or electric-furnace process, in which the volume of gas required cannot be produced in the steel and evolved from it in the mold to give the effervescence desired. Any steel ingot, when teeming is finished, is of a certain size or volume. Leaving out of consideration for the moment the lessening of the over-all dimensions of the ingot through contraction due to loss of heat, the ingot may be placed in one of three classes: It may settle, losing in volume; it may stand, that is, remain constant in volume; it may rise, that is, increase in volume.

Jan 9, 1919

By H. C. Fiedler

The solubility of sulfur in Si-Fe was determined by the metallographic examination of heat-treated and quenched samples. In the absence of manganese, the solubility in 3.1 pct Si-Fe was found to be about 0.010 pct at 1000o C, 0.015 pct at 11000C, and 0.020 pct at 1150°C, which is substatntially less than hitherto reported. Increasing the silicon content was found to decrease the solubility of sulfur, which is consistent with the increase in the activity coefficient of sulfur with increasing silicon content that has been reported for Fe-Si alloys. Manganese additions were studied in alloys containing 3.1 pct Si and between 0.013 and 0.015 pct S. At low manganese levels the solubility product of manganese sulfide was found to be lower than previously reported. THE solubility of sulfur in pure polycrystalline iron has been reported by Rosenquist and Dunicz1 and by Turkdogan et al.2 Samples were equilibrated in atmospheres containing different ratios of H2S/H2. Both groups of investigators found a solubility limit in y iron of 0.013 pct at 1000oC and 0.031 pct at 1200°C. In addition, Rosenquist and Dunicz1 found a solubility limit in a iron of 0.020 pct at 900°C. Ainslie, Hoffman, and seybolt3 found significantly higher sulfur contents in polycrystalline iron samples than in single-crystal samples after heating at 890°C in a sealed tube containing a mixture of powdered iron and FeS made with s35. Whereas the single crystals contained 0.013 and 0.016 pct S (± 0.005 pct), the polycrystalline samples contained between 0.016 and 0.026 pct S. Autoradiographs suggested that the excess sulfur in the polycrystalline samples was due to the segregation of sulfur in solution at grain boundaries. Ainslie and seybolt4 have reported on the solubility of sulfur in 3 pct Si-Fe. Their samples were sealed in capsules containing hydrogen and sufficient sulfur as cobalt sulfide to saturate the sample. After heat treating, the sulfur-rich phase on the surface was removed by abrading, and the sulfur content of the sample was taken as the equilibrium value for that temperature. Before the equilibrating heat treatment, the samples were heated to 1300°C to coarsen the grains. The resulting grain size, which was about 3/18 in. in diam, was considered sufficiently large to preclude a sensible increase in sulfur solubility due to grain boundary segregation. They reported the solubility to be 0.029 pct at 900oC, 0.063 pct at 1000oC, 0.076 pct at 1100°C, 0.122 pct at 1200°C, and 0.098 pct at 1300°C.

Jan 1, 1968

By Gregoire Gutzeit

The development reported in this paper was begun by the author a number of years ago, while he was a lecturer on complex chemistry and metallurgy at the University of Geneva, Switzerland, and in charge of that institution's research laboratory. Completion of the development and reduction to practice did not occur until last year at the Westport mill, laboratories and testing plant of the Dorr Company, where this method is now in general use for identifying and localizing the mineral constituents of both metallic and nonmetallic ores. It has proved to be a practical tool of the metallurgical staff at the Westport mill, devising unusual milling flowsheets for complex and refractory ore bodies. In a number of instances the findings have been successfully used as fundamental factors in the design and specification of complete metallurgical plants. Seven examples of the use of this method in solving practical milling problems are included in this paper. General Outline The microscopic study of an ore, at first only of scientific interest, has proved extremely useful both in practical geology and in ore dressing. The binocular magnifying lenses for rough observation of the products of an ore-dressing plant have been in use for a long time; but only within the last few years has a systematic microscopical examination of ore samples become a normal tool of any research laboratory dealing with ore-dressing problems. Such an investigation avoids considerable loss of time as well as empirical trials and useless experimentation. It will generally indicate the correct grinding and often will suggest the proper method of treatment. . The petrographic determination of transparent minerals in thin sections, or even in grains, has been perfected, and very accurate methods have been devised to meet any requirement, such as Feodorof's rotating stage on the petrographic microscope. Almost all transparent minerals can be positively identified by their optical properties; i.e., isotropism, anisotropism, color, pleochroism, refractory index, cleavage, crystal form, birefringence, and others. The identification of opaque minerals is a much more difficult problem and can be done only by using polished specimens. Unfortunately, most of the valuable metallic ores, and even some of the nonmetallic ones, are not transparent; therefore it has been necessary to develop a special technique for the determination of these minerals. Some optical properties—for instance, isotropism, anisotropism, color, cleavage, reflecting power-—are often adequate in roughly classifying the mineral. Only "reflecting power" is a measurable value, provided special photometric equipment (ocular photometer or Orcel's photoelectric cell) is available. The other optical properties mentioned are more or less relative,

Jan 1, 1943

By Ralph V. Higgins

This paper concerns the magnitude of the amount of supersaturation that occurs in an underground reservoir during the flow of oil and gas to wells and to the amount of undersaturation that occurs during repres-suring of an oil reservoir where some effective permeability to gas exists. The study is based on earlier laboratory findings of other investigators on the rate of diffusion of gas in oil as a function of the depth of oil. Utilizing these relationships and the principles of reservoir mechanics, a quantitative estimate of undersaturation and super-saturation was calculated. The results showed that the diffusion of the gas is rapid enough that for all practical purposes no supersaturation exists during the flow of oil to wells or undersaturation during repressuring in reservoir sands having some effective permeability to gas. The reason diffusion of the gas virtually keeps the oil saturated is the long time required in radial flow for oil to reach the well and the slow rate at which pressure in reservoirs is increased during repressuring. INTRODUCTION Knowledge of the phase relationships during flow of gas and oil in an underground reservoir is essential to operating the reservoir in the most efficient manner. In material-balance calculations and in fluid-flow studies, the oil is assumed to contain all the gas that it will dissolve at given temperature and pressure. Pressure-volume-temperature relationships are normally obtained in the laboratory using "bottom-hole" or combined samples of the reservoir fluids. In such laboratory determinations equilibrium is obtained between the oil and gas in the pressure cells by mechanical agitation. During the flow of oil and gas in reservoirs, however, no comparable agitation occurs to mix thoroughly these fluids to aid in effecting equilibrium between the two phases. During repressuring of a partly depleted underground reservoir, the gas is usually injected into the reservoir faster than the oil can absorb it; consequently, the oil is undersaturated. On the other hand, as the oil flows through the reservoir to the wells during producing operations the pressure decreases faster than the gas in solution can diffuse through the oil to the gas phase. The oil therefore is supersaturated with gas. Where the oil is undersaturated, gas diffuses away from the gas-oil interface, and where it is supersaturated the gas diffuses toward the interface. In either case the gas moves from a higher to a lower saturation. This report contains the results of a study of the factors influencing the degree of nonequilibrium of the phase relations of oil and gas in porous mediums during the flow of oil through reservoirs to wells and also during the injection of gas into partially depleted sands. Data from an underground reservoir are presented and the degree of supersaturation during the flow of the oil through the reservoir to the well is approximated. Also data from another reservoir are used and the degree of undersaturation during the repressuring operation is calculated. In addition, the flow rates of oil in laboratory experiments and in underground reservoirs are compared, as data from the laboratory are often used to interpret events in the reservoir, and the rates of flow influence appreciably the degree of nonequilibrium. Much of the contents of this report was prepared in 1943; but, because of other activities during and since the war, the manuscript was left untouched until 1952, when it was decided to include an estimate of the amount of undersaturation during repressuring as well as supersaturation during flow.

Jan 1, 1955

By Karl L. Fetters

In the process of making steel in the open-hearth furnace the refining of the metal during the working period of the heat is largely accomplished through the agency of the slag. From the birth of the process until the present day steelmakers have recognized the importance of the slag in determining the composition of the metal and the quality of the product. The general relationships between slag composition and metal analysis have long been known, at least in a qualitative or approximate fashion. For examples, the iron oxide content of the slag is higher on lower carbon heats; the more basic slags are higher in iron oxide for a given carbon content; certain amounts of iron oxide and lime arc required for phosphorus removal and a high lime-silica ratio is needed if the sulphur content of the metal is to be diminished. In recent years a number of quantitative relationships involving these and other variables have been developed through plant and laboratory studies by numerous investigators in this country and abroad. The direct comparison of laboratory and open-hearth data involves the question of the degree to which each approaches the conditions of chemical equilibrium, a question which, from the open-hearth standpoint, we are scarcely yet in position to answer. And, although a considerable body of dependable equilibrium data has been obtained in the laboratory, this work has not yet been extended to cover the ranges of slag composition encountered in basic open-hearth practice. In the present study we shall not attempt to draw comparisons between data from the two sources; nor do we attempt to draw conclusions as to the approach to chemical equilibrium in the open-hearth furnace. Many of the operating variables that are likely to be erratic or unrecorded during the earlier stages of the heat become more consistent and arc more readily subject to observation and control during later stages. For example, undigested lime or ore gradually goes into solution, the rate of carbon drop levels off, and the temperature of the metal is brought under control. For these and other reasons a greater degree of self-consistency is likely to be found among data obtained during the

Jan 1, 1940

By C. B. Daellenbach, T. D. Tiemann

The prevention of quartz flotation by chelation of activating ions with the tetrasodium salt of EDTA in oleic acid flotation was investigated using a small vacuum flotation cell. It was found that flotation of quartz could be entirely suppressed in the presence of activating ions during complete flotation of hematite. It was further shown that the concentration of activating ions liberated from Wisconsin Gogebic taconite is sufficient to float quartz in an oleic acid system. Large tonnages of low grade siliceous iron ores occur on the iron ranges of the Lake Superior district. Although the lower grade nonmagnetic types are currently not of economic importance, they constitute a large future potential source of iron and steel, and hence have been the subject for extensive research on their beneficiation. TACONITES Of particular interest to the Dept. of Minerals and Metals Engineering at the University of Wisconsin have been the low grade nonmagnetic taconites of the Wisconsin Gogebic Range. These occur as five members of the iron formation and have been described in detail elsewhere.' Essentially they consist of an intimate mixture of hematite, goethite and quartz, with minor amounts of siderite, magnetite, iron containing silicates, and manganese minerals. A typical mean analysis based on the Bureau of Mines analyses' is: SiO2-52.50%, Fe2O3-43.40%, (Fe-30.38%), A12O3-1.15%, P2O5-0.07%, Mn2O3-0.29%, CaO-0.07%, (S-0.03%), Loss on ignition-2.00%. The quartz in these ores is of a microcrystalline variety,2 and so intimately associated with the iron oxide minerals that extremely fine grinding, in the order of minus 325 mesh, is required for liberation. During grinding and subsequent flotation, the concentration of quartz activating ions in the pulp becomes sufficiently high to activate quartz which floats along with the iron minerals in the presence of oleic acid. cook3 and co-workers concluded that oxidized iron ores released appreciable quantities of quartz-activating ions in water pulps. This is shown to be true in the present investigation. As a matter of fact, application of this phenomenon, as well as the intentional addition of activating calcium ions, is made use of in the an ionic flotation of silica from the iron oxide minerals.4,5 In view of the above, it becomes almost impossible to effect a sharp separation of quartz in the oleic acid flotation of the iron oxide minerals from these taconites, even with satisfactory liberation. This fact led to the current investigation to find a means of linking the activating ions with a chelating agent. The aim was to establish basic data for the quartz-water-oleic acid system which might not only be applicable to iron ores, but also to the flotation of other siliceous ores as well. EXPERIMENTAL METHODS Vacuum Flotation Cell: The vacuum flotation used in this investigation is similar to that used by previous investigators.6,7,8 The cell consisted of a 100 ml graduated cylinder with the lip removed. Vacuum from a water aspirator was applied to the cell through a trap; suitable tubing, and a rubber stopper inserted in the top of the cell. Constant absolute pressure was maintained by means of a manometer connected to the trap with a tee. Flotation: The required amount of activating ion solution was pipetted into a beaker. This was then diluted to 99.0 ml with water having a pH below that desired for the test, or so adjusted with HC1. After addition of 1.0 ml of oleic acid solution (2.0 mg oleic acid per ml), the pH was readjusted to the desired value with NaOH, and the entire solution transferred to the cell containing 1.5 gm of quartz. After vigorously agitating the cell and its contents for 2 min, the vacuum was applied to the cell and the estimated degree of flotation observed for a 3-min period. Activating ions studied included Ca++, Mg++, Al+++, and Fe+ + + added as chloride solutions. In addition,

Jan 1, 1964

By Clarence E. Sims, Donald W. Williams, George A. Moore

INTRODUCTION DURING the past several years, the steel casting industry has made studies of heavy castings in which the test bar has been taken from heavy sections rather than from attached or separately cast coupons. It has been noted that the ductility properties of these heavy sections are often lower than those normally expected. Such lowered ductility is usually accompanied by a spotty test bar fracture, and the ductility values can often be greatly improved if a low-temperature aging treatment is given to the casting. A loss of ductility of this type is considered "abnormal," since it is not accompanied by an increase of tensile strength or hardness, and "temporary" when the ductility can be restored by aging. The cure of such an abnormal condition represents a real improvement in the quality of the steel, Several types of abnormal loss of ductility can be distinguished, of which those caused by excessive amounts of inclusions of undesirable type and those caused by unsuitable grain size and ingot structure are well known. The particular type of abnormal lowered ductility currently under consideration may be distinguished by the fact that the low-temperature aging treatment necessary for its relief is insufficient to cause any visible change in the microstructure as ordinarily observed. As this aging will in fact eventually occur at room temperature, the phenomenon of present interest may be given the symptomatic definition, "Temporary Abnormal Low Ductility." Some hundreds of previous investigations, largely qualitative in nature, have established, beyond reasonable doubt, that hydrogen is normally present in newly manufactured steel and that this gas, in small amounts, can cause a temporary abnormal loss of ductility. The commonly observed association of high gas content and low ductility has given strong evidence for the presumption that hydrogen-, possibly assisted by other gases, is the primary cause of the low ductility observed. Accordingly, The Steel Founders' Society of America has, since Nov. 1, 1944, sponsored investigations at Battelle Memorial Institute whose primary objective is to obtain quantitative information on the relation of the amount of hydrogen and nitrogen in steel, together with associated methods of steelmaking and treatment, to low-ductility effects and porosity. The interest of this investigation thus extends to permanent abnormal losses of ductility, such as are caused by the inclusions which sometimes result from special deoxidizing practices and possibly from metallic nitrides, but as these can be distinguished from the temporary effect of hydrogen, they have been excluded from the work reported here except when they

Jan 1, 1948

By E. R. Borcherdt

Methods and equipment are subject to study in the Butte district at all times in order that advantage may be taken of any new developments that might serve to increase efficiency and lower costs. Detailed time studies of each operation involved in the entire mining process have been of invaluable assistance in analyzing the individual operation for possible improvement. In other words, the fact that a practice has been in vogue for many years does not exempt it from change provided an easier and cheaper method can be found. Exploration Ore occurs in the Butte district in such manner that structures must be drifted on, no matter how small or unimportant they appear when intersected by a crosscut. Parallel structures also add to the crosscut requirements. This prospecting work, which formerly was done entirely by drifting and crosscutting, is now being supplemented by diamond drilling, to aid in greatly decreasing the amount of waste. In long-shot prospecting, or in second or third class prospecting, where the chances of developing commercial ore are not very great, diamond drilling is of particular value. In prospecting where chances of encountering commercial ore are certain or where crosscuts can be used later for haulage or ventilation, drilling obviously is not applicable. Improvement in drilling machines and bits has contributed greatly to the present success of diamond drilling. For many Years square-set filled stoping was the principal mining method used in the Butte district. Later timbered and untimbered rill stopes were used, also some horizontal cut-and-fill stoping where both Ore and walls were particularly strong. Because of the amount of timber required for square-set stoping, and the relatively low production per stope unit, experiments with horizontal cut-and-fill stopes were begun in Ore bodies of which many had fairly weak walls. It was felt that increase in the speed of the stoping operation, followed closely by filling, to avoid weight being produced by permitting ore and walls to remain insufficiently supported over comparatively long periods, would maintain the walls and backs in safe condition without the use of timber and without ore dilution from wall slough. Cycles of drilling, scraping ore, and filling were devised, which have materially increased stope production and decreased timber consumption, so that both stope labor and supply costs were lowered appreciably without materially affecting grade control. In the larger mines of the district, where wide veins favor this stoping method, half of the total production is now being mined by horizontal cut-and-fill stopes (Fig. I). The increase of the filling rate demanded by the increased stoping rate was the greatest obstacle encountered in the accelerated stoping operations. Finally this problem was solved by replacing the time-honored method of transferring filling waste by small cars, which were hoisted or lowered in the auxiliary shaft, by a transfer

Jan 1, 1943

By H. M. Kraner, E. B. Snyder

This paper shows that volume stability, low porosity and decreased pyroplasticity are desirable for blast-furnace linings, partitularly for the hearth. It shows further that a hot load test is a valuable means of testing the fusion or softening behavior of a refractory at operating temperatures. The effect of carbon monoxide on commercia1 blast-furnace refractories in their as-received condition and after refiring is reported, showing that many commercial blast-furnace refractories disintegrate badly but that refiring decreases the effect and certain special refractories are now available which are almost free of the tendency. Factors Affecting Choice of ._ Refractories If one were to depend entirely upon experience or trial in the selection of clay refractories, the solution of a problem would be a slow process. Furnace campaigns are so long and attended by so many variables that it is difficult to draw fine distinctions within a reasonable period of time in regard to the quality of refractories used. It could be said, of course, that if service results do not yield the proper information for intelligent choice, there is no difference in the quality of brick being considered, but this is not necessarily true. Conventional ceramic tests are designed to give the ceramic engineer information as to the refractoriness and firing tempera- . ture, which he in turn internrets in terms of volume stability, ability to withstand load at high temperature (pyroplasticity), permeability, chemical stability and re-. sistance to the action of slag. In most refractory applications . several of these factors are involved. In a particular instance, one requirement may be predominant, while in others some other factors may be of primary importance. In this country, clay refractories are generally made from mixtures of plastic and flint fire clays. The process of firing a clay refractory is one of slowly melting the constituents, and during this operation its porosity is gradually reduced. The process is arrested, of course, in its incipient Stages and the Progress is determined by measuring slight changes in porosity, volume, bulk gravity, etc., that have taken place. Often the temperatures to which clay refractories are exposed in service are higher than those employed in their firing. However, if the manufacturer were to fire them at such high temperatures the brick would distort. Therefore it would be difficult for the manufacturer to fire all of his clay refractories to temperatures at which they are to be used, although in many cases it would be desirable from the user's point of view if he would do so. The porosity of clay refractories decreases by firing, to a minimum limit, after which a further increase in the temperature causes expansion in certain clay constituents and bloating in others. Both may occur in the same refractory containing two such clays.

Jan 1, 1944

By Albert Sauveur

The following propositions and corollaries are intended to present, as concisely as possible, some of the evidences gathered while studying the microstructure of steel. Each proposition is accompanied by photo-micrographs showing the structure of illustrative samples. But it must be understood that the special instances thus chosen for illustration are by no means the only ones on the examination of which the propositions are based. On the contrary, they have been taken almost at random among a great many, in some instances more than a hundred, similar cases. Proposition I. A slow and undisturbed cooling from a temperature x or higher produces crystallization. Plate L, Plate II., Fig. 1, and Plate V., Figs. 1, 2, 3 and 4 show the crystalline structure of several pieces of steel. Plate I. reveals this structure in the center of a slowly-cooled Bessemer ingot, 1.5 feet from the top. Plate II., Pig. 1, is from a small 2-in, square testingot of the same heat, slowly cooled. Plate V., Figs. 1, 2, 3 and 4 show the structure of different parts of steel rails. The original photographs were all magnified 70 diameters, and have been reduced in engraving to 63, or to 55 diameters, as shown in the plates. Proposition 11. Undisturbed cooling from an initial temperature lower than x is not accompanied by crystallization. Plate III., Fig. 5, shows the structure of a piece of rail-steel forged from a white heat until it had fallen to dull-red. The structure is almost amorphous. Practically no crystallization has taken place during the subsequent cooling. Corollary.—Pieces of steel finished at a temperature lower than x do not take a crystalline structure.

Jan 1, 1894