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By E. T. Turkdogan

The activity of sulfur was determined as a function of composition of ferrous sulfide by equilibrating with hydrogen sulfide-hydrogen gas mixtures at 670° , 800°, and 900". The present results supplement the available data over the composition range from 36.6 to 39.5 pct S. The X-ray lattice spacing measurements made are in accord with the available data and indicate that the limiting composition FeSl.008 may be taken for the iron-iron sulfide equilibrium. The growth rate of ferrous sulfide on iron was measured by reacting iron strips or blocks in hydrogen sulfide-hydrogen gas mixtures. Owing to the slow approach to equilibrium between the gas phase and the surface of the sulfide layer, The sulfidation experiments were carried out for several days. It is shown that the growth rate ullimately proceeds in accordance wilh the parabolic rate law. From the parabolic rate constants and the thermodynamic data on iron sulfide the self-difiusivity and chemical diffusivity of iron in ferrous bisulfide are evalualed. The self-diffusivity of iron thus derived zs found to increase with increasing sulfur content. THE ferrous sulfide known as "pyrrhotite" is a non-stoichiometric phase having a wide composition range from about 50 to about 58 or 60 at. pct, depending on the sulfur activity. RosenQvistl studied the thermodynamics of this phase over wide ranges of temperature and composition. Hauffe and Rahmel' and Meussner and ~irchenall~ studied the parabolic rate of sulfidation of iron in sulfur vapor. By using markers, these investigators showed that the iron cations were the predominant diffusing species in iron sulfide. This is confirmed decisively by the self-diffusivity measurements of condit4 who showed that the self-diffusivity of sulfur in ferrous sulfide is several orders of magnitude lower than the self-diffusivity of iron. Although much has been learned from these studies about the Fe-S system, further research on this subject was considered desirable for better understanding of the physical chemistry of iron sulfide. This work was confined to the study of the kinetics of sulfidation of iron in hydrogen sulfide-hydrogen gas mixtures. The results of this study are given in two consecutive parts. Part I, the present paper, is on the parabolic rate of sulfidation of iron and the diffusivity of iron in ferrous sulfide. The second paper, Part 11, is on the kinetics of the surface reaction between hydrogen sulfide and ferrous sulfide. EXPERIMENTAL Three types of experiments were carried out: i) equilibration of ferrous sulfide with gas of known E. T. TURKDOGAN, member AIME, is Manager,Chemical Metallurgy Division, Edgar C. Bain Laboratory for Fundamental Research, U. S. Steel Corp., Research Center, Monroeville, Pa. Manuscript submitted March 6. 1968. ISD sulfur potential; ii) X-ray studies of ferrous sulfide; and iii) measurements of the parabolic rate of sulfidation of iron. Equilibrium Studies. About 1 g of iron powder or foil. contained in a small recrystallized alumina crucible ind suspended from a calibrated silica spring, was reacted with a hydrogen sulfide-hydrogen mixture of known ratio until no further change in weight was observed. %hen the gas composition was changed and the new state of equilibrium was established after several hours of reaction time. The composition of the sulfide was obtained from the initial weight of the sample and the weight after equilibration. X-Ray Studies. The lattice parameters of some of the equilibrated samples were determined using the General Electric XRD-5 diffractometer with a cobalt tube (no filter) set at 40 kv apd 10 ma; the CoK, radiation was taken as 1.79020A. Observed 220 and 311 diffraction peaks of silicon served as an internal comparison standard to correct for possible misalignment of the goniometer. The lattice parameters of the sulfide phase were calculated from the corrected Bragg angles of the 110 and 102 peaks. Rate Studies. In the initial experiments attempts were made to measure the parabolic rate of sulfidation by measuring the gain in weight of a thin iron strip, -0.05 cm thick, suspended from a silica spring in the reacting atmosphere. The preliminary experiments showed that this technique was not reliable for the measurement of the parabolic growth rate of the iron sulfide layer. In the subsequent experiments the data on growth rate were obtained by measuring, on a microscope stage, change in the thickness of the sample after reaction for a specified time in a hydrogen sulfide-hydrogen mixture of known sulfur activity. For each reaction time a new sample was used. Precision-machined iron blocks, 0.5 by 2 by 5 cu cm, were de-greased and annealed in hydrogen for several hours prior to the sulfidation rate measurements. The experiments were carried out at 670°, 800°, and 900°C in gas mixtures having the ratios, and 1.0 for periods of times from a few hours up to 8 days. Apparatus and Materials. A vertical globar tube furnace with a 3-in.-long uniform temperature zone was used. The glass tube fittings were fused on the zircon reaction tube, 1.5 in. diam. The temperature was measured with a Pt-10 pct Rh/Pt thermocouple placed in the hot zone of the furnace inside the reaction tube (an alumina thermocouple sheath was used). A separate thermocouple was used for the temperature controller which maintained the furnace temperature constant within about 2°C. Anhydrous liquid hydrogen sulfide and oxygen-free dry hydrogen from gas tanks were used in preparing the gas mixtures by the constant head capillary flow-meters. In all cases volume flow rate was 1000 cu cm per min at stp, corresponding to a linear velocity of about 6 cm per sec at 800°C; under these conditions

Jan 1, 1969

By B. W. Frazier

AT a recent meeting of the North of England Institute of Mining and Mechanical Engineers, during a discussion upon the compression of air, attention was called to an apparent anomaly in the phenomena attending the compression. At a subsequent meeting this apparent anomaly was explained by Prof. Herschel, and all the facts observed shown to be strictly in accordance with the laws of thermodynamics. Upon reading the report of the discussion in the published transactions of the society, it occurred to me that an attempt to determine mathematically the amounts of energy (whether in the form of heat or of work) expended and absorbed in compressing air, and causing it to perform work by expansion, might prove of use to some who have not access to any treatise upon the application of the laws of thermodynamics to the compression of air, and who have not the time or the inclination to make such application for themselves. The apparent anomaly noticed was this: If air be compressed, and at the same time, by the sufficient application of a cooling medium, kept at a constant temperature, the indicator diagrams in the

Jan 1, 1874

By AIME AIME

THE best meeting ever held, was the opinion expressed by a number of those who attended the annual meeting of the Institute in New York, Feb. 18 to 21, and there was an atmosphere of friendliness and good fellowship about it that fully justified the feeling. In numbers it was not quite so large as last year and unless the Engineering Societies should build for themselves a new building it is probable that no meeting can be larger, in respect to numbers, than that held in 1928, which was only made possible by the circumstance that the eighth floor of the building happened to be, temporarily vacant at the time. The number of rooms available for -sessions that were provided when the building was built long ago proved inadequate, and it is only by the expedient of obtaining the temporary use of the board and committee rooms of other societies that it is possible to arrange for the over 40 sessions that must be spread over the four days of the meeting. The-fifth floor, where. a buffet lunch is served each-day, has reached its full capacity and it seems quite evident that any future development of Institute meetings must be along the lines of quality, not size.

Jan 1, 1929

By Benjamin Petkof

The mineral mica, which has been known to man since ancient times, has played an impor¬tant role in the development of our modern industry. In the latter part of the 19th century sheet mica began finding use as a dielectric insulating material in the newly developing electrical industry. Later, when modern elec¬tronics began to develop, it became a vital insulating and dielectric material for use in electronic equipment. Both the electrical and electronic industries were greatly dependent on some form of natural mica. The manufacture of electric motors of varying sizes, electronic tubes, and other electronic items was dependent on an adequate supply of sheet mica. During World War II this material was so vital to national defense that special efforts were made to mine it in the United States as well as to obtain it from overseas mica-producing areas. However, advancing technology has successfully begun the progressive development of man-made mica-based and non-mica-based materials that can replace mica for many uses. In addition, developing technology has dictated changes that have made sheet mica unnecessary for some uses. As the demand for sheet mica declined, the demand for scrap and flake mica has continued to increase. In fact, today the domestic production and use of scrap and flake mica far outshadows the necessity for good¬quality sheet mica in this country. Historically the United States has always been dependent on foreign sources of material for good-quality sheet mica and imports practically its entire requirement. In the case of scrap and flake mica, the United States is the dominant world producer and consumer. End Uses Sheet mica (Chowdhury, 1941; Rajgarhia, 1951; Skow, 1962) is available in many com¬mercial forms, but these forms can be broadly classified into manufactured and unmanufac¬tured mica. Manufactured mica consists of mica that has been shaped, punched, or other¬wise processed into some form, suitable for a particular end use. Unmanufactured mica con¬sists of partially hand-trimmed or processed material that has not been prepared for any particular end use. Unmanufactured mica is broken into two commercial classes consisting of sheet mica and scrap and flake mica. These classes of mica differ greatly in their ultimate end uses and marketed forms. Sheet muscovite mica can be classified by color, degree of prep¬aration of the crude material, thickness, size, visual appearance, and electrical quality. In addition, phlogopite mica is also classified by its thermal stability. Scrap and flake mica consist of mine, trimming shop, and factory scrap that occurs as remnants from mining, processing, and manufacturing operations, and small particle size mica that is available from the beneficiation of pegmatites, clays, schists, or other mica-rich host rock. The end uses for sheet mica vary so greatly from those of scrap and flake mica that it is necessary to discuss them separately. Sheet Mica Sheet mica consists of relatively flat sheets of material which have been mined as naturally occurring books or runs of mica. These sheets are hand-trimmed to remove any imperfections and are punched or stamped into specified shapes for industrial use. Sheet mica can be further processed and is described or specified as block, film, or splittings based on thickness. Block mica is not less than 0.007 in. thick with a minimum usable cross-sectional area of 1 sq in. Film mica is split from the better quali¬ties of block mica to specified thickness groups ranging from 0.0012 to 0.004 in. Splittings are sheets of mica with a maximum thickness of 0.0012 in. and a minimum usable area of 0.75 in. Other small sized, lower quality block mica

Jan 1, 1975

By C. W. Spencer, J. Singer

A PARTIAL phase diagram for the As-Te system is given in Hansen.' The only compound reported is As2Te3, melting at 362°C. Stoichiometric quantities of reagent-grade elements were reacted in evacuated quartz and directionally cooled. The resulting ingot consisted of very thin threadlike crystals from which only very small single-crystal fragments were isolated. A powder diffraction diagram disclosed nonisomorphism with the analogous V-VI compounds insofar as these have been reported; Sb2S3, As2S3, Bi,S,, and Bi2Te3 data in the ASTM index of powder patterns, together with the single-crystal data on Sb2Se3,2 were used for the com- parison with the observed spacings. Single-crystal data confirmed the uniqueness of the As2Te3 structure. Single-crystal Weissenberg diagrams have so far yielded the following data: As2Te3 is monoclinic, space group C-m (OkO data still lacking), a = 14.4A, b = 4.05A, C = 9.92A, ß = 97". The cell volume is about 5802. The set of isomorphous ortho-rhombic cells of Sb2Se3, Sb2S3, and Bi2S, are apparently related to As,Te, in having one lattice constant close to 4.0 and with cell volumes as large as 540A8. Assuming Z = 4 for As2Te3 also, the density is calculated as 6.1 which agrees well with a roughly determined value of 6.0. A complete structure analysis is under way.

Jan 1, 1956

By George H. K. Schenck, Peter G. Donald

There is an accelerating acceptance of change by management of cement companies. Diversity of response is noticeable in efforts across the country to reverse the downward trend in profits that brought margins in 1966 to the lowest point in 20 years. New concepts are emerging among managers as they seek to increase the efficiency in use of the basic corporate resources of men, capital and technology. The shift towards computerized control of cement manufacturing is making new gains as is diversification of cement companies into allied fields such as production and sale of natural and light- weight aggregates, crushed stone and concrete products. Increased interest in special products such as white cement and further moves overseas are also significant. Perhaps the most dramatic event of recent years occurred in Washington at hearings before the Federal Trade Commission where cement producers split on whether there should be FTC guidelines that would prevent ownership of ready-mixed concrete producers by cement companies.

Jan 4, 1967

By Carl R. Christiansen

Since the first pay hole in Missouri's "New Lead Belt" was drilled in 1955, this district has become one of the world's leading sources of lead. The belt extends from north of Viburnum in a southerly direction to near Eminence, a distance of about 35 miles. The St. Joseph Lead Company was the discoverer and first to develop new mines in the Viburnum area. Since the discovery of the New Lead Belt, many companies have engaged in exploration programs and several major companies have become active in development of new mines. These include Cominco American, Inc., which operates a joint venture with Dresser Industries; Ozark Lead Company, a subsidiary of Kennecott Copper Company; and Missouri Lead Operating Company, a joint venture of Arnax and Homestake. St. Joseph Lead Company, with over 100 years of experience in the Old Lead Belt, has served as a leader in development of equipment and mining techniques, making its properties some of the most efficient mining operations in the world. The new producers give the district the benefit of fresh viewpoints, as their engineers are mostly from outside of Missouri and their previous experience has been considerably different from conventional lead belt practices. While all operations are similar in that they are room-and-pillar, the diverse experience of the operators has produced a group of mines that employ a variety of equipment and mining techniques to give increased efficiency

Jan 1, 1970

By K. A. Slagle

Hydraulic analysis of the wellbore has become increasingly inzportant for designing cementing operations and selecting equipment, materials and techniques to complenzent modern well-c-ompletion practices. Non-Newtonian fluid technology has advanced beyond the point where former empirical methods of analysis adequately define the hydraulic system and fluid properties. In view of these factors, this paper describes a series of rheological calculations which have been found practical, through field usage, for assistance in selecting a cementing program. A relatively simple laboratory method using standard viscometric equipment is suggested for determination of the rheological properties of slurries, and clrrta are presented on some of the more common cementitrg conzposition.A. A criterion for divergence from laminar-flow characteristics has been proposed. Usefulness of the calculations is indicated by examples of cementing operations where they have been used. INTRODUCTION With the changing aspects of well-completion practices during the past few years, it has been increasingly important to have a relatively simple method of analyzing the flow conditions existing in the well during cementing operations. This is particularly true in view of the improved economics toward which most of the changes have been directed. Rheological characteristics of slurries used for cementing should be a major consideration in the trend toward smaller casing sizes, either single or multiple strings. Receiving increased attention is the practice advocated in 1948 by Howard and Clark' of attaining turbulent flow with the fluids circulated during a primary cementing operation. While there may still be a difference of opinion concerning this technique, most available information indicates that superior primary-cementing results are generally obtained when high displacement rates are employed. Fluid properties of the slurry to be used must be available, as well as calculation methods, to determine what flow rates should be attained and the probable consequences in terms of frictional pressure and horsepower utilization. It would certainly be inappropriate to attempt high displacement velocities if sufficient pressure might be developed to create lost circulation. Since cementing slurries are non-Newtonian fluids, it is not possible to define their rheological or fluid properties by the single factor of viscosity and then make calculations for the quantities just described. Because the shear stress-shear rate ratio is not constant: it becomes necessary to establish at least two parameters for adequate fluid-flow calculations. It is not the purpose of this paper to delve into the mathematical development of non-Newtonian technology, nor to discuss the arbitrary classification system under which a single fluid may resemble two or three different classes depending upon experimental conditions. Rather, the intention is to present a useful series of calculations based on a concept applicable to both Newtonian fluids and to the preponderance of non-Newtonian fluids encountered in the oil-producing industry. Development of this approach was begun some 32 years ago,' and has most recently been brought to fruition by Metzner and his co-workers at the U. of Deleware. Some non-Newtonian fluids encountered in the petroleum industry, other than cementing slurries, have also had the benefit of this method of analysis."' The two parameters required to define the fluid are usually denoted by the symbols n' and K' and, for the purposes of this discussion, are called "flow behavior index" and "consistency index", respectively. These two slurry properties permit calculation of the Reynolds' number and the "critical" velocity, or the velocity at which departure from laminar flow begins. EXPERIMENTAL DETERMINATIONS The two principal instruments used for rheological studies are the pipeline (capillary-tube) viscometer and the rotational viscometer. When conveniently possible, a capillary-tube viscometer (where the pressure drop and flow rate of the material can be measured) is the better method for rigorous determination of the flow behavior index and consistency index for non-Newtonian fluids. With pressure-drop data at various flow rates, it is then possible to prepare a logarithmic plot of shear rate as the abscissa-shear stress as the ordinate. For fluids which do not exhibit time-dependency, these data will usually produce a straight line. The flow behavior index n' represents the slope of this line, while the consistency index K' becomes the intercept of this line at unity shear rate in accordance with the mathematical derivations associated with this concept of rheology. Due to the difficulties anticipated in maintaining a uniform, pumpable cement slurry for the time interval required to obtain measurements from the pipe viscometer, the n' and K' data reported herein were obtained using a direct-indicating rotational viscometer (Fig. 2). The

By H. N. Hall

Reservoir and producing characteristics can govern the decision to use either a one-, two- or three-dimensional model for making predictions for gravity-drainage reservoirs. Examples of conditions requiring one-, two- and three-dimensional calculations are given. In 1961 the author presented a method for predicting one-dimensional gravity-drainage performance. This work has been exrendcd to obtain a three-dimensional model, which is described and for which a sample problem is presented. Introduction Many papers on gravity drainage or gas-cap drive'-3 have been presented for conditions where the reservoir is treated as a single areal segment so that, in effect, only one-dimen-sional flow is considered. Other authors'-Q ave given evidence showing that the one-dimensional concept would be unsatisfactory to predict reservoir performance for certain types of reservoirs. Experience has indicated that specific reservoir and producing conditions govern whether one-, two- or three-dimensional concepts must be used as a basis for reliable reservoir performance predictioils. Previously the author presented a paper outlining a method for predicting the performance of gravity-drainage reservoirs.' That paper treated the reservoir as a single areal segment so that it was applicable for only one-dimensional flow. The work has been extended to obtain a three-dimensional model that can be used to predict performance of gravity-drainage reservoirs. Although capable of being three-dimensional, it can be used equally well for one- and two-dimensional predictions. This paper discusses those reservoir and producing conditions governing the choice of model, and also describes a three-dimensional model suitable for predicting reservoir performance in the more complex situations. Discussion The Choice of Model To predict reservoir performance, it is necessary to represent the reservoir by a physical model. A mathematical model, based on the assumed physical model, then is used to predict the movement of oil and gas within the reservoir. The word "model" is used here to connote the combination of both a physical model and a mathematical model based on the physical model. Certain types of reservoir situations may be predicted suitably with a one-dimensional model, whereas two- and three-dimensional models may be required for other situations. This section illustrates reservoir conditions associated with the use of a specific type of model. Many types of reservoir structures are such that gravity drainage possibly could be an important factor in oil production. Production practices, as well as the nature of the structure. can influence the type of model that should be used. obviously, it is impossible to discuss all combinations of reservoir structure and production practices that might be encountered in gravity-drainage reservoirs. The following are typical examples of conditions where a choice must be made among a one-, two- or three-dimensional model to predict reservoir performance satisfactorily. Conditions Requiring a One-Dimensional Model Fig. la shows contours for an asymmetrical anticline in which gravity drainage might be expected to be important. Fig. Ib depicts a cross-section along Line A-A in Fig. la. Existence of a gas cap is a good clue that gravity drainage will be an important factor in producing oil from this type of reservoir. However, it is not essential since a gas cap will form as oil is produced from the reservoir. If the proper combination of reservoir permeability and withdrawal rates is present, the reservoir will behave like a

Jan 1, 1969

By Arthur F. Taggart, Nathaniel Arbiter

The fact that the floatability of minerals with fatty-acid collectors changes as the pH of a pulp varies was utilized in the early days of flotation, when sulphuric acid was used with oleic acid to float sphalerite and galena. from gangues which themselves float with fatty acids in alkaline pulps. Gaudin1 showed that this difference in floatability is a regular function of the extent of the change in pH. The present paper offers an explanation of the phenomenon, and on the basis thereof sets up recommendations for control of soap-flotation operations. Experimental Parallelism between floatability of a mineral in a given environment and its contact angle in that environment is so well established,2 and the contact angle is so readily and rapidly measurable, that contact angles have been used throughout the experimental work to indicate relative floatability. Experiments comprised contact-angle measurements on a number of representative minerals and metals, and a variety of subsidiary tests designed to check and to amplify the contact-angle indications. Contact-angle measurements were made by the method described in detail by del Giudice.3 Sequence of procedure for determination of the points of Fig. I was: I. Polish specimen. Most specimens yielded zero contact angle after polishing; a few showed a slight "cling." Cling is characteristic of specimens that pit on polishing; it is due to a residue of organic contamination, originally on the particle surface, which persists in the pits. The cling did not change total contact angle after conditioning, and is not, therefore, additive in the upper part of the curves of Fig. I. It may have broadened the bases of the curves for the affected minerals slightly. 2. The specimen was next conditioned in soap solution for 5 minutes. 3. The conditioned particle was transferred, under conditions that precluded surface drying, to an aqueous solution of the pH desired and contact angle determined. 4. The particle was thereupon transferred, again without surface drying, to water. The confirmatory tests will be described at the places pertinent in the argument. Discussion of Results Gaudin and Vincent4 have shown that contact angles with heptoic acid as a collector decrease for a given specimen when the concentration of collector present falls below a certain value. A similar reduction in angle occurs with collector-conditioned particles that are visibly slime-coated, and varies roughly with the extent of coating. Since in the last case the reduction in angle is certainly due to reduction in the proportion of total conditioned mineral surface presented to the bubble, the authors believe that the same condition prevails in the first case cited, and that similar reduction in angle and floatability will occur whenever starvation quantities of collector are present, whether by design or by reason of excessive consumption.

Jan 1, 1943

By Nathaniel Arbiter, Arthur F. Taggart

The fact that the floatability of minerals with fatty-acid collectors changes as the pH of a pulp varies was utilized in the early days of flotation, when sulphuric acid was used with oleic acid to float sphalerite and galena. from gangues which themselves float with fatty acids in alkaline pulps. Gaudin1 showed that this difference in floatability is a regular function of the extent of the change in pH. The present paper offers an explanation of the phenomenon, and on the basis thereof sets up recommendations for control of soap-flotation operations. Experimental Parallelism between floatability of a mineral in a given environment and its contact angle in that environment is so well established,2 and the contact angle is so readily and rapidly measurable, that contact angles have been used throughout the experimental work to indicate relative floatability. Experiments comprised contact-angle measurements on a number of representative minerals and metals, and a variety of subsidiary tests designed to check and to amplify the contact-angle indications. Contact-angle measurements were made by the method described in detail by del Giudice.3 Sequence of procedure for determination of the points of Fig. I was: I. Polish specimen. Most specimens yielded zero contact angle after polishing; a few showed a slight "cling." Cling is characteristic of specimens that pit on polishing; it is due to a residue of organic contamination, originally on the particle surface, which persists in the pits. The cling did not change total contact angle after conditioning, and is not, therefore, additive in the upper part of the curves of Fig. I. It may have broadened the bases of the curves for the affected minerals slightly. 2. The specimen was next conditioned in soap solution for 5 minutes. 3. The conditioned particle was transferred, under conditions that precluded surface drying, to an aqueous solution of the pH desired and contact angle determined. 4. The particle was thereupon transferred, again without surface drying, to water. The confirmatory tests will be described at the places pertinent in the argument. Discussion of Results Gaudin and Vincent4 have shown that contact angles with heptoic acid as a collector decrease for a given specimen when the concentration of collector present falls below a certain value. A similar reduction in angle occurs with collector-conditioned particles that are visibly slime-coated, and varies roughly with the extent of coating. Since in the last case the reduction in angle is certainly due to reduction in the proportion of total conditioned mineral surface presented to the bubble, the authors believe that the same condition prevails in the first case cited, and that similar reduction in angle and floatability will occur whenever starvation quantities of collector are present, whether by design or by reason of excessive consumption.

Jan 1, 1943

By Jack R. Elenbaas, Donald L. Katz

A radial turbulent flow formula has been developed which permits the computation of the pressure drop for radial flow in gas wells whether the flow is laminar, turbulent, or partially laminar and partially turbulent. Using the formula a complete back-pressure curve has been calculated and analyzed by a comparison with existing back-pressure curves. A procedure is presented for computing the permeability of the porous media when the porosity, sphericity and average particle diameter are known. Introduction Recent studies on the flow of fluids through porous media have provided new methods for computing flow under turbulent conditions. The present study was initiated as an investigation of pressure -drop computations for flow through porous sands in gas wells and as an analysis of present-day back-pressure tests. Although laminar flow exists in the producing formation of gas wells under normal flow rates, turbulent flow does take place adjacent to the well bore. As the flow rate is increased, turbulent flow exists further and further into the producing formation and under open-flow conditions in relatively deep wells a considerable portion of the flow through the sand will be turbulent. In order to calculate a complete backpressure curve for relatively deep wells without resorting to extrapolation of curves drawn from data obtained in back-pressure tests or calculations made in the completely laminar region, it was necessary to have some means of calculating pressure drop for flow through porous sands under turbulent conditions.4.6 As a result, a radial turbulent flow formula was derived from the equations recently presented by Brownell and Katz.1 A rigorous solution of this equation involves a trial and error graphical integration. By making the assumptions of average viscosity, temperature and compressibility factor of the flowing gas, it was possible to graphically integrate the relation for the general case of radial flow of gases through the porous sand of gas wells. A chart has been prepared relating the value of the integral to the radius of the well bore and to the Reynolds number of the flowing gas. The chart actually performs the graphical integration and the solution of the formula is then reduced to a simple trial and error calculation. A typical back-pressure curve is calculated to show the transition from laminar to turbulent flow. This paper will briefly describe the pro-cedurcs for computing flow through porous media, including a method for predicting sand permeability from porosity and grain size and shape. Flow through Porous Media Brownell and Katzl recently reported a correlation for computing flow of fluids through porous media by the use of an enlarged Reynolds number and friction factor in which the porosity of the bed is included as an additional prime variable. The enlargcd Reynolds number com-

Jan 1, 1948

By Donald L. Katz, Jack R. Elenbaas

A radial turbulent flow formula has been developed which permits the computation of the pressure drop for radial flow in gas wells whether the flow is laminar, turbulent, or partially laminar and partially turbulent. Using the formula a complete back-pressure curve has been calculated and analyzed by a comparison with existing back-pressure curves. A procedure is presented for computing the permeability of the porous media when the porosity, sphericity and average particle diameter are known. Introduction Recent studies on the flow of fluids through porous media have provided new methods for computing flow under turbulent conditions. The present study was initiated as an investigation of pressure -drop computations for flow through porous sands in gas wells and as an analysis of present-day back-pressure tests. Although laminar flow exists in the producing formation of gas wells under normal flow rates, turbulent flow does take place adjacent to the well bore. As the flow rate is increased, turbulent flow exists further and further into the producing formation and under open-flow conditions in relatively deep wells a considerable portion of the flow through the sand will be turbulent. In order to calculate a complete backpressure curve for relatively deep wells without resorting to extrapolation of curves drawn from data obtained in back-pressure tests or calculations made in the completely laminar region, it was necessary to have some means of calculating pressure drop for flow through porous sands under turbulent conditions.4.6 As a result, a radial turbulent flow formula was derived from the equations recently presented by Brownell and Katz.1 A rigorous solution of this equation involves a trial and error graphical integration. By making the assumptions of average viscosity, temperature and compressibility factor of the flowing gas, it was possible to graphically integrate the relation for the general case of radial flow of gases through the porous sand of gas wells. A chart has been prepared relating the value of the integral to the radius of the well bore and to the Reynolds number of the flowing gas. The chart actually performs the graphical integration and the solution of the formula is then reduced to a simple trial and error calculation. A typical back-pressure curve is calculated to show the transition from laminar to turbulent flow. This paper will briefly describe the pro-cedurcs for computing flow through porous media, including a method for predicting sand permeability from porosity and grain size and shape. Flow through Porous Media Brownell and Katzl recently reported a correlation for computing flow of fluids through porous media by the use of an enlarged Reynolds number and friction factor in which the porosity of the bed is included as an additional prime variable. The enlargcd Reynolds number com-

Jan 1, 1948

By Clyde E. Williams

THIS review of the progress made in iron and steel metallurgy during the past year is confined to developments in this country. It attempts to give examples to illustrate progress made rather than to appraise results. As a result of the gradually diminishing supply of rich iron ores and of predictions made as to the probable life of the iron-ore reserves of the Lake Superior District, attention of iron and steel executives was directed to the question of beneficiation of iron ores. Laboratory and plant-scale experimental work was conducted on the wash ores .of Minnesota and an investigation, was, begun on the Old Range low-grade ores.

Jan 1, 1931

By Alwyn Birchmore Cox, Ian William Wark

Different parts of the world in which mineral separation by flotation is practiced experience vastly different natural temperatures, and in some districts there is a big difference between summer and winter temperatures. It will be shown in this paper that the temperature is of considerable importance where it is desired to separate pyrite or arsenopyrite from other minerals. It is probable that some of the differences obtained in the flotation of these minerals at plants working under otherwise similar conditions are due to temperature variations. The influence of temperature on the flotation of galena, chalcopyrite and sphalerite by xanthates is less marked than its influence on pyrite flotation. Experimental Method The methods used have been described previously.l-4 In each test the clean mineral specimen was immersed in a solution prepared by adding the reagents in the following order: (1) sodium carbonate and hydrochloric acid as necessary to buffer the solution and to give approximately the pH value desired, (2) sodium cyanide, (3) copper sulphate, (4) ethyl xanthate, followed by (5) a final adjustment of pH value. After ½ hr. the mineral was tested for a xanthate film by bringing a bubble of air into apparent contact with the submerged polished surface. If true contact (spreading) was not obtained within ½ min. and after cleaning the surface by wiping with a small linen pad, it was concluded that the adsorption of a xanthate film had been prevented. Following the method already described (ref. 2), curves have been constructed such that for a solution composition corresponding to any point below the curve, contact between mineral and air is possible, whereas for a solution composition corresponding to any point above the curve, contact is impossible.

Jan 1, 1939

By Ian William Wark, Alwyn Birchmore Cox

Different parts of the world in which mineral separation by flotation is practiced experience vastly different natural temperatures, and in some districts there is a big difference between summer and winter temperatures. It will be shown in this paper that the temperature is of considerable importance where it is desired to separate pyrite or arsenopyrite from other minerals. It is probable that some of the differences obtained in the flotation of these minerals at plants working under otherwise similar conditions are due to temperature variations. The influence of temperature on the flotation of galena, chalcopyrite and sphalerite by xanthates is less marked than its influence on pyrite flotation. Experimental Method The methods used have been described previously.l-4 In each test the clean mineral specimen was immersed in a solution prepared by adding the reagents in the following order: (1) sodium carbonate and hydrochloric acid as necessary to buffer the solution and to give approximately the pH value desired, (2) sodium cyanide, (3) copper sulphate, (4) ethyl xanthate, followed by (5) a final adjustment of pH value. After ½ hr. the mineral was tested for a xanthate film by bringing a bubble of air into apparent contact with the submerged polished surface. If true contact (spreading) was not obtained within ½ min. and after cleaning the surface by wiping with a small linen pad, it was concluded that the adsorption of a xanthate film had been prevented. Following the method already described (ref. 2), curves have been constructed such that for a solution composition corresponding to any point below the curve, contact between mineral and air is possible, whereas for a solution composition corresponding to any point above the curve, contact is impossible.

Jan 1, 1939

By Robert D. Pehlke, Weldon L. Daines

The reduction of manganese oxide from a basic slag by silicon dissolved in liquid iron at steelmaking temperatures was studied to determine the rate-controlling step for the process. The experiments were carried out under an argon atmosphere in a resistance-heated vertical-tube furnace. The two liquid phases, slag and metal, were held in zirconia crucibles. Sampling and chemical analysis of the slag phase led to time-concentration curves for the system. Results obtained by varying parameters such as temperature, stirring rate, concentration, and melt geometry defined the limiting reaction mechanism. The reduction of manganese oxide by silicon is a fast reaction and reached equilibrium within 90 min. The rate of stirring has a marked effect on the reaction rate, while, on the other hand, the effect of temperature is very small. This identifies the rate-controlling step as diffusion rather than interfaciul chemical reaction. The variation of other parameters revealed that a) diffusion of manganese in the iron phase is the slow step, b) the value of D/6 for manganese in iron at 1550°C is 7x 10-4 cm per sec, c) the energy of activation for the apparent rate constant is 7 kcal per mole, and d) increasing the amount of silicon in the iron decreases the diffusion coefficient of manganese. THE equilibrium relations pertinent to the reduction of manganese oxide from a steelmaking slag by silicon dissolved in liquid iron have been studied, but little is known about the mechanisms that control the rate of the process. The purpose of the present investigation was to study the rate of reduction by silicon and to determine the rate-limiting step. The effects of stirring rate, temperature, composition, and melt geometry were investigated as a means of identifying the controlling step. On the laboratory scale, relatively little work has been done in the area of slag-metal kinetics, primarily because of the problems confronted in attempting to contain liquid slags and metals in laboratory crucibles at steelmaking temperatures. Since graphite is an ideal material for a crucible, several investigations have been carried out on the reduction of various oxides from a slag by carbon in graphite-saturated iron and on the transfer of sulfur between a slag and graphite-saturated iron. Most of this work has been performed in induction furnaces. Studies where the container was not graphite are extremely limited. A single kinetic study of manganese transfer between molten iron and basic slags was carried out by Sano, Shiomi, and Matsushita.' These investigators prepared calcium oxide and titanium oxide crucibles to contain the two-phase system. Only a few experiments were carried out and the results had to be treated qualitatively. Despite the paucity of kinetic data, a large quantity of information is available in the literature concerning the thermodynamics2-12 and physical properties'3-21 of the slags containing manganese oxide and the dilute liquid iron alloys containing manganese and silicon which were involved in this research program. EXPERIMENTAL METHOD A vertical-tube resistance-heated furnace was used in this investigation to study the slag-metal reaction Although most previous slag-metal studies were carried out in induction furnaces, a resistance furnace has several advantages including better control of temperature and stirring rate. Hence, a resistance furnace was selected for this study, and its design is shown schematically in Fig. 1. Slip-cast, fine-grained, low-porosity, lime-stabilized cubic zirconia crucibles were used for the kinetic experiments. The crucibles were 4 1/2 in. high and 2 1/8 in. OD with a 1/16-in. wall. The crucibles were only slightly

Jan 1, 1969

By C. G. Dunn

IDENTIFICATION Of the kinds of orientation relationships that may exist among crystals is an important problem in the metallurgical field. As an aid to its solution standard orientations of several orders of twins would be very useful for rapid analyses to discover high-order as well as low-order twin relationships. Although data have been published that give orientations for three generations of twins, these data are not readily useful in the form presented; i.e., in a stereographic projection with one pole per orientation.1 However, accurate data based on calculations of the positions of all {100} planes for such groups would be very useful when presented in tabular form. Therefore, calculations have been made for a group of four orders of twins and the data are listed in Table 3. Illustrative applications are considered briefly, with the idea of pointing out what may be done with large groups of orientations. METHOD OF COMPUTING ORIENTATION OF A TWIN It is common practice to describe the orientation of a crystal in terms of the positions on a stereographic net of the poles of certain planes of the crystal. A single position on a net may be given it terms of two angle variables, two sets of which appear in the following equations: [Polar NetWalff Net x=rsinOocos4pyx=rcos0. y=rsinB,sin4,ny-rsin0.cos¢,, z=rcos0,,z=rsin0.sin4,,] The three numbers x, y and z determine a length r as well as a direction [(0, 0)] in an X, Y, Z coordinate system. In the present case, r will be set equal to (h2 + k2 +12)1/3, where h, k and 1 are the usual Miller indices for a crystallographic plane, a restriction that facilitates determination of the positions of poles of new planes from those of old or known ones,2 as will become evident later. Furthermore, since twinned lattices have certain planes in common, it is an easy matter to determine the orientation of a twin of a crystal if the orientation of the crystal itself is known. We start therefore with a crystal of known orientation (positions of three {100} poles given) and determine where the cube poles occur in first, second, third and fourth-order twins. Methods for identifying twinned lattices and for making the calculations to find the orientation of a twin have been published.3 4 Reference 4 will be illustrated in the calculation of the orientation of a twin, even though this method differs from the one used by the writer in obtaining the following data on four orders of twins. Consider a crystal S and its twin A1, A1 being one of the four {112} or {III}

Jan 1, 1945

By C Gunther

The term metamorphism as commonly used means any change in a rock in either form or composition, from whatever cause. By metasomatism, according to Lindgren, is meant a metamorphism that involves a change in the chemical composition of a rock by the addition or subtraction of substance. Certain types of metamorphism are due to the action of mineralizing solutions, and are closely connected with ore deposition; they form, therefore, valuable guides in the exploration for ore-deposits. Other types of metamorphism are due to regional processes, and are not connected with ore deposition. By dynamo-regional metamorphism is meant a primary alteration of rocks over large areas under conditions of pressure, flow- age, and heat. This process produces schists and gneisses from either sediments or igneous rocks. It is thought that there is little migration of minerals or of elements in dynamo-regional metamorphism, and that the changes are due chiefly to recrysallization and rearrangement of original minerals in bands with their major axes oriented normal to the direction of greatest pressure. Under these conditions limestones are commonly altered to marble, and sandstones to quartzite, basic igneous rocks to greenstone or serpentine, while rocks of normal or acid com- position commonly yield the usual types of schist or gneiss. Dynamo-regional metamorphism, extending over large areas, has no connection with mineralizing processes, and is, therefore, no guide to ore deposits; while this process has certain features, such as characteristic mineral associations, in common with contact metamorphism, the results of the two processes may usually be distinguished without difficulty.

Jan 1, 1932

FRank FirmstoNe, Easton, Pa.: The effect of lead on brass seems to have been recognized by Berthier, and the facts published by him as early as 1818 (Ann. des Mines, 1st ser., iii., 1818, p. 347 et seq.). He there says expressly that copper containing lead makes " dry " (see) brass, and that, for the same reason, blast-furnace

Jan 1, 1898