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By C. L. Kinney

The rapid increase in the amount of steel produced by the basic open-hearth process is an index of its ability to produce high-grade steel from raw materials of the most, varied physical character and chemical analysis. This inherent adaptability of the process has resulted in a lack of care in the selection of raw materials, so that in far too many cases charges are used of a chemical and physical character not justified by local economic conditions. A practice, or series of practices, should be used that will result in the greatest economy for the plant as a whole; therefore, the operations of blast furnace and open hearth must be considered together. In this paper, an effort has been made to show those variations in both open-hearth practice and cost that follow changes in the analysis of the pig iron arid it may be said that the theoretical costs shown are worthy of careful study and consideration. Carbon, manganese, silicon, phosphorus, and sulfur constitute the principal metalloids in basic pig iron and play the leading role in the production of steel by the basic open-hearth process. The percentages of each of these metalloids, with the exception of carbon, is a variable that has its genesis in the economic relation of the blast-furnace plant to its ore and fuel supplies. As the amount of carbon in the iron is a saturation function of the temperature at which it is produced, the variation in the amount carried is, for any given locality and grade of iron, practically negligible and is so considered in the eight heats discussed in this paper. The melting and refining reactions in an open-hearth furnace, either acid or basic, are essentially oxidizing and vary greatly with the type and age of the furnace, as well as the character of the fuel employed. The outstanding characteristic of the basic process, and the one that explains its predominance over the acid, is its ability to form out of the lime charged and the phosphorus oxidized from the charge a stable

Jan 1, 1924

By R. D. Schoone, J. T. Michalak

Recovery, recrystallization, and texture development of a cold-rolled aluminum-killed steel have been studied during simulated box annealing. Two different initial conditions existed prior to cold rolling: 1) essentially all of the nitrogen in solid solution and 2) most of the nitrogen precipitated as AlN. The combined effect of nitrogen and aluminum in solid solution before annealing was to inhibit recovery and sub-grain growth at temperatures above about 1000°F and to raise the recrystallization temperature range on continuous heating at 40°F per hr from 1000"-1050°F to 1065"-1085°F. For the material with nitrogen and aluminum initially in solution there was an inhibition in the nucleation of the (001) [110] texture component and an enhancement of the (111) [110] texture component. The differences in annealing behavior mzd texture development are attributed to preprecipitation clustering of aluminum and nitrogen at subboundary sites developed by prior cold working. THE annealing of cold-worked aluminum-killed steels has been the subject of numerous investigations.'-'2 These studies have been concerned with kinetics of recrystallization, with microstructure and texture development, and with the individual and combined effects of composition, thermal history prior to cold rolling, and heating rates during subsequent annealing. It has been shown that the inhibition of recrystallization, and the development of the pancake-shaped grain and recrystallization texture characteristic of aluminum-killed steels, can be associated with the precipitation of A1N particles during a recrystallization anneal involving heating rates in the range 20" to 80°F per hr. If the AIN is precipitated before cold rolling or if more rapid heating rates are employed, the cold-rolled steels recrystallize more rapidly to an equiaxed grain structure and texture comparable to that of rimmed low-carbon steel. The retardation of recrystallization, the development of the elongated grain structure, and the pronounced (111) texture have been attributed to: 1) precipitation of A1N at prior cold-worked grain boundaries to form a mechanical barrier to grain boundary migration;' 2) precipitation on the boundaries of the growing recrystal-lizing grains as well as on cold-worked grain boundaries;'" and 3) preprecipitation clustering or precipitation on subboundaries to retard recovery, nucleation, and growth. The present study was undertaken to study in more detail recrystallization and texture development during commercial box annealing of cold-rolled aluminum-killed steels. Comparison of the annealing be- havior after cold rolling, for two different conditions prior to cold rolling, was made in an attempt to define more clearly the role of aluminum and nitrogen in forming the recrystallization texture. A) MATERIAL AND PROCEDURE The material used in this investigation was a commercial low-carbon aluminum-killed steel which was hot-rolled with a finishing temperature of about 1565"F, then coiled at about 1020°F. The composition, in wt pct, was: 0.050 C, 0.30 Mn, 0.007 P, 0.019 Si, 0.03 Cu, 0.02 Ni, 0.02 Cr, 0.045 Al, and 0.004 N. Two 4.5 by 13 by 0.078 in. sections were cut from the center section of a hot-rolled panel and one of these was reheated to provide two different conditions prior to cold rolling: low AlN: as commercially hot-rolled, with aluminum and nitrogen in solid solution; and high AlN: as commercially hot-rolled, then reheated at 1300°F for 3.5 hr to precipitate most of the nitrogen as AlN. ~etallc&a~hic examination indicated that the reheating did not change grain size nor carbide distribution (some spheroidization of pearlite was noted). Texture analysis at half-thickness level showed that both sections had the same substantially random as-hot-rolled texture. The results of check chemical analysis of each sample are given in Table I. Both sections were cold-reduced 65 pct on a laboratory rolling mill to a final thickness of 0.027 in. Cold rolling, in one direction only, was in the direction of the prior hot rolling. Specimens 1.0 by 1.25 in. were cut from the cold-rolled sheets and given a simulated box anneal in an atmosphere of 2 pct HZ-98 pct He. Specimens were heated at a constant rate of 40°F per hr from room temperature to various temperatures in the range 750" to 1300°F and cooled immediately by withdrawal to the water-cooled end of a tube furnace. The temperature in the 6-in. uniform hot zone of the furnace was controlled within 3"F. Selection of the individual specimens was made to give a random distribution of annealing temperatures with respect to location in the cold-rolled sheet. At least two specimens of each condition were annealed to the same temperature and smaller specimens for light microscopy, transmission electron microscopy, and X-ray studies were prepared from each of these. Rolling-plane sections for each of these studies were taken at half thickness. Light microscopy and transmission electron micro-

Jan 1, 1969

By Clarence Zener

THE heat-treatment of steels will not pass from the stage of an art into that of a science until the mechanism of the phase transformations associated therewith is thoroughly understood. Such an under- standing will involve two distinct types of inquiry: (I) the direction of the trans- formation, (2) the speed of the transformation. The first type of inquiry, which involves only the equilibrium relations between the various phases in steel, is the subject of the present and of a succeeding article; the second type, which involves the kinetics of transformations, will be the subject of a later article. In order that a theory of equilibrium relations may give useful information, certain experimental data must be put into the theory. It is customary for these data to be of a thermal nature. In the system discussed here in steel such thermal data are very scarce. In medium-alloy steels another type of data might possibly be used. In these steels the concentration of solute is so low that it may be possible to use the approximation of dilute solutions, an approximation that leads to linear relationships. The unknown functions, or constants, may then be determined in some cases from the binary iron- alloy system and in other cases from the ternary iron-carbon-alloy system. From the functions, or constants, so determined may then be computed the equilibrium relations in more complex medium-alloy steels. In the present article this second approach is used, the necessary experimental data being obtained from the simple binary and ternary equilibrium diagrams. FUNDAMENTAL EQUATIONS In this article are derived the equilibrium relations between the gamma, alpha and cementite phases. In these three phases all important alloying elements except carbon form substitutional solutions, each alloying atom occupying a potential site for an iron atom. Carbon, on the other hand, forms an interstitial solution. In the face-centered cubic gamma phase, the interstitial positions are at the center of the unit cube and at the centers of the cube edges. There are therefore four interstitial positions per unit cell, or one per iron atom. In the body- centered cubic alpha phase, the interstitial positions are probably at the face centers, and also at the centers of the edges, which are crystallographically equivalent to the face centers. There are therefore six interstitial positions per unit cube, or three per iron atom. In cementite, (Fe, Alloy)3C, the carbon atoms may be regarded as filling all the lattice positions of a given type. The introduction of the fundamental equations of equilibrium has presented the author with a quandary. These equations are formally so similar to other equations that have been derived1,2 for related systems that they may appear to some readers

Jan 1, 1946

By Louis D. Huntoon

AFTER the completion, in 1905, of the Hammond Mining and Metallurgical Laboratory of the Sheffield Scientific School, Yale University, it became necessary to secure and assay a large assortment of ore-samples, and to arrange the results in such a manner as to admit of use with the least amount of work on the part of the instructor. At first, pulp-samples, together with their respective assays, were secured from the mines, smelters, and public assayers, but this practice did not prove satisfactory. It was not only difficult to secure a sufficiently large supply of material, but it was also impossible to secure the proper assortment required for instructing students. It involved considerable work for the donors to select the samples and furnish a record of the assays, and also for the instructors to examine each pulp and determine its character. Some of the samples did not contain a sufficient quantity of pulp for the student to check his work in case his first assay did not correspond to the record. In order to increase the number of samples and to vary the character of the material, pulp-samples were later mixed with barren rock and with sulphides, but this method also was unsatisfactory and has been discontinued. At present., small lots of ore are secured by gift or purchase from engineers, public assayers, and the managers of mines, mills, and smelters. These lots weigh from 10 to 100 lb. each, and are rarely finer than 0.25 in. in size. The larger samples permit of a careful study by the instructor in order to determine the best method of assaying to be followed. In universities in which assaying is taught the record of the samples should fulfill the following requirements

Nov 1, 1909

By B. C. Allen

Liquid surface tensions of copper and 18 Group IV-A to VIII transition metals (Ti, Zr, Hf, V, Cb, Ta, Mo, W, Re, Ru, Rh, Pd, Os, Ir, Pt, Fe, Ni. Co) have been measured by the static pendant-drop and dynamic drop-weight methods on the same rod sample. The drops were formed by electron-bombardment heating in high vacuum. Application of necessary corrections enabled determination of surface tensions to k2 pct and agreement between methods to * 1 to 4 pct for all the metals studied. Evidence is presented that the liquid surface was well screened by metal vapor, suggesting negligible adsorption of gaseous impurities and that the surface tensions measured are characteristic of the metals involved. Correlations between liquid surface tension and melting point, molar volume, heat of vaporization, and atomic number are presented and discussed. Temperature coefficients of surface tension were calculated using Eötvös' law. SURFACE tension and interface energies of metals are the result of incomplete atomic coordination resulting in a force perpendicular to the boundary, tending to minimize its area. These energies are important in many phases of metallurgy, including microstructure, sintering, joining, electronic emission, and lubrication, which in turn affect many physical and mechanical properties of metals. Liquid surface tension refers to the interface between the liquid and its own vapor or nonreactive atmosphere, and is considered a physical property of the liquid. Since equilibrium shapes can be readily obtained with liquids, the units of surface tension (force per length) and interface energy (energy per area) are interchangeable. Thermo-dynamically, the surface tension ?LV is given by the change in free energy F with surface area A at constant pressure P, temperature T, and composition N: for commercially important refractory metals, vanadium, columbium, tantalum,13,14 molybdenum,14 and tungsten,l5 and none for the rare platinum-group metals and rhenium. Measuring the surface tensions of transition metals is difficult because of their high reactivity and melting points. Of the many techniques available,16-18 the pendant-drop 19-21 and drop-weight methods17,22 are considered superior because they can be modified to eliminate persistent sources of contamination such as supports and capillaries necessary in the popular sessile drop, capillary rise, and maximum-bubble-pressure techniques. The necessary modification is to melt a drop on the tip of a vertical rod, which provides support through a solid of the same composition.13,15 The object of the work was to study the surface-tension behavior of copper and transition metals, having reasonably low vapor pressures. Liquid surface tension of each pure metal was systematically determined by using a combination of the static pendant-drop and dynamic drop-weight methods on the same rod. Liquid drops were formed by electron-bombardment heating in high vacuum. EXPERIMENTAL WORK As indicated in Table I, the metals studied were high purity and generally were obtained in rod form. The exceptions were titanium and zirconium, which were machined from crystal bars, and molybdenum (tot 11, osmium, and ruthenium, which were sintered and arc cast into rods. All the metals were ground or swaged to desired sizes between 1- and 7-mm diam, and centerless ground round and smooth to a finish better than 50 µ in., rms. Each rod was thoroughly cleaned with steel wool, degreased, acid etched, and dried. In a typical run, the rod was vertically clamped in a modified floating-zone electron-bombardment furnace designed after Calverley23 and Carlson.24 The specimen was outgassed and maintained positive at several kilovolts in a dynamic vacuum of 10-5 to 10-7 mm. The bottom end was enclosed by a tantalum pillbox and heated by electrons emitted from a hot concentric tungsten filament mounted on a movable bracket. The bombardment power was slowly raised until melting was observed. Power requirements ranged from 30 w for copper to 1300 w for 4-mm tungsten. The stabilized and out-gassed drop of near-maximum size was photographed at 4. 1X on panchromatic film at desired time inter-

Jan 1, 1963

By Simon T. Johnson

Potential applications for boom tunnelling machines requires reliable assessment of in-situ performance. The majority of existing classification schemes concentrate on the prediction of excavation rate, neglecting the important influence of tool consumption rates. A statistical approach is taken to the analysis of the performance data, which was obtained first-hand through in-situ monitoring, and laboratory testing of representative rock samples. A statistical discrimination technique is used to produce a scheme for the prediction of performance groups, each of which covers a limited range of cutting rate and/or tool consumption rate.

Jan 1, 1984

By John Chipman, Theodore B. Winkler

In order to understand more fully the complexities of the reactions occurring between the liquid steel and the slag in the basic open-hearth steelmaking furnace, investigations in this country and. abroad have turned to laboratory equilibrium studies. This paper is one of a series of reports on investigations being conducted at the Massachusetts Institute of Technology. The experimental work was completed early in 1942. The slag systems found in the basic open hearth are very complex, being made up of at least eight major components and as many others whose effect might be classified as minor. The first two papers of the series, by Fetters and Chipman,l,2 as well as the paper by Taylor and Chip-man,3 dealt with the simplest possible slag system that would resemble those found in the basic ope), hearth—the slag system consisting of CaO-MgO2-SiOz-FeO. (Taylor's rotating induction furnace eliminated the necessity of contamination of the slag by MgO.) Having arrived at some reasonable conclusions regarding the physical chemis- try of the reactions between molten iron and the simple slags at equilibrium, the next step was to investigate more complex slag systems. The major purpose of the present investigation was to determine what factors control the distribution of phosphorus between molten iron and the more complex basic slags at equilibrium, and to what extent these factors are influential. The slags used contained CaO, MgO, SiO2, FeO, Fe2O3, P2O6, MnO, Al2O3 and CaF2, but not all of the slag samples contained all of these components at one time. Review of Literature Although a number of interesting papers have been published on the subject of dephosphorization of an iron bath, there are as yet no results from laboratory studies that give thoroughly reliable information on the dephosphorization reaction. Even for the supposedly simple Fe-O-P system involving iron-phosphorus melts and iron oxide-iron phosphate slags, the experimental results are contradictory and no formulas have been established that adequately fit the equilibrium conditions. The Fe-O-P system has been studied by Schackmann and Krings,4 von Samson-Himmelstjerna,6 Oelsen and Maetz,6 Bischof and Maurer,7 Diepschlag and Schürmann,8 and Herty,9 and the results of their investigations appear in Table I. A number of different equilibrium constants and distribution . Ratios

Jan 1, 1947

By Theodore B. Winkler, John Chipman

In order to understand more fully the complexities of the reactions occurring between the liquid steel and the slag in the basic open-hearth steelmaking furnace, investigations in this country and. abroad have turned to laboratory equilibrium studies. This paper is one of a series of reports on investigations being conducted at the Massachusetts Institute of Technology. The experimental work was completed early in 1942. The slag systems found in the basic open hearth are very complex, being made up of at least eight major components and as many others whose effect might be classified as minor. The first two papers of the series, by Fetters and Chipman,l,2 as well as the paper by Taylor and Chip-man,3 dealt with the simplest possible slag system that would resemble those found in the basic ope), hearth—the slag system consisting of CaO-MgO2-SiOz-FeO. (Taylor's rotating induction furnace eliminated the necessity of contamination of the slag by MgO.) Having arrived at some reasonable conclusions regarding the physical chemis- try of the reactions between molten iron and the simple slags at equilibrium, the next step was to investigate more complex slag systems. The major purpose of the present investigation was to determine what factors control the distribution of phosphorus between molten iron and the more complex basic slags at equilibrium, and to what extent these factors are influential. The slags used contained CaO, MgO, SiO2, FeO, Fe2O3, P2O6, MnO, Al2O3 and CaF2, but not all of the slag samples contained all of these components at one time. Review of Literature Although a number of interesting papers have been published on the subject of dephosphorization of an iron bath, there are as yet no results from laboratory studies that give thoroughly reliable information on the dephosphorization reaction. Even for the supposedly simple Fe-O-P system involving iron-phosphorus melts and iron oxide-iron phosphate slags, the experimental results are contradictory and no formulas have been established that adequately fit the equilibrium conditions. The Fe-O-P system has been studied by Schackmann and Krings,4 von Samson-Himmelstjerna,6 Oelsen and Maetz,6 Bischof and Maurer,7 Diepschlag and Schürmann,8 and Herty,9 and the results of their investigations appear in Table I. A number of different equilibrium constants and distribution . Ratios

Jan 1, 1947

By H. M. Morse

This report covers the period from Jan. I, 1943 to Dec. 31, 1943. During the year, II2 wells were drilled in Mississippi, as foilows: wildcats drilled and abandoned, 54; wildcats producing oil, 4; oil wells drilled in oil fields, 26; oil wells drilled in fields, dry and abandoned, 10; sulphur-test wells drilled, 14; salt-water-disposal wells, 3; core tests, I. Prospecting Geophysical work in Mississippi during 1943 amounted to 1127 crew weeks, divided as follows: reflection seismograph, 809 weeks; gravity meter, 285; magnotometer, 30; torsion balance, 3. A considerable amount of core drilling was done over a large part of the state. The complete data on this activity are not available at the present time. Salt Domes To date, the following salt domes have been discovered in Mississippi: Midway, Edwards, Glass, Newman, Tatum, Oak-vale, Kings, Halifax, D'Lo, Hazlehurst, Byrd, Leedo, Prentiss, Carson, Moselle, Monticello, Ruth, Keno, Taylorsville. New Oil Fields Lincoln County.—On March 10, 1943, the California Company completed its Smith No. I in sec. 4, T. 7 N., R. 7 E., Lincoln County, as an oil well and produced 29 bbl. of 25" gravity oil in 24 hr. through a fi-in. choke. Two outpost wells have been drilled in this area by the California Company, and both have been abandoned as dry holes. Madison County. —Love Petroleum Co. completed its J. R. Anderson No. 2, sec. 2, T. 8 N., R. I W., Madison County, on Sept. 7, 1943. This well produced 135 bbl. of approximately 30" gravity- oil in 24 hr. through a )/4-in. choke. The production comes from a sand or porosity in the upper part of the Chalk formation of the Cretaceous age. Adams County.—The California Company drilled its National Gasoline Co. of Louisiana No. I in sec. 52, T. 7 N., R. I W., to a total depth of 10,383 ft., and at 10,280 ft, it perforated and obtained gas and a condensate. The well had several showings in the Wilcox of the Eocene age. Several of these showings were tested and the well finally was completed at 5888 ft. on Oct. 6, 1943, producing 44" gravity oil in the second sand in this formation. No other wells were completed in this field during the year. However, a number of wells are contemplated in the near future, and locations have been staked by the California Company. The Oklahoma Pipe Line Co. will market the oil through its pipe-line facilities. Wayne County.—The Gulf Refining Co. drilled Davis No. I in sec. 2, T. 9 N., R. 9 W. in Wayne County. After several stem tests 545'-in. casing was set at 6850 ft. and production was obtained in the so-called Massive Sand of the Lower Tuscaloosa. The well produced 359 bbl. of oil in 24 hr., and it Was completed on Oct. 4, 1943. Other locations have been staked ill this area and probably will be drilled in 1944 by

Jan 1, 1944

By H. M. Morse

This report covers the period from Jan. I, 1943 to Dec. 31, 1943. During the year, II2 wells were drilled in Mississippi, as foilows: wildcats drilled and abandoned, 54; wildcats producing oil, 4; oil wells drilled in oil fields, 26; oil wells drilled in fields, dry and abandoned, 10; sulphur-test wells drilled, 14; salt-water-disposal wells, 3; core tests, I. Prospecting Geophysical work in Mississippi during 1943 amounted to 1127 crew weeks, divided as follows: reflection seismograph, 809 weeks; gravity meter, 285; magnotometer, 30; torsion balance, 3. A considerable amount of core drilling was done over a large part of the state. The complete data on this activity are not available at the present time. Salt Domes To date, the following salt domes have been discovered in Mississippi: Midway, Edwards, Glass, Newman, Tatum, Oak-vale, Kings, Halifax, D'Lo, Hazlehurst, Byrd, Leedo, Prentiss, Carson, Moselle, Monticello, Ruth, Keno, Taylorsville. New Oil Fields Lincoln County.—On March 10, 1943, the California Company completed its Smith No. I in sec. 4, T. 7 N., R. 7 E., Lincoln County, as an oil well and produced 29 bbl. of 25" gravity oil in 24 hr. through a fi-in. choke. Two outpost wells have been drilled in this area by the California Company, and both have been abandoned as dry holes. Madison County. —Love Petroleum Co. completed its J. R. Anderson No. 2, sec. 2, T. 8 N., R. I W., Madison County, on Sept. 7, 1943. This well produced 135 bbl. of approximately 30" gravity- oil in 24 hr. through a )/4-in. choke. The production comes from a sand or porosity in the upper part of the Chalk formation of the Cretaceous age. Adams County.—The California Company drilled its National Gasoline Co. of Louisiana No. I in sec. 52, T. 7 N., R. I W., to a total depth of 10,383 ft., and at 10,280 ft, it perforated and obtained gas and a condensate. The well had several showings in the Wilcox of the Eocene age. Several of these showings were tested and the well finally was completed at 5888 ft. on Oct. 6, 1943, producing 44" gravity oil in the second sand in this formation. No other wells were completed in this field during the year. However, a number of wells are contemplated in the near future, and locations have been staked by the California Company. The Oklahoma Pipe Line Co. will market the oil through its pipe-line facilities. Wayne County.—The Gulf Refining Co. drilled Davis No. I in sec. 2, T. 9 N., R. 9 W. in Wayne County. After several stem tests 545'-in. casing was set at 6850 ft. and production was obtained in the so-called Massive Sand of the Lower Tuscaloosa. The well produced 359 bbl. of oil in 24 hr., and it Was completed on Oct. 4, 1943. Other locations have been staked ill this area and probably will be drilled in 1944 by

Jan 1, 1944

By Donald K. Weaver

THERE have been eight different oil zones identified and produced at Santa Fe Springs, of which three or four are in turn divided into two or three parts. These zones are, from top to bottom, the Foix, difference of opinion over this nomenclature, with reference to the different zones referred to as Clark, it has no particular bearing on the water problems. Each of these oil zones has had waters of varying salinity associated with it, either within or at the bottom of the 'zone. Table 1 is a tabulation of the zones, their maximum thicknesses, salinity and heads of various waters. Surface waters are fresh, and of high head, giving artesian flow in some instances.

Jan 1, 1930

By E. A. Gulbransen, W. S. Wysong, K. Andrew

The reaction of carbon in solid solution in a metal with the surface oxide fim on many metals may be inferred from thermo-dynamic calculations for high vacua and high temperature conditions. Holm has recently shown that oxide films may be removed from ferrous materials by heating in a vacuum at high temperatures and that carbon is the essential element in the reaction. considerable work has been described in the literature on the de-carburization reaction. Several general references may been 2,3,4 However, the nature of the mechanism involved in the decarburization is not well understood. Our interest in this reaction resulted from many attempts to degas and to reduce by pure and dry hydrogen the surface oxides on strips of various types Of chrome-nickel alloys. Some of the early experiments On the behavior Of '3 pct chrome-iron in vacua of the order of 5 X lo' mm and at a temperature Of 600°C have been reported.5 These experi-merits showed a 'low reaction with the residual Oxygen Or water vapor in the system and no reaction with hydrogen. This is in accord with thermodynamic data which would lead to the prediction that it is extremely difficult to maintain a hydrogen atmosphere at 600' C pure enough to reduce Crz03 formed On the surface. The crystal structure of the superficial oxide film formed on 13 pct chrome- iron and Nichrome V has been investigated in the thin film range by Gulbransenr Phelps and Hickman,' and shown to be "203. It Was surprising to us to note that when a specimen of Nichrome V containing approximately 80 pet nicke1 and 20 pet chromium was heated to 850°C in a high vacuum, the specimen lost weight. The rate Of weight loss was very temperature sensitive. A study of this reaction in vacua and in a hydrogen atmosphere is the subject of this communication. Type Reactions Let us consider the various reactions which may occur when a metal is heated in vacua, in a hydrogen atmosphere, or in an oxygen atmosphere. The number and kind of reactions will depend upon the chemical nature of the metal, its alloying constituents and the location of the alloying constituents. The metals used in this study are chrome-nickel alloys of the heater type, They consist essentially of chromium, nickel and iron, small amounts of carbon, silicon and manganese and traces of zirconium, calcium, aluminum and magnesium. The trace elements are added to improve the lifetime and other characteristics of the alloy when used as a heater. Seven of the more important reactions with which we are going to be concerned here are as follows: 1. Metal . (gas) F? metal + gas — degassing of the metal 2. zM(s) + y }i Oi(g) M MIOu(s) -oxidation

Jan 1, 1949

By Charles Maier

PART I DENSITY AND ENERGY CHANGES IN COLD-WORKED COPPER IT has long been supposed that when crystalline materials are com-minuted the energy used in the production of increasingly smaller grain sizes is not entirely dissipated as heat but that a certain portion is "stored" as a part of the internal energy of the material. This portion usually has been called the "surface energy" of the particles. The practical interest of the Bureau of Mines in this subject in connection with the energy requirements of crushing processes has led' to the author's attempt to measure the "stored" energy in finely divided calcite by heat-of-solution methods1. The experiments on calcite showed that "storage" of energy could not be proved for this material, because fine grinding caused a lack of chem-ical homogeneity evidenced by loss of carbon dioxide and subsequent adsorption of water on the surfaces of the calcite particles. When thermochemical correction was made for composition changes the cor-rected heat of solution was less for fine material than for coarse. Con-tinuation of the experimental work into the problem of comparing work and heat in the deformation of metallic crystals, where the calorimetric difficulties were less, showed, however, that in the case of copper and aluminum a real discrepancy between work and heat could be shown. Similar results had previously been obtained by Farren and Taylor2 and Hort3 and more or less simultaneously with the author's work by

Jan 1, 1936

By John Gjers

Being on a visit to your great and prosperous country, and having been favored with an invitation to attend this meeting of your Institute, the author has been requested by your Secretary to give a short account of his invention of the " soaking-pit," which he has great pleasure in doing. The object of the soaking-pit is the rolling of steel ingots with their own initial heat, that is, to supply the missing link in that chain of metallurgical operations which Sir Henry Bessemer began in 1857, when he proved how it was possible to produce malleable iron or steel direct from the fluid cast-iron out of the blast-furnace, without any further direct use of fuel. The great Bessemer invention has revolutionized iron and steelmaking throughout the world; but it stopped short at producing the ingot, which, it was found, had afterwards to be heated in a furnace to enable it to be rolled or hammered; and it is only lately, twenty-five years after Mr. Bessemer's announcement, that the author of this paper has been able to show that furnacing can be dispensed with, and that it is practicable to roll a steel ingot into say a bloom, a rail, or a billet, with its own initial heat. It has no doubt suggested itself to many that there ought to be heat enough in the ingot just cast, for the purpose of rolling; and from time to time attempts have been made to utilize this heat; but such attempts always ending in failure, it became a settled opinion in the trade that it could not be done—an opinion which the author is aware that your late lamented countryman, Mr. Holley, than whom there was none more conversant with Bessemer steel-making, also entertained. But settled opinions sometimes prove to be great fallacies. As an instance, it is not many years since the opinion prevailed in the trade that steel ingots could not be rolled successfully, that is, so as to make good rails, unless they were first allowed to get quite cold, and afterwards heated. No greater boon was ever conferred on the

Jan 1, 1885

By Ben-Zion Weiss, Melvin R. Meyerson

Chromium diffusion coatings on commercial Armco iron lead to carbide precipitation at the grain boundaries in and below the coatings. High compressive stresses are introduced into the coating and, as a result, tensile stresses are introduced into the base material below the coating. In coated samples, fatigue cracks form at the grain boundaries below the coating after only a limited portion of the total lifetime (5 to 10 pct). Residual tensile stresses and a stress concentration caused by precipitated carbides seems to be responsible for early crack nucleation. Stage I of Propagation may be divided into two substages: I-a in which the crack Propagates along grain boundaries, and I-b in which the crack propagates along slip boundaries according to a shear mode. In uncoated samples, the cracks form at slip bands after 40 to 50 pct of the total lifetime. In coated samples the Propagation process takes longer than in uncoated samples because of the moderate rate of crack extension until the crack breaks through the coating. The chromium-diffusion coating causes little if any increase in fatigue life. CHROMIUM diffusion is one of the most popular processes used to apply coatings to iron alloys. This popularity stems from the fact that the diffusion treatment is comparatively easy to carry out, and it improves certain surface properties such as corrosion and wear resistance as well as some other properties. Very little effort has been devoted to the investigation of the effect of chromium-diffusion coatings on mechanical properties and particularly on fatigue properties. Since the chromium coating usually represents a small fraction of the total volume of the base material it is generally assumed that the macro properties are dependent principally on the base material rather than the coating. Insofar as fatigue is concerned, there are indications that the fatigue life of the chromium coating is not less than that of the basic material and the fatigue properties are generally not reduced by it.' But chromium diffusion causes drastic structural and chemical changes in the region of the material surface2-4 which introduce additional residual stresses. Such changes must affect fatigue crack nucleation and may sometimes affect the initial stages of propagation. Furthermore, it is conceivable that the secondary stages of the crack propagation could be influenced by some irreversible structural changes in the core of the material, which stem from the long-time heat treatment at high temperatures required to apply the coating. This paper analyses the structural and compositional changes produced in commercial Armco iron by a chromium-diffusion coating and the effect of the coating on fatigue crack initiation and propagation. EXPERIMENTAL PROCEDURES The investigations were carried out with commercial Armco iron. The chemical composition of the iron, the number of specimens tested, the grain size produced during chromizing and heat treating, and the thickness and microhardness of the chromized layers are shown in Table I. Samples were chromized by a gas diffusion process. The temperature and time of the diffusion coating process were chosen according to a previous grain growth study. It had been found that at a temperature of 970°C and a holding time of between 3 and 9 hr there are practically no changes in grain size. To describe the grain size more accurately the ASTM method5 was supplemented by a statistical analysis of the mean volume diameter as outlined by Fullman6 and The The mean volume diameter was deter- mined from D = p/2m where D is the mean volume diameter, and m is the mean reciprocal value of grain diameters as seen on the micrograph. The shape and the size of the asymmetrical sample, see Fig. 1, were chosen so as to facilitate the study of fatigue crack initiation. Before coating, the samples were machined and the surface of the groove was polished. After chromizing, the two side surfaces were machined and polished so as to retain the coating only on the top surface of the groove. Residual stress in the chromized layer was measured on the top of the grooved section of the specimen after the diffusion process. The inclined incident X-ray beam procedure was used.9'10 The computations were performed with the initial assumption of a zero surface normal stress component. An electron microprobe analyzer was used to obtain the relative amounts of chromium and iron con-

Jan 1, 1970

By L. S. Darken

The manufacture and treatment of metals comprises operations whose effectiveness depends in large measure upon diffusion phenomena. The significance of such phenomena has, for a few simple cases, long been understood, but in more complex cases it has not been adequately recognized. This paper presents a mathematical analysis of some of the cases in which diffusion leads to the formation of a new phase within the metal, and this analysis provides a basis for interpreting quantitatively many apparently diverse experimental observations recorded in the literature, some of which are outlined in the following pages. OBservt1ons Recorded in Literature An outstanding instance is the general type of phenomenon in which diffusion of an element into an alloy is followed by a phase change, which most frequently is a reaction (precipitation) of the diffusing element with one or more components of the alloy to form a compound. Thus in certain alloys heated in contact with oxygen not only the usual oxide scale appears but, in addition, beneath the surface, a well-defined zone in which free oxide particles are dispersed with notabIe uniformity. This zone, commonly referred to as the subscale or zone of internal oxidation, is remarkable in that the visible boundary between it and the unaltered metal is usually sharp. Such a subscale, which appears to have been recognized first in oxidized copper alloys, has been described and studied by C. S. Smith,l by Rhines,2 and by Rhines, Johnson and Anderson;3 but it appears also in other alloys when they are exposed to conditions that bring about the precipitation of some compound, not necessarily an oxide. Another clear case of this same kind is the diffusion of carbon into a steel containing an element such as molybdenum, chromium, vanadium or tungsten, whose carbide is less soluble in iron than iron carbide, the result being that some part of that element is precipitated as a dispersed carbide. A similar phenomenon may occur on the welding of two alloys each of which contains one of a pair of elements that react to form a compound or a new phase of any sort. But in addition to the precipitation of a compound formed from the diffusing element, other effects may result merely from the presence of the diffusing element. For instance, if homogeneous austenite, nearly saturated with respect to carbon, is heated in contact with silicon in the absence of oxygen, one would expect to find, behind the several iron-silicon phases analogous to a scale, a zone of austenite containing dispersed carbide, because of the fact that silicon decreases the solubility of carbon in iron. As still another example, oxidation of an alloy may result in diffusion toward the surface of one or more of the constituents; for instance, during oxidation of a steel containing an element such as "copper, which is less prone to oxidation than iron, there is a notable enrichment of copper just beneath the scale-metal interface. AS an example of a yet more

Jan 1, 1942

By L. S. Darken

The manufacture and treatment of metals comprises operations whose effectiveness depends in large measure upon diffusion phenomena. The significance of such phenomena has, for a few simple cases, long been understood, but in more complex cases it has not been adequately recognized. This paper presents a mathematical analysis of some of the cases in which diffusion leads to the formation of a new phase within the metal, and this analysis provides a basis for interpreting quantitatively many apparently diverse experimental observations recorded in the literature, some of which are outlined in the following pages. OBservt1ons Recorded in Literature An outstanding instance is the general type of phenomenon in which diffusion of an element into an alloy is followed by a phase change, which most frequently is a reaction (precipitation) of the diffusing element with one or more components of the alloy to form a compound. Thus in certain alloys heated in contact with oxygen not only the usual oxide scale appears but, in addition, beneath the surface, a well-defined zone in which free oxide particles are dispersed with notabIe uniformity. This zone, commonly referred to as the subscale or zone of internal oxidation, is remarkable in that the visible boundary between it and the unaltered metal is usually sharp. Such a subscale, which appears to have been recognized first in oxidized copper alloys, has been described and studied by C. S. Smith,l by Rhines,2 and by Rhines, Johnson and Anderson;3 but it appears also in other alloys when they are exposed to conditions that bring about the precipitation of some compound, not necessarily an oxide. Another clear case of this same kind is the diffusion of carbon into a steel containing an element such as molybdenum, chromium, vanadium or tungsten, whose carbide is less soluble in iron than iron carbide, the result being that some part of that element is precipitated as a dispersed carbide. A similar phenomenon may occur on the welding of two alloys each of which contains one of a pair of elements that react to form a compound or a new phase of any sort. But in addition to the precipitation of a compound formed from the diffusing element, other effects may result merely from the presence of the diffusing element. For instance, if homogeneous austenite, nearly saturated with respect to carbon, is heated in contact with silicon in the absence of oxygen, one would expect to find, behind the several iron-silicon phases analogous to a scale, a zone of austenite containing dispersed carbide, because of the fact that silicon decreases the solubility of carbon in iron. As still another example, oxidation of an alloy may result in diffusion toward the surface of one or more of the constituents; for instance, during oxidation of a steel containing an element such as "copper, which is less prone to oxidation than iron, there is a notable enrichment of copper just beneath the scale-metal interface. AS an example of a yet more

Jan 1, 1942

By C. E. Sims

THE following presentation is more a summation of observations made and conclusions drawn over a period of three to four years than a report of experiments made with a definite objective. Tests were made, of course, to verify hypotheses, but the large mass of data was collected incidental to other work. Lack of space forbids the presentation of more than a few of those data. On the other hand, it is unfortunate that some of the most illustrative examples are not available. The work is admit¬tedly incomplete but is presented in the hope that it will stimulate further work along a similar line. The answers to many of the questions left unanswered by this paper will be found only after long and painstaking study, such as is scarcely possible in a commercial laboratory where problems of immediate importance consume most of the time. It is also hoped that this study will in some measure throw light on some of the dark spots of steelmaking, and help to clarify some of the annoyingly vague references to "good practice." Only cast steel was studied and the conclusions apply to cast steel, but it is the authors' opinion that the quality of rolled or forged steel is largely dependent on the quality of the ingot, which is a casting. Although this discussion deals almost entirely with inclusions, it is important that the reader understand that only those natural inclusions which owe their origin to the solubility of certain materials in steel and to the chemical reactions of steelmaking are considered. Accidental inclusions, such as entrapped particles of slag, nozzle, runner, or mold are outside its province and are not considered. Such accidental inclusions are always dangerous and should be carefully avoided.

Jan 1, 1932

By W. O. Philbrook, K. Natesan

A mathematical model was derived for the temperature change in a particle undergoing heterogeneous chemical reaction and heal exchange with a stream of fluid. The model has been applied specifically to the exothermic oxidation of spherical particles of zinc sulfide. Very good agreement was obtained between the theoretical prediclion and experimental observation. It was found that at no stage of the reaction was the particle subjected to a state of thermal instability. In studies of gas-solid reactions, it is generally assumed that the gaseous and the solid phases are at the same temperature throughout the reaction period. This is not strictly true since most of the reactions are either exothermic or endothermic in nature. This paper deals only with heterogeneous gas-solid reactions of noncatalytic type. In the case of exothermic reactions (e.g., roasting of sulfides), there may result an increase in temperature of the particle due to the release of the heat of reaction, and this increase in temperature may enhance the reaction rate and thus cause further release of heat. Such a "spiralling" effect may lead to a thermally unstable situation within the particle. On the other hand, in the case of endothermic reactions (e.g., calcination of limestone), there may occur a decrease in temperature of the particle as the reaction proceeds, leading to a virtual "quenching" of the reaction front. A general discussion of autothermic processes with emphasis on properties and reactor design is given by Van Heerden. 1 Levesque and cubicciotti 2 observed self heating of the sample in the oxidation of thorium. Anous et al. 3 observed self cooling of the sample in their dehydration studies on chrome alum. Cannon and Denbigh, 4 and Ong et al.5 reported self heating of the sample in their studies of the kinetics of oxidation of zinc sulfide. A typical plot of heat generation and heat loss rates with reaction temperature is shown in Fig. 1.'14 The Sigmoid curve represents the heat generation rate while the straight lines represent the heat loss rate. The main objectives of this analysis are to estimate the temperature increase of a single particle undergoing an exothermic reaction and to study the possibility of a thermally unstable situation within the particle. Also, a study of the dependence of the tempera- ture increase on different process variables has been attempted. A "she ll-by-shell" method has been proposed to analyze the problem. The shells may be made as small as necessary, and equations may be set up for heat transfer by various mechanisms. Such equations will have to be solved for each shell, with the boundary conditions for ith shell being obtained from the (i - 1)th shell, using a high speed digital computer. The oxidation of spherical particles of zinc sulfide is considered for this analysis, but the treatment is general enough to be applicable to other reactions and particle shapes. The oxidation reaction can be written as AH =« -115 kcal/mole ZnS [1] Such a reaction has been found to proceed in a topo-chemical manner; i.e., as the reaction proceeds, a progressively thicker outer shell of zinc oxide is formed, while the inner core of unreacted sulfide decreases. It has been found experimentally, both in the present work and in the previous investigations,4-6 that the particle retains its original dimensions. Therefore, at any given time, the particle may be

Jan 1, 1970

By John E. Murphy, Ernest L. Ohle

Hematite-magnetite ore bodies at Iron Mountain, Missouri, have produced nearly 9 million tons of iron ore concentrates since 1844. The ore minerals occur principally as open-space filling in fractured and brecciated andesite porphyry with very minor replacement of the wall rocks. The enclosing rocks are Precambrian in age and consist of a series of dacite, rhyolite, and andesite flows aggregating about 2000 feet in thickness. All of the ore is in andesite and the mineralization is Precambrian in age. The shape of the ore bodies, the breccia character of the ore, and the gangue mineralogy are believed to be unique. One of the two main ore bodies is crudely dome-shaped with a tendency for development of concentric mineralized shells; the other is an elongated lense in plan but hook-shaped in cross section. Both have strong linear elements striking northeast, east-west, or northwest. Various modes of origin for the structures and for the tension breccias have been suggested, but none is completely satisfactory. Hematite is the main ore mineral; magnetite is subordinate. Important gangue minerals are andradite, quartz, calcite, actinolite, apatite, epidote, and chlorite. Although some evidence favors injection of an iron-rich melt, other evidence suggests ore formation by a high temperature, water-rich solution.

Jan 1, 1968