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By J. H. Westbrook

UNTIL very recently the development of high temperature alloys has been strictly empirical. It is, in fact, a great tribute to the intuition, perseverance, and industry of the practicing metallurgists of this country and abroad that the amazing increases in gas turbine service temperature over the past 15 years have been achieved with so little fundamental knowledge. The result of this development has been the realization of successful but highly complex alloys possessing five, six, or more alloying elements and correspondingly complex microstructures. Within the last few years, considerable effort has been devoted to the identification of the secondary phases in these alloys and to the correlation of the presence or absence of such phases with alloy properties. Little attention, however, has been given the problem of identification of the mechanism (s) by which such phases enhance the properties of the alloy and especially to the assessment of the particular properties of the secondary phase (either in- trinsic or relative to the matrix phase) which are basically responsible for the improvement. Conceivable mechanisms which might apply include dispersion hardening and precipitation hardening. In both cases geometrical factors—particle size, dispersion, volume fraction, etc.—and agglomeration re-

Jan 1, 1958

By Walter Crafts, D. C. Hilty

The liquidus diagram for the iron field of the Fe-S-O system has been derived experimentally. The solubility of oxygen in molten Fe-S alloys has been measured at several temperatures and found first to decrease slightly and then increase rapidly with increasing sulphur content. IT is well-known that the types, distribution, and amount of inclusions in any given steel are closely allied with the oxygen and sulphur contents of the metal, so that the term "deoxidation" as conventionally applied in steelmaking refers not only to the control of oxygen and oxide inclusions but to collateral modification of sulphide inclusions as well. Inclusions commonly occur in steel as mixtures of oxides and sulphides, sometimes closely associated and sometimes apparently completely divorced. Their effects on the properties of the metal may vary widely depending on their types and distribution as well as on their quantity. The mechanism by which inclusions form, however, and the means for controlling it are exceedingly complex and not well understood. Nevertheless, as described by Benedicts and Lofquist' and by Wentrup' all oxide and sulphide inclusions, excluding mechanically entrained matter, must result from specific modifications of the basic equilibria of the Fe-S-O system. In an investigation of the mechanism of deoxidation and inclusion formation being carried out at the Union Carbide and Carbon Research Laboratories, it became evident that quantitative data for the fundamental Fe-S-O system were essential to a better understanding of the problem. Consequently, the liquidus surface of the portion of the Fe-S-O diagram of interest in steelmaking has been determined, and the solubility of oxygen in liquid iron containing sulphur has been measured. Fe-S-O Diagram The portion of the Fe-S-O diagram of specific interest in steelmaking is the Fe-FeS-FeO corner. Of the contiguous binary diagrams for this partial system, only those for Fe-FeO and Fe-FeS are known with reasonable certainty.3 Several attempts to derive the FeO-FeS diagram have been made, chief among them being the work of Giani as reported by Oberhoffer,4 and, more recently, that of Vogel and Fulling." Although both Giani and Vogel and Fulling published diagrams for the FeO-FeS system, their observations indicated that the oxide component approximated Fe3O4 rather than FeO, so that there is doubt whether the system is truly binary. Benedicts and Lofquist and also Wentrup published qualitative sketches of the ternary diagram based on the assumption that it was of the type described by Marsh for a ternary system in which two of the contiguous binary systems are simple eutectic systems and the third exhibits a solubility gap in the liquid. Apparently, however, the only previous effort to establish the diagram experimentally was that of Vogel and Fülling whose results are reproduced in Fig. 1. Although defining approximately the limits of the miscibility gap and the location of the ternary eutectic, point E in Fig. I, Vogel and Fülling's diagram must be considered only semiquantitative. It was derived from a limited number of observations mainly along two quasi-binary sections, and the directions of the tie-lines and the location of the critical point, K in Fig. 1, were estimated by computation. Experimental Procedure The experimental technique employed for the present investigation involved melting mixtures of ferrous sulphide and ferric oxide in contact with iron. Since it was considered that in this part of the system the vapor pressures of sulphur and SO, are so low that they would not affect the results significantly, the melting was carried out in a current of argon to sweep out products of any initial re-

Jan 1, 1953

By P. W. Neurath

IN recent years the domain theory of ferromag-netism has been put on a sound experimental and theoretical basis. But its application to one of the most widely used high quality magnetic materials, the cold-rolled grain-oriented 3 pct Si-Fe used in transformer cores, has been rather difficult because of the complexity of the domain structure of the poly crystalline sheet material. This paper presents some experimental data for this material, showing the relation between plastic and elastic stresses, 60-cycle watt losses, and the domain structure as observed visually. Only a very tentative qualitative explanation of the effects will be attempted. Some initial results were reported earlier.'

Jan 1, 1957

By F. Lynwood Garrison

There is probably no subject for study in the metallurgy of iron and steel of greater interest than the effect of manganese upon the properties of iron. Some of the peculiarities of iron and steel containing appreciable quantities of manganese were observed many years ago by Heath, Robert Mushet, and others; but it was not until the introduction of the Bessemer process, when a demand was created for large quantities of iron-manganese alloys, that such compounds of iron and manganese became articles of commerce. Since that time the demand for these alloys has steadily increased, the use of ferro-manganese not only becoming an absolute necessity in the ordinary Bessemer practice, but also essential to the manufacture of open-hearth, crucible steel and steel castings; in fact it is the only source of supply for all the manganese used in metallurgical opera-

Jan 1, 1893

By Richard S. McCaffery, Morrison B. Yung

While assaying some copper carbonate ore from the Frazer claims, Similakameen, B. C., I noticed that on parting the gold button a deep orange solution was formed. The button gave off pink bands in the nitric acid, which became deep orange at a short distance from it; and as it traveled over the surface of the porcelain dish, it left a deep orange track behind. As the button brightened in the cupel, it appeared to have a bronze color; but I have since found that when amarillium is in large excess of the gold, the button is a very dark gray. The button parted easily. To the orange solution I added a salt (NaCl) solution, shook in a silver testbottle, and filtered. With H2S I obtained a precipitate, which I supposed due to platinum. However, on further tests, it did

Jan 1, 1903

By Ivan E. Goodner, Charles H. Fulton

The subject of the constitution of copper-iron mattes has received considerable attention in recent years by Keller,' Belles,2 Hofman,3 and Gibb and Philp.4 Still more recently Friedrich, Röntgen, Wiedmann, Heyn and Bauer, and Leroux have published, in some instances, elaborate researches on the various systems of the sulphides, and the snlphides and their respective metals, which enter into the constitution of mattes, and have added very greatly to the knowledge of the subject. The work of Friedrich has been especially fruitful. But to' date no effort has been made to correlate the data obtained in the latter researches and apply them to the study of the product called " matte," which is made in such large quantities by copper- and lead-smelters. In this paper we propose to determine, by metallographic and chemical means, the constitution of copper-iron and copper-lead-iron mattes in the light of the recent data above mentioned. We do not discuss copper-nickel mattes or speisses (artificial arsenides). The paper is divided into three sections: I. A review and discussion of the various binary systems of the metallic sulphides, and the binary systems of various metals and their respective sulphides entering into the constitution of mattes; also a discussion of the physical properties of these sulphides. II. A description of the results obtained from the chemical and microscopic examinations of the samples of copper-iron and copper-lead-iron matte obtained from various plants.

Jan 1, 1909

By A. T. Tye

REGARDING the results of preferential flotation at Cananea, Weinig has stated that "The concentrating mill of the Cananea Consolidated Copper Company at Cananea, Mexico, furnishes an excellent example of modern flotation practice. The complete figures are given because they present so forcibly the advantages of modern selective flotation."' L. 0. Howard notes that "Perhaps the outstanding example so far published of improvements in results through the use of selective flotation is that at Cananea, Mexico."2 The following notes indicate the conditions under which the results were obtained at Cananea; also the effect of preferential flotation at the concentrator and at the smelter. In the majority of cases the full benefit of selective flotation is not fully realized, as the concentrates are shipped from the mill to smelters owned by other companies. The saving made at a certain concentrator by this method of flotation may be well understood but the saving resulting at the smelter from the results of preferential flotation at the mill is not so apparent, as the data are contained in the smelting records of some other company. Even at the smelter the great gains following preferential flotation may not be noted, as a variety of ores and concentrates from various sources are received and the difference from the changed concentrator operations of a certain mill may be obscured. As noted by Professor Weinig and Professor Howard, the results obtained at Cananea brought about a veritable metallurgical revolution at the smelter.

Jan 1, 1927

By D. J. Weintritt, J. C. Cowan

Methods of studying oilfield mineral .scale deposition in the laboratory do not work for barium sulfate because only small nonadhering crystals ore formed. On the other hand, barium sulfate scale found in down-hole or surface equipment is strongly adhering and may contain very large crystals. Results suggest that most of the difference derives from the extremely low .solubility of barium sulfate. Firm adherence of scale and the consistent development of oriented crystals 100 microns and larger suggest a relationship between scale adherence and crysta1 growth. Data from this study indicate some reasons for barium sulfate's occurring as a deposit in oilfield waters. The unique characteristics as well as the associative properties of barium sulfate scale as related to calcium carbonate and calcium sulfate ere shown. INTRODUCTION The first observed deposition of barium sulfate scale in oilfield production equipment is unknown but probably coincides closely with the beginnings of the oil industry itself. Moore' described barite oolites in some producing wells in the Saratoga field, Tex., in 1914. Currently, positive identification of barium sulfate deposition is recorded in most of the major oil-producing areas of the United States. As efforts continue to identify the composition and functions of the materials found in scale deposits, the geographic and economic importance of the part played by barium sulfate will become even more important. This belief is based on the following Facts. 1. Many oil fields in the U.S. are in or entering their mature phase and the volume of produced water is increasing; thus, the cumulative effects of low-solubility minerals become more significant. 2. Secondary recovery techniques and increased emphasis on waste disposal systems require controlling the behavior of all constituents of water to prevent formation plugging. 3. The more general use of instrumental analysis has reduced the time and improved the accuracy of complete scale and water analysis. 4. Once formed, barium sulfate scale is resistant to present methods of chemical removal; therefore, costly mechanical methods are necessary. Thus, new methods of prevention and control will require specialized chemical techniques and better knowledge of the causes of scaling. Consider the results of some simulated field deposition studies illustrating this need (Fig. 1). The studies utilized a Scale Deposition Test Cell* and each coupon was exposed to 8,000 ml of a 300 me/liter solution of the various types of mineral scale. All tests were conducted at 140F. Only the calcium sulfate and calcium carbonate deposited scale. The solution containing 300 me/liter of barium sulfate exhibited copious amounts of precipitate, but none of the precipitate adhered. The fluids from the effluents were also allowed to impinge on glass slides. Fig. 1 shows the relative adherence of the three types of scale on unetched glass. The barium sulfate failed to deposit in the same manner as the calcium carbonate and calcium sulfate solutions.

By Thomas J. Crocker, Galen G. Waddell, Eugene H. Skinner

This paper describes a method of measuring initial and long-term deformations which occur in the medium surrounding mine accessways, and discusses the importance of this type of measurement in assessing support-problem areas. Delineated are (1) description of the rock-deformation monitoring equipment, (2) results of two field tests which monitored rock deformation around 4-foot-diameter raise bores, and (3) a numerical-analysis (finite-element) technique to correlate theoretical with experimental results. Instrumentation developed provided the sensitivity and resolution needed to measure rock deformation around a full-scale raise bore during excavation. Results of the tests conducted at the Lucky Friday mine, Mullan, Idaho, show the relationships between (a) de- formation vs. time, and (b) deformation vs. bit progress. Based on theoretical evaluation of the initial deformation, the medium appeared to behave elastically. Using an estimated field stress of 5,500 psi and Poisson's ratio of 0.20, the gross modulus of elasticity of the rock was calculated to range from 3.15 to 6.0 x 106 psi (with one outlier which was determined to be >12 x l06 psi).

Jan 1, 1971

By E. C. Harder, D. F. Hewitt

Since early in 1916, when it became apparent that the steel industry of the United States could not depend for the duration of the war on several important foreign sources of manganese and might have to depend entirely on domestic ores, the U. S. Geological Survey, with the assistance of several cooperating organizations, has made a comprehensive investigation of domestic manganese resources. The work has included field studies in a number of states well as annual, quarterly, and monthly canvasses among operators concerning current and future production. In order that the interested public might have access to the important results of the studies, preliminary reports concerning the field work as well as periodic summaries of production were issued as promptly as possible. Although numerous summaries of production l2, l3, l4 have been prepared from time to time for the use of the several boards and committees responsible for the conduct of the war, it has been thought for some months that those engaged in the industry, as well as others, might be interested in a preliminary summary of the accumulated geologic and production data. The cessation of hostilities, in November, 1918, probably detracts from the usefulness of much of the material that is here presented, but apart from the historic interest in the performance of an important industry in war time, there is a possibility that some of the conclusions may be helpful to those who continue to exploit domestic deposits, as well as to those who wish to measure the country's independence in mineral supplies. Appropriate final geologic reports are being prepared by the geologists who did the field work. The present authors, having done but a small part of the recent field work, acknowledge with great appreciation the use of preliminary and unpublished reports and the cordial informal cooperation of the following geologists in the preparation of this paper: F. L. Ransome, G. W. Stose, F. C. Schrader, J. T. Pardee, E. L. Jones, Jr., H. D. Miser, Laurence LaForge, J. B. Umpleby, Arthur Keith, F. J. Katz, and E. S. Larsen, of the U. S. Geological Survey. Field work in Virginia was carried out in cooperation with the Virginia Geological Survey, T. L. Watson, State Geologist; in Georgia, with the Georgia

Jan 1, 1920

By David R. Mitchell, E. A. Reilly, G. R. Gardner, F. P. Lasseter

THE methods that may be applied to the treatment of slurries and water, as these are related to practical coal-preparation problems, are concerned essentially with the movements of solids suspended in water. It is assumed that there are no fundamental differences between the principles involved in the treatment of coal slurries and the phenomena encountered in general mineral-dressing practice, and the latter are-presented in some detail. Basic principles are correlated with present practice for both the anthracite and the bituminous coal fields, and methods are discussed which are designed to utilize best all the material subjected to treatment and suggest a sound approach to the solution of problems relating to the return of clear water to process or to streams. In order to approach the practical phases of the subject with sufficient understanding of the basic principles, it is necessary to discuss two types of phenomena that are applicable. The first is flocculation and the second is sedimentation. Descriptive matter is given covering the various methods and types of equipment employed to conduct these operations, with emphasis on their application to water and coal-slurry treatment. DEFINITION OF TERMS Definitions of terms are consistent with modern developments, and conform, in general, with their usage in mineral-dressing practice. Because of variations in coal-preparation methods, it is impossible to define a rigid upper limit of particle size for a coal slurry or sludge which will apply generally. Limits vary somewhat with the particular treatment method employed at a given plant. For purposes of definition, this limit is chosen as the particle size for which preparation methods such as Chance comes and jigs are usually dispensed with, and other methods, such as the Hydro-tator, tables, and froth flotation, are employed. Generally the limit will be 10 to 6 mesh.

Jan 1, 1950

By George Burrell

J. S. HALDANE, M. D., F. R. S., Oxford, England (communication to the Secretary?).-The valuable paper of Messrs. Burrell and Gauger is of special interest to me as, through the courtesy of the management, I had an opportunity of visiting the Portland mine, Cripple Creek, in 1911, in connection with the investigations on acclimatization to high altitudes, carried out on Pike's Peak, near Cripple Creek, by Professors Yandell, Henderson and Schneider, Dr. Douglas and myself.1 The analyses of one or two samples of the vitiated air were entirely confirmatory of those of the authors. A fatal accident owing to two men being lowered down a shaft filled with the gas had occurred in a neighboring mine just before our visit.

Jan 12, 1916

By Walter L. Maxson, Fred C. Bond

THIS paper is a continuation of two earlier papers, l, 2 and presents new data on the grindability of various ores and other materials-the results of several years of intermittent research work on the nature of grinding and interpretation of test results. It is divided into five parts: 1. The tabulated results of several hundred grindability tests on a wide variety of ores. 2. A method of correcting screen analyses and calculating from them the surface and other properties. 3. A description of a new method of measuring the "surface energy" of an ore by pendulum impact tests. 4. Test results. 5. A general discussion of the test results and their application to grinding problems. 1. GRINDABILITY OF VARIOUS ORES This part is a continuation of the paper listed as reference No. 1. The method of testing is described in detail in that paper. The sample to be tested is crushed to all through 6 mesh in rolls set at x6-in. opening in closed circuit with a screen. Of this sample 700 C.C. is ground dry in a laboratory ball mill under constant conditions of mill speed and ball charge in closed circuit with a screen of the desired size at 250 per cent circulating load. The mill is cylindrical, 12 by 12 in., and rotates at 70 r.p.m. It contains a charge of 285 iron balls weighing 20,125 grams and ranging from 1 ½ to ¾ in. in diameter. Each test is continued for a sufficient number of periods to establish equilibrium at 250 per cent circulating load, or until the composition of the circulating load is constant for successive periods. Tests are conducted at the mesh size to which the ore is to be ground in practice, and the results are expressed as the net production in grams of screen undersize per revolution of the mill. This is designated as the

Jan 1, 1938

By Charles Eichrodt

THE ore that is being treated by the present plant lies between the leached zone, or capping, and the mixed sulfide and oxide zone. The principal copper minerals are chalcanthite (CuSO4.5H20), brochantite (CuS04 3Cu (OH)2) and atacarnite, (CuC12.3Cu (OH)2). There are, in addition, some other minerals such as cuprite and kröhnkite (CuSO4. Na2SO4.2H20). These minerals, with many others, occur in a greatly crushed granodiorite rock. Most of the copper-bearing minerals occur in the cracks and veinlets, but there are disseminated values and it is probably the relative proportion of these that accounts for some otherwise unexplainable variations in extraction. The entire mineralization of the ore is complex and varies with depth. This variation, the problems presented thereby, and the effect of various constituents of the ore will be taken up in detail. An analysis of an unweighted composite of the ore treated during 1927 follows:

Jan 1, 1930

By B. Silliman

THE remarkable outflow of natural gas recently developed in Western Pennsylvania, and along the valley of the Ohio and its tributaries, has called attention to an important series of patents for improvements in glass-fnrnaces and the manufacture of glass, which the brothers Siemens have made since 1872. The basement-patent of this series, is No. 127,806 of the U. S. Patent office, and is of date June 11th, 1872. This has been followed by eleven other patents (including one re-issue), all for improvements in glass-furnaces, or methods of manufacture, of which the latest is of date July 11th, 1882. Nine of these patents were issued in 1880-82. The following is the list of these patents, in order of dates, viz.: 1872. June 11th. No. 127,806 (U. S. office), Improvement in glass-furnaces; 17 sheets drawings, 5 pages text. This is the basement-patent. 1877. April 17th. No. 139,800. Improvement in the manufacture of glass; 3 sheets drawings, 2 pages text. Boats and floating vessels swimming in the liquid glass of the tank-furnace. Re-issued in 1880. q. v. 1880. April 27th. No. 226,931. Furnace for annealing and tem pering glass. " July 13th. No. 220,846. Glass-melting-furnace. " August 3d. No. 230,668. Glass-melting-furnace; 4 sheets drawings, 2 pages text.

Jan 1, 1885

By Arthur F. Colombo, Donald W. Frommer

With the opening of the Tilden mine near Ishpeming, MI, a new era in iron ore beneficiation was begun. A description of a U. S. Bureau of Mines investigation is summarized to illustrate the selective flocculation-deslime-flotation process developed by the Bureau and used at the Tilden concentrator, which is also briefly described. The operating parameters for the selective flocculation-cationic flotation of an oxidized taconite from the Mesabi range are discussed. A water reclamation system using lime and a cationic flocculant was applied to reclaim the effluents from a 900-pound-per-hour flotation pilot plant. About 80 percent of water requirements were recovered, and the calcium content of the reclaimed water was found to be more important than clarity in influencing the selective flocculation and flotation processes. Although reclaimed waters with about 10 ppm calcium registered turbidities of approximately 5,000 ppm SiO2 equivalents, the concentrates produced using these waters contained 64 percent Fe and 55.0 percent SiO2 and had accompanying iron recoveries of 75 percent. Lower grade concentrates resulted from using reclaimed water with higher calcium contents and lower turbidities.

Jan 1, 1976

By F. Lynwood Garrison

It is not intended to make in the present paper any deduction or to formulate any theories from the results obtained by experiments. The further expenditure of considerable time and labor would be required to obtain a sufficient basis for positive assertions as to the microscopic structure of the different varieties of iron and steel, and the structural changes which take place in them. It is therefore my purpose at this time to offer simply a synopsis of the general results arrived at in a few months' work, a brief description of apparatus used, and a few hints as to the preparation and preservation of the material which it is intended to investigate. The study of the microscopic structure of iron and steel is not altogether new. Some attention has been given it in both England and Germany. But the foreign publications on the subject have thus far been confined, so far as I am aware, to two papers, one by Herr Martens, of Berlin, contributed to the Verein zur Befoerderuny des Gewerbfleisses and the other a lecture by Dr. H. C. Sorby of Sheffield. Dr. Sorby, it seems, was induced to investigate the subject as bearing on the structure of meteoric iron ; and the results he obtained are certainly very interesting. At the Boston meeting of this Institute, in February, 1883, Mr. J. C, Bayles called attention to the subject in a neat and exceedingly interesting paper, in which the work of Messrs. Martens and Sorby was summarized,* and original suggestions were added. It is at present difficult to say what will he eventually the practical value of the microscope, thus employed, in the sciences of engineering. The role which it seems most likely to play is that of' an adjunct to the testing-machine, and not (as some have supposed) a rival to the chemical laboratory. That it will be a most valuable accessory seems, to say the least, highly probable. I need hardly go at length into the details of preparing the material for examination. Mr. Bayles has described the process in such a plain and comprehensive manner that if his instructions are

Jan 1, 1886

By H. H. Uhlig

SINCE its first mention in the literature in the eighteenth century1,2 the phenomenon of passivity in metals has stimulated much speculation and attendant controversy as to its nature and cause. No one of the numerous theories so far proposed has been generally accepted. ? Faraday,7 in 1836, associated the passivity of iron with a protective film over the surface of the metal, which materially prevents or slows down reaction with corrosive environments. His theory was that oxidizing acids like nitric acid form an unstable oxygen or oxide layer over the iron surface, which protects the underlying metal from further attack. This concept was simple yet plausible, and without alteration has frequently been assigned in present-day discussions as explanation of the passivity of many metals. With the advent in recent times of stainless steels, it is not surprising that this oxide film theory of passivity proposed by Faraday has been used to explain the phenomenal corrosion resistance of stainless steels and other passive alloys. The passive alloys, such as the chrome-iron alloys, are supposedly covered with a protective oxide film, which forms on exposure of the alloy to air, is extremely stable and self-healing, and accounts for the remarkable resistance of these alloys to corrosion. Within the past few years, several investigators, following the theory of film protection, have attempted to gauge the resistance of the supposed film on steels. Brennert8 and Donker and Dengg9 determined the poten-tial at which a negative ion (e.g., Cl-) moving in an electric field reacted with the metal anode, as detected by increased current flow or change in potential of the steel electrode in an electrolytic cell. The potential corresponding to reaction Brennert called the film break-through potential.

Jan 1, 1939

By Richard B. Reese, George R. St. Pierre, Robert A. Rapp

The vapor pressures of pure iron and pure chromium have been measured using a Knudsen cell coupled with a mass spectrometer. The experimental results agree well with some previously reported data; heats of sublimation and vaporization have been calculated. From vapor pressure rr~easurernents, the activities of iron and chromium in their binary alloys have been determined for NcY = 0.10 to 0.65 over a 1400" to 1700~ temperature range. The activity of chromium in the liquid alloys was found to exhibit positive deviation from ideal behavior when referred to solid chromium as the standard state; however, for the activity of chromium referred to nonequilibrium undercooled liquid chromium as standard state, the activity behavior is almost ideal. ALTHOUGH the Fe-Cr system is important as the basic system of alloy steels, the thermodynamic properties of this system have not been thoroughly investigated at elevated temperatures. In view of the potential practical applications of such data as well as their contribution to alloy theory, further study of the Fe-Cr system was undertaken. In addition, further development of experimental techniques for equilibrium measurements at high temperature is required. The present research involved an application of the Knudsen effusion method in conjunction with a time-of-flight mass spectrometer. Belton and ~ruehan' have measured the activities in Fe-Ni and Fe-Co alloys by a similar method. Speiser, Johnston, and lackbburn' have determined the vapor pressure of pure solid chromium between 1283" and 1561°K by a Langmuir free evaporation technique. The vapor pressure of chromium was described by the expression: over the temperature range 1283" to 1561°K. McCabe, Hudson, and paxton3 have measured the vapor pressures of pure iron and pure chromium by the Knudsen cell technique around 1500°K. The vapor pressure and heat of sublimation at O°K, AH,", for pure chromium agreed within experimental error with the measurements of Speiser et al. at 1200°C. Kubaschewski and HeYmer~ determined the vapor pressure of pure solid chromium in the temperature range 1170" to 1400°C by the Knudsen effusion technique combined with a radioactive tracer analysis of crS1. Their results agreed with the work of previous investigators. Edwards, Johnston, and Ditmars5 have measured the vapor pressure of pure solid iron by the Langmuir technique between 1356" and 1519°K. The vapor pressure of solid iron in the temperature range studied was given by: The data of McCabe, Hudson, and paxton3 on the vapor pressure of pure iron around 1500°K by the Knudsen effusion technique were in good agreement with those obtained by Edwards et a~.~ Hultgren, Orr, Anderson, and Kelley give the selected values for the AH: of pure iron and pure chromium as 98,990 *200 and 94,340 * 500 cal per mole, respectively. These values are the average values determined in the several investigations by different methods. The Fe-Cr phase diagram7 is shown in Fig. 1. Previous determinations of activities in this system have been carried out by several investigators, but most of the work has been done on solid alloys. Using a Knudsen effusion method with cr5', Kubaschewski and Heymer4 reported that the Fe-Cr system exhibits positive deviation from the ideal behavior for compositions ranging from NCr = 0.0398 to 0.699 at 1170"

Jan 1, 1969

By J. W. Hickman, E. A. Gulbransen

In a previous paper' the authors have investigated the structure of the oxide films formed on most of the metals that make up the alloys of this study. The metals were studied in order to provide basic information on the structures, both physical and chemical, of the oxide films and to determine how these structures are effected by the temperature, time of oxidation, and surface preparation. It was felt that an understanding of the physical and chemical structure as well as the stability of the oxide film might furnish clues as to the nature of the reaction process and the protective quality of the film. The oxidation of the metals was studied over the temperature range 300' to 7o0°C. except for copper, wherc the range selected was 100' to 500°C. The results of these studies were presented in graphical form as existence diagrams of the oxides on a time-temperature scale. For some of the metals the existence diagrams were simple and showed few chemical transitions, but there were numerous cases where the physical state of the oxide surface was a function of time and temperature. In general the physical state of the oxide surface changed with increasing temperature so as to increase the sharpness of the diffraction patterns and to cause orientation effects to be more pronounced. Deviatiois in lattice Darameters from X-ray values were noted. In general these deviations were of positive nature and may be due to solid solution of the metal in the oxide lattice. This effect might be expected in thin oxide films. In a study of the oxidation of alloys containing two or more metals, there may arise the complicating factor of identification of the oxides formed. A thorough understanding of the oxides formed on the pure metals, therefore, was, essential before investigation of the oxidation of alloys. In this paper it is our purpose to present a study of the following problems: 1. The existence diagrams of various alloys. 2. The effect of the structure of the alloying metal on the existence diagram of iron. 3. The effect of the percentage of chromium on the oxides formed on Fe-Cr alloys. 4. The relationships, if any, between the oxides formed and the protective quality of the oxides. The following alloys are included in this study: alloys of iron with body-centered cubic, face-centered cubic and other metals, 13 Cr-Fe, 18-8 stainless steel, K4²B, Nichrome V, Hipernik, Inconel, Stellite "²I," Refractaloy, Kovar, mild steel, a series of Cr-Fe alloys and a series of Co-Fe alloys. Since many of the commercial alloys in this list contain more than two metals, various complicating factors in the identification of the oxides formed may arise.

Jan 1, 1947