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Jan 1, 1907

By A. A. Brant

In this presentation, concepts of the formation and evolution of the universe, the earth, and the cyclic civilizations of man are broadly outlined. The 5 billion or more years of the universe and the 4% billion years of the earth are contrasted to the 5000 years of modern society and the 100 years of objective scientific breakthrough. THE UNIVERSE Let us start back as far as possible, to the beginnings of this universe, some 5 billion or more years ago. This is a time interval that can be crudely underestimated by the moon-earth tidal friction effects that have increased the length of the day by about 1/1000 second per century — from a 5 to 7 hour day to its present 24 — and have moved the moon away at 5 inches per year to its present 240,000 miles. The oldest stony meteorites from interplanetary space give an age dating of some 4.6 billion years, approximating the time of formation of our earth. Further, certain stars pulsate, the period of pulsation being related to their absolute brightness. Measuring apparent brightness and comparing, gives the distance away. Thus Hubble and Shapley of Harvard, from 1925 on, were able to show that the universe reached as far as our telescopes could scan. The Doppler shift of the hydrogen red lines could only mean that the nebulae, or galaxies, were moving away away at velocities increasing with their distances, by 180 km/sec velocity increase for every million light year's distance. In short, the universe is expanding like an exploded bomb. Comparing the velocity increase per million light year's distance again indicates a zero time of some 5 billion years' Thus it appears that this universe had a finite beginning. Physical measurements and present theories permit some picture of our universe's birth. We know since Einstein that many forms of energy are equivalent, e.g., mass, and electromagnetic radiation, aspects of which are heat and light. Now with expansion, radiation density or equivalent mass decreases as a length factor to the 4th power, while mass as matter decreases at a length factor cubed. The temperature in outer space is now perhaps 100° absolute and the radiation mass equivalent is but 1/1000 the rarefied interstellar gas densities. Decompressing the universe to a starting point, however, raises temperature more rapidly than mass density, and results in a high radiation mass energy fraction, which since it is proportional to temperature to the 4th power suggests a zero point temperature of several billion degrees, brighter than any sun. "Let there be light and there was light," according to Genesis 1-3. Now what further initial conditions must there be to explain the relative abundance of the elements in the universe, which by spectral analyses of the earth's crust, stony meteorites, and the sun and stars is surprisingly uniform throughout. Some 55% of all cosmic matter is hydrogen, some 44% is helium and only 1% is made up of all the heavier elements in much the same proportions as on earth. These latter decrease logarithmically in abundance up to atomic weight 100, then level out. This consistent abundance distribution of elements in the universe may be generally explained by taking at Time Zero a hot neutron gas of density about 10-3 grams per cc, at a temperature of several billion degrees Centigrade, with a high radiation energy fraction. Generally neutrons break down into positrons and electrons within about ten minutes, but at the initial high temperature and radiation pressure would recom-bine. However, with rapid expansion and decrease of temperature and pressure, the neutron disintegration would run uncompensated and aggregation would result from neutrons and protons uniting in different degrees of complexity. The total calculated element aggregation time would be about one hour while the temperature still remained above one billion degrees. The element abundances formed would depend on density of the nuclear gas, simplicity of the atom formed, and the neutron capture cross section. Thus a higher density

Jan 1, 1964

By Harry Seltz

SEVERAL investigators have measured the heat capacity of cementite, using different methods of attack, but the agreement between the values obtained cannot be considered good. Naeser1 has made measurements of "average heat capacities" of iron carbide between 1026° and 85° K., using a water calorimeter. His computed true specific heat at 78.1° K. is 11.22 cal. per gram-formula mass, which, if correct, is much too high for any reasonably accurate extrapolation to 0° K. The cementite used by Naeser was obtained from a steel containing 0.9 per cent carbon, by electrolytically dissolving out the iron in a neutral bath of ferrous chloride. The cementite remained as a coarse, crystalline, gray powder. Andes" has measured the specific heat of iron carbide, from 102° to 323° K., as it exists in steel. The specific heats of several slugs of steel of known iron carbide content were determined, and the specific heat of the iron carbide (Fe3C) calculated by plotting specific heat versus percentage of carbon, and extrapolating to pure Fe3C (6.7 per cent C). The heat-capacity values for temperatures below 100° K. were obtained by comparing the temperature-specific heat curve for Fe3C to that of Fe. Since the two were very similar in the range examined experimentally and approach more closely at low temperatures, it was assumed that near the absolute zero the form of the curve for Fe3C would be similar to that of Fe. Andes calculates for the entropy of Fe3C, S298 = 23.55 e.u. The heat of formation of Fe3C has been studied by several workers. Kelley' has reviewed these measurements and calculations, and selects those of Roth4 and Naeser5 as worthy of most consideration. Roth has given ?H = 5400 cal. ± 30 per cent as a result of his own and other work. Naeser has determined the heat of formation from Fe and different forms of carbon, and for graphite (ß) he finds OH = 5600 cal. Kelley accepts the rounded figure ?H = 5500 as the heat of formation at 298.1° K., but this value is quite uncertain.

Jan 1, 1939

cation received from Brigadicr General Thos. G. Hanson said: "It is my painful duty to communicate to you the fact of the loss of your son, Martin F. Bowles. About 11 o'clock on the night of September 3, Lieutenant Bowles, with Lieutenant Joseph B. Keckler, 355th Infantry, in command of a reconnoitering patrol of our troops, encountered the enemy. In the ensuing engagement your son received a rifle bullet through his heart. His death was instantaneous and painless. His remains were intcrred with full military honors on the 4th of September." He was promoted to First Lieutenant, but his commission did not reach him before his death. He was president of the Missouri Mining Association, Missouri School of Mines, for the year 1916-17.

Jan 1, 1920

By Walter Harvey Weed

CONTENTS. [ ] INTRODUCTION. THIS paper deals with certain ore-deposits whose structural features or mineral contents (or both) result, directly or indirectly, from igneous intrusions and their after-effects. It is largely a discussion of contact metamorphic ore-deposits based upon the physical changes in rocks due to contact action. It involves a classification of ore-deposits only so far as is abso-

Jan 1, 1913

By J. C. Mertz

ACCURATE knowledge of the solid solubilities of the elements that dissolve in the important base metals is needed for guidance in the preparation and heat-treatment of the alloys derived from these compo-nents. While there is still difference of opinion concerning the merits of the X-ray and microscopic methods of determining such solubilities, it is certainly true that the recent extensive use of X-ray diffraction to review the existing constitutional data has revealed many glaring inaccu-racies and has brought about a much improved knowledge of phase-boundary locations, which will inevitably come to include all of the important alloy systems. When the work is done with all necessary precautions it appears that in the majority of cases where the solubilities extend beyond a few tenths of a per cent the X-ray back-reflection technique is capable of furnishing the best of information in this field. For the most prolonged and thorough studies it is obviously advisable to combine the results of several methods, in particular, to obtain an agreement between X-ray and microscopic data. This paper reviews the work previously done on the solubilities of phosphorus, arsenic, antimony and bismuth in copper and, in considera-tion of the uncertainties thus made apparent, presents, new X-ray data obtained with the first three members of this group.

Jan 1, 1936

By Andrew Hodge

ISSUES IN MINING LABOR The examination of mining labor issues is often confined to health, and safety. There are other issues, including the present state of mining manpower availability and utilization, and the nature of mineral industries' industrial relations, which are worthy of consideration. The state of the labor market for mining skills, the availability and utilization of mining engineers and related disciplines, the state of research and its employment of scientists and engineers, and the condition of mining industrial relations with all these groups, all have an important effect on the viability and economic health of the minerals production sector. PRODUCTION LABOR Why examine an industry's production labor market? People involved in an industry should be aware of what labor supplies will be relative to industry requirements. This advance information allows industry and government to plan ahead to alleviate problems by moving to affect labor supplies or to accommodate production to expected labor supplies. This is less costly and less painful than responding after the fact to labor market changes. Any industry requires some form of labor. Labor is especially important to the mining industry. Mining labor is well paid. Average annual earnings are higher than in manufacturing. Average hourly wages are also higher. Payroll costs form a high percentage of total cost in coal mining and nonmetallic minerals mining. In metal mining the percentage is comparable to the average for manufacturing. Payroll cost in oil and gas extraction is quite low, but a major proportion of cost is in the form of income to proprietors, i.e., unincorporated businesses. Mining labor is worthy of specific attention. The minerals extraction labor is unique in many ways. Mining labor and especially underground miners are differentiated from other "unskilled" labor. Miners cannot be considered as part of a larger labor pool. The mining labor market has exhibited a unique combination of characteristics. Mining is the only large sector of United States employment in which hourly wages are high and continuing to rise, yet employment declines. Although industry has introduced new labor-saving investments, and labor requirements continue to decline, there is evidence of a mining labor shortage. Specific problems have arisen in the mining labor market such as a present labor shortage in nonfuels mining. Understanding the causes and remedies for these specific problems is also important. These various problems and questions may be handled in a unified manner by examining the relationships of certain economic variables. The relationship that exists between changes in output, employment, labor productivity, and hours worked per week may be stated explicitly:

Jan 1, 1976

Inflation, fuel shortages, environmental restrictions, and a worldwide recession that sharply curtailed the demand for goods and services, were the main causes for the poor performance & virtually all industrial minerals in 1975. This poor showing was not a surprise. As Felix Shay correctly predicted in his introductory remarks to last year's industrial Minerals Review (ME, Feb. 1975, p. 70), ". . . the minerals industry will soon be facing falling demand as a consequence of sharp declines in auto production, housing, appliances, and other consumer goods. Moreover, when sales weaken. the high-volume, low-priced industrial minerals will incur sharply.

Jan 3, 1976

By P. Farrar, H. Margolin

The Ti-Pb diagram was investigated in the region 0 to 58 pct Pb and from 500°C to liquidus temperatures. Three reactions were encountered: I—ß?a+Ti Pb at 725 10°C; 2—ß+L?Ti4Pb at 1305+ 10°C; and 3—the possible eutectic L-+Ti,Pb and y between 1200" and 1300°C. LEAD-RICH alloys have been investigated by Nowotny and Pesl,' who used sintered compacts and studied the region from 37.5 to 100 pct Pb by X-ray diffraction analysis. The only phase found in addition to titanium and lead was the hexagonal compound Ti Pb. Alloy systems of lead with metals of the transition group, such as iron, chromium, tungsten, cobalt, nickel, or manganese, generally show little liquid or solid solubility.' Craighead et al.,3 however, indicated that lead is soluble in a and ß titanium to at least 2.1 pct. They also found that approximately 50 pct of the lead added was lost during the arc-melting of Ti-Pb alloys. In the present investigation, are-melting also was used to prepare Ti-Pb alloys and similarly large lead losses were encountered. Experimental Procedure Alloy Preparation: Considerable difficulty was encountered in the melting of the Ti-Pb alloys and a number of experiments were performed before the method described was developed. Alternate layers of lead and titanium were wrapped with titanium sheet and compacted. This "sandwich" was annealed at 300" to 350 °C and was melted according to the procedure described by Cadoff and Nielsen.' Using a low current, 150 amp, and an argon atmosphere, four to eight 10 to 20 sec melts were made on each alloy, with the button being turned over between each melt to insure homogeneity. In the high lead range, the preliminary sintering was found to be of doubtful value and was eliminated. In the region above the nominal composition of 70 wt pct Pb, the alloys prepared in this manner always consolidated into two phases. The outside appeared to be composed entirely of lead and the inside was a Ti-Pb alloy. In order to determine whether this phenomenon was caused by a miscibility gap, master alloys with a nominal composition of 40 wt pct Pb were machined and mixed with various percentages of lead sheet. This mixture was compacted and melted in the same manner as the other alloys. Although these alloys were not homogeneous, they did not show the layering that was observed

Jan 1, 1956

By Woolsey McA. Johnson

In metallurgical circles it is known widely, but somewhat vaguely, that the ease of reduction of metallic oxides depends largely on the way they hare been prepared. It is likewise known that different forms of carbon have different and greatly varying reducing powers. It is the purpose of this paper to show somewhat more definitely and scientifically these facts. Some years ago the writer published an account of pyrometric determinations of the reduction temperature of zinc oxides variously prepared and of several kinds.' In said paper it was shown that the temperature at which zinc oxide evolves zinc according to the equa-tion ZnO + C = Zn + CO depends upon the nature of the two reacting bodies. The determina-tions had a range of accuracy of from 2° to 6°C., whereas differences were found to amount to an extreme of 90' C. So the differences are real ones and must have a definite cause. The equation of boiling water, (H2O)4 D 4 (H2O) has a fixed temperature for equilibrium of 100° C. at 760 mm. pressure. In general, all equations reacting in the liquid or the gaseous phase have well-defined constant physical conditions which govern the equilibrium point and reaction velocities. In a reaction where we have one or more solid phases, the tempera ture conditions requisite for the unbalancing of the stable system are found to vary. These variations are due to the fact that in a solid there is a very complex molecule and it is not a question solely of the tearing away of two interlocked atoms, but also of the destruction of a complex molecule containing hundreds, or possibly thousands, of smaller molecules. In other words, there are two forces to be overcome: a certain

Jan 1, 1914

Jan 1, 1942

By Donald L. Katz, Leslie J. Noaker

Experimental data are presented for hydrate formation conditions for mixtures of hydrogen sulfide and methane. Vapor-solid equilibrium constants for hydrogen sulfide are also presented. Equilibrium constants, defined here as the ratio of the mole fraction of hydrogen sulfide in the vapor phase (dry basis) to the mole fraction of hydrogen sulfide in the solid phase (dry basis), were calculated using the vapor-solid equilibrium constants for methane presented in an earlier paper. The conditions at which a natural gas will form gas hydrates with water may be computed from its composition, when hydrogen sulfide is present in addition to carbon dioxide and the paraffin hydrocarbons. INTRODUCTION Many gases are known to form solid hydrates in the presence of liquid water at temperatures above 32°F. This hydrate formation is of importance to the natural gas industry inasmuch as most of the constituents found in natural gases will form hydrates. The attention of the industry was called to hydrates by Hammer-schmidtl0 in 1934. A number of papers have been written giving the temperatures and pressures at which these hydrates will form3,4,5,6,7,8,9,10,13,14,15,18,19 and a bibliography on the subject has been compiled13. Deaton and Frost4,5,6,7,8 report work for various pure gases and for some natural gases. Katz and co-workers3,4,13,14,18,19 have reported data for various gases at high pressure. They developed a method of predicting conditions for hydrate formation from equilibrium constants3,19 and from gab gravity." The effects of anti-freeze agents on the formation of hydrogen sulfide hydrate were reported by Bond and Nelson.' The hydrogen sulfide-water system, including hydrate, has been the subject of recent investigation by Sage and co-workers." Mixtures of hydrates behave as solid solutions and an equilibrium exists between the vapor phase and the solid phase that appears to be comparable to the equilibrium between vapor and liquid phases.3,10 By means of the vapor-solid equilibrium constants which have been published for methane, ethane, propane, iso-butane, and carbon dioxidel6 it is possible to determine the temperature and pressure at which hydrates will form for a specific gas mixture when water is present. Hydrogen sulfide which is frequently found in natural gases has a very strong tendency to form hydrate and must enter the solid solution when present in a natural gas forming a hydrate. To determine the effect of hydrogen sulfide when computing the conditions for gas hydrate formation, it is necessary to have the equilibrium constant giving the ratio of the concentration of hydrogen sulfide in the gas phase to the concentration in the solid phase. This paper presents data on hydrate formation for mixtures of hydrogen sulfide and methane and presents the equilibrium constants which were calculated from these data. EXPERIMENTAL PROCEDURE The apparatus used to determine the conditions of hydrate formation for the methane-hydrogen sulfide system was similar to that employed by previous investigators.3,18,19 A charge gas cylinder was used to supply the hydrogen sulfide-methane mixtures, called the charge gas, and to supply the pressure up to 1.000 psia. This

Jan 1, 1955

The regulations governing the filing of claims under the War Minerals Relief Act have been amended so as to allow claimants to file a brief with the questionnaire. It has been decided that hearings will be conducted by the War Minerals Relief Commission when good reason for such action can he shown. When justified, the Commission will conduct the hearing at a point easy of access from the mining district concerned. Applications for relief are beginning to reach the Commission in considerable volume. Thirty claims have been filed in such condition as has permitted of their formal filing with the Commission. Many others have been returned with instructions as to the information required and the procedure it is necessary to follow.' An effort was made to induce the Secretary of the Interior to open a Pacific Coast branch office of the War Minerals Relief Commission; this he has declined to do, claiming that it is impracticable to divide the work.

Jan 5, 1919

J. D. Fast and J. L. Meijering (Philips Research Laboratories, N. V. Philips' Gloeilampenfabrieken, Eindhoven, Netherlands)— After the departure of our friend Dijkstra to the United States, investigations on the effect of alloying elements on the behavior of nitrogen in a iron were continued in Eindhoven. We too found internal friction curves with two separate peaks for iron containing nitrogen in addition to 0.5 atomic pct V or 0.5 atomic pct Mo. Our first publication on these investigations" appeared almost simultaneously with the paper now under discussion. At first sight our experimental results seem to be in harmony with their conclusions, but a closer examination reveals that in the case of the Fe-V-N alloy the abnormal peak is not controlled by one time of relaxation only. Whereas iron containing 0.5 atomic pct Mn or Mo absorbs an amount of nitrogen of about the same magnitude as that absorbed by pure iron under identical conditions, iron containing vanadium absorbs in addition one nitrogen atom for every vanadium atom. This last amount, far exceeding the first amount in the case under consideration, combines chemically with the vanadium and causes no internal friction. The "free" nitrogen in the vanadium alloy gives rise not only to a damping peak corresponding to that in pure iron but— due to the presence of VN particles in the metal—also to the abnormal peak at higher temperatures. The VN particles create interstitial sites around themselves where the free nitrogen atoms are bound much tighter than in the normal interstices. These abnormal interstices, therefore, will capture free nitrogen atoms rapidly, whereupon these give rise to the abnormal damping. The binding energy in the abnormal interstices is not the same for all, and with coarsening of the VN precipitate the distribution of these energies is displaced toward the side of stronger binding. This is deduced from a shift of the summit of the second peak toward higher temperatures (from 80" to 88°C in our experiments) caused by prolonged heating at 950°C. From the intermediate state where they cause the abnormal damping, the nitrogen atoms pass over rather rapidly into the fully precipitated state (iron

Jan 1, 1954

By William Fink

NICKEL is used as an alloying element in several complex commercial aluminum alloys, among which are found some very interesting proper-ties, such as relatively high strength at elevated temperatures, relatively low coefficient of expansion, the absence of permanent growth, ability to take a good polish, and a bright, pleasing as-cast surface. For that reason the aluminum-nickel system was included in the list of binary aluminum systems that are being studied as a preparation for the investigation of more complex commercial alloys. This paper is the fifteenth of a series from the Research Laboratories of the Aluminum Company of America reporting the results of investiga-tions of equilibrium relations in aluminum-base alloys of high purity. The aluminum-nickel equilibrium diagram from 0 to 18 per cent nickel was determined, using the purest material available.

Jan 1, 1934

Jan 1, 1925

By W. M. Weigel

WHILE electric lamps both of the cap and hand type are being introduced into many mines requiring the use of safety lamps, the oil-burning safety lamp is still used in the great majority of cases, and even where the former are used the latter must continue to be employed when testing for gas. It is not the intention to discuss here the relative merits of the two types, but simply to give a comparison of the illuminating effect or candlepower of several kinds of ordinary safety lamps used for general work and for testing. Few data have been published in recent years on this subject and because of this it is hoped that the following information may be of some interest and value. The lamps tested were in all cases. of standard size and in good condition, all practically new, and were selected from a collection of about 100 with a view to obtaining results on as many different common types as possible. With the exception of the gasoline-burning lamps, five different oils were used in each lamp to determine whether -particular oils were suited to particular lamps and whether there was any great difference in the illuminating power of the different oils, or whether some oils would maintain their illuminating power better than others throughout a working period of 8 hr. No attempt was made to determine the amount or cost of oil burned by each lamp, but the condition of the lamp, wick, glass, and gauzes was noted after each test.

Jan 8, 1916

THROUGH the courtesy of the Southern Appala-chian Coal Operators' Association, a joint meeting of the Southern Appalachian Efficiency Associa-tion and local members of the A. I. M. E. and A. S. M. E. was held at Knoxville, Tenn., on Nov. 12. In introduc-ing the subject and stating the object of the meeting, H. Foster Bain, speaking for the. Institute members, said "Shoveling coal is the largest job of hand labor re-maining in this country, with the exception of the mis-cellaneous work on the farms, and even there nearly all the big jobs are now performed with the help of machines. The men in the coal mines, by hand labor, dig, each year, more cubic yards than were taken out of the Panama Canal. It has been a natural ambition of engineers, operators and men alike to follow here the characteristic lead of American industry and to substi-tute as far as possible the work of machines for the work of men; to promote the latter to the position of con-trolling and directing mechanical power rather than being themselves the machines that lift the coal from the floor of the room into the mine car. "Handling materials is one of the regular jobs of mechanical engineers, and the American Society of Me-chanical Engineers maintains a Materials Handling Division for discussion of the technical problems con-cerned. Having in mind the excellent results that had flowed from application of mechanical power and de-vices to these problems in factories, port terminals, warehouses, and other above-ground plants, the Me-chanical Engineers began to consider the possibility of introducing similar methods underground. Individual-ly, many were called upon to design, erect and operate machines for such use and at once they found them-selves faced by many novel conditions and difficulties. The Division thereupon planned a general meeting in New York in March, 1926, for consideration of problems and progress in this field. The Mining Engineers. and representative coal operators were invited to attend and

Jan 12, 1927

By J. A. Scott, F. R. Hensel

The paper deals with the investigation of two types of coreless induction furnaces, one of 60 cycles, the other of 5000 cycles. Nickel was used as test material and the absorption of oxygen by molten nickel was chosen for determining the influence of the frequency on the metallurgical characteristics of the furnaces. Dr. Herty's aluminum method, slightly modified, was found suitable for determining the nickel oxide content in nickel. Also an electrolytic method for determining alumina in nickel was worked out. The solubility-temperature relations for nickel oxide in molten nickel were determined approximately. It was found that the solubility of nickel oxide increases with the temperature. Comparative tests on the rate of oxygen absorption made in a 60 and a 5000-cycle furnace showed that the absorption of nickel oxide in nickel is an increasing function of turbulence, time and temperature. The rate of oxygen pickup in the 60-cycle furnace is about three times as great as in the 5000-cycle furnace. In the 60-cycle furnace the maximum oxygen content of the melt comes close to the saturation limit. Melting under an oxygen-free atmosphere prevents oxidation in both types of furnaces. DISCUSSION (Iloward Scott presiding) H. Scott, East Pittsburgh, Pa.—When Professor Desch was in Pittsburgh recently he mentioned that the induction furnace has practically replaced the crucible furnace in Sheffield except for the carbon tool steels. Dr. Hensel is to be congratulated on the development of analytical methods for determining inclusions and for getting two different methods to agree. F. R. Hesnsel—Recently the purification of molten metals with hydrogen or other suitable gases has become an important issue and a number of patents have been taken out covering gaseous treatments of molten metals. In this connection I wish to call

Jan 1, 1933

By R. J. Fruehan

The oxygen activity and concentration were measured in Fe-Cr-0 melts in equilibrium with an oxide phase at 1600°C (2912°F). The activity was determined by ,use of the following solid oxide -electrolyte galvanic cell CY-Cr8,(s) I ZrOz(CaO) I Fe-CY-G(saturated)(l) The oxygen concentration decreases with increasing Cr concentration to about 270 ppm 0 at about 7pct CY and then increases gradually. The activity coefficient of oxygen (fo) decreases with increasing Cr. In melts containing up to about 20 pct Cr, log f is approximately a linear function of wt pct Cr with a slope (e q 2) of —0.037. The activity of chromium was calculated and found to exhibit a small negative deviation from Raoult's law. From the activity and solubility data for low chromium melts, the free energy of formation of chromite, FeCr204, was found to be -79.8kcal per mole where pure liquid chromium and oxygen at I wt pct in Fe are the standard states. ThE effect of chromium on the chemical behavior of dissolved oxygen in liquid iron is of great importance in controlling the deoxidation of steels containing a significant amount of chromium. Chen and chipman' equilibrated Fe-Cr melts in the presence and absence of slag with hydrogen-water vapor mixtures. They concluded that at 1595°C chromite was the oxide phase in equilibrium with Fe-Cr alloys containing less than 5.5 pct Cr while at higher chromium concentration Cr,O, was the stable phase. In the composition range 0 to 10 pct Cr they found that the interaction coefficient, was equal to -0.041. Turk-dogan,' Schenck and Steinmetz,, and pargeter4 measured egr) in a similar manner and found the value to be -0.064,-0.04, and -0.052, respectively. McLean and Be11 evaluated egr) from their data on the equilibrium of Fe-Cr-Al-0 alloys with H2/H20 mixtures and found it to be -0.058. However, McLean and Bell's value should only be considered an estimate because the effect of aluminum on the activity coefficient of oxygen is about a hundred times greater than that of chromium. Consequently, an error in the value of egl) used, which at the present time is not well-known, or an error in aluminum analysis, which is present in very small quantities, will result in a significant error in egr). Fischer et a1.6 determined the interaction coefficient (eEr) in Fe-Cr-0 melts not in equilibrium with an oxide phase and containing less than 18 wt pct Cr at 1600°C electrochemically. They determined a value of -0.031 for egr). Hilty et aL7 measured the oxygen content of Fe-Cr melts in equilibrium with an oxide phase containing up to 50 pct Cr. They found that the solubility of oxygen decreased as the chromium content increased to about 6 pct Cr and then increased gradually. They concluded that the equilibrium oxide phase was chromite below 3 pct Cr, distorted spinel from 3 to 9 pct Cr, and Cr,04 above 9 pct Cr. Adachi and lwamotoa also investigated this system, but did not find Cr30,. They X-rayed the equilibrium oxide phases and did not find the presence of Cr,O,. They also X-rayed the oxide phase extracted from a 65 pct Cr melt which was heat treated and did not find metallic chromium as would be expected if Cr3O4 were the equilibrium oxide phase as indicated by the reaction : 3Cr3O4 — 4Cr2O:, + Cr [lj It was the purpose of the present investigation to determine the effect of chromium on the activity coefficient of oxygen in Fe-Cr melts by measuring the activity and solubility of oxygen equilibrated with an oxide phase in the composition range 0.18 to 50.5 wt pct Cr at 1600°C (2912°F). The activity of oxygen in the melts was determined by use of the following galvanic cell: The relationship between the partial pressure of oxygen in equilibrium with the melt and the reversible electromotive force of the cell (E) is where 11 = 4, F is the Faraday constant, pb, is the oxygen pressure in equilibrium with the meit and is the oxygen pressure in equilibrium with Cr203 as determined from the free energy data compiled by Elliott et al? The oxide phase in equilibrium with pure chromium was assumed to be Cr If Cr30, were the equilibrium phase the activities derived would be approximately the same, since the best estimated free energy of formation of Cr,O,, if it does exist, is approximately % the free energy of formation of The activity of chromium in Fe-Cr alloys at 1600° C was also determined from the measured electromotive force. The activity of chromium (aCr) is related to the electromotive force as follows: , The oxide phase in equilibrium with pure chromium and Fe-Cr melts from 10 to 52 pct is assumed to be Cr203 so that n equals three. If future work proves the existence of Crs04 in equilibrium with Fe-Cr melts and pure chromium, the experimental results can be reevaluated using a value of $ for n in Eq. 141. A value of ^ for n will make the activities about 10 pct higher. In order for Eqs. 131 and [4J to be valid the electrolyte, ZrOa(CaO), must exhibit predominantly ionic conduction at the temperature and oxygen partial pressure of its use. Previous work1' has demonstrated that ZrOz(Ca0) is predonlinantly an ionic conductor

Jan 1, 1970