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CONTENTS PAGE Need for Research in Foundry Pig Iron. By Richard Moldenke. (With Discussion) 1 Carbon Characteristics of Copper-bearing Pig Iron. By W. B. Coleman. (With Discussion) 12 A Pig Iron, Low in Total Carbon, is in Demand for Use in Various Industries. By Enrique Touceda. (With Discussion) 24 Carbon in Pig Iron. By Ralph H. Sweetser. (With Discussion) 28 Second Session (Discussion) 37 Need for Research in Foundry Pig Iron BY RICHARD MOLDENKE,* WATCHUNG, N. J. So FAR as the quality of the product is concerned, the history of the production of pig iron for foundry purposes is one of constant retrogression. The steps in this deterioration began with cold-blast charcoal pig iron, then anthracite iron, coke iron; then gradually warm to hot-blast coke iron, with the charcoal furnaces also heating their blast to get greater tonnages, and finally the present-day hot-blast coke irons with scrap additions to the ordinary burden that, according to one European report, have gone as high as 65 per cent. Parallel with this quality retrogression is the enormous increase in furnace tonnages from about 15 to over 1000 tons per day in exceptional instances of modern practice. The key to this situation is economic pressure. The effect is a growing differentiation between furnace production for gray iron and malleable foundries and, for the

Jan 1, 1927

By Max Hebgen

I. Natural Features of State Affecting Power Development .. 792 II. Early Developments. 1. Big Hole Plant................. 792 2. Canyon Feny Plant............... 793 3. Madison Plant No. 1............... 593 4. Black Eagle Plant................ 795 III. Later Developments. 1. Madison River System .............. 795 2. Missouri River System.............. 797 3. Great Falls System............... 797 4. Missoula River Development............ 797 5. Big Fork Development.............. 802 $ IV. Present Capacity of Power Developments....... 802 V. Transmission System...............: . 802 VI. Character of Load. 1. Lighting and Small Power Uses........... 804 2. Street Railways ................ 804 3. Mining................... 804 4. Railroads.................... 808 5. Irrigation................... 810 VII. Operation of System................. 812 VIII. Increase in Use of Power............... 811 IX. New Power Developments............... 814 X. Undeveloped Powers................. 815 It is estimated that the total stationary power now used in the United States. steam. water and gas. is probably over 30.000.000 h. p. The total developed water power is about 6.000.000 h. p. The water power in the United States now economically capable of development probably exceeds 25.000.000 h. p. The total developed and undeveloped power is

Jan 1, 1914

By W. L. Saunders

IMPORTANCE OF ROCK DRILLING. IT has been estimated that the value of the mineral products of the United States is about $2,000,000,000 a year; that about $25,000,000 is expended. annually for explosives and that about double this sum is paid in wages where blasting is done. The value of the mineral products does not adequately express the importance of the industry involved in the excavation of rock and ore because of the enormous sums of money expended in tunnel driving, in quarries, and in open-cut excavation generally. We know that the Catskill Aqueduct in the neighborhood of New York, which is now nearing completion, has cost some $165,000,000 and that about one-third of this may be rated as rock excavation. These illustrations are given in order to call attention to the great importance of an industry the extension and development of which in our industrial life depend so much upon the economics of rock drilling. Reference has been made to the new Catskill Aqueduct. There are three aqueducts leading into New York, each built at periods separated by some 20 years of time. 'The first one, known as the Old Aqueduct, conveys the waters of the Croton river to New York City in a manner which reminds one of the old Roman aqueducts, the ruins of which are still in evidence. The engineers who laid out these old conduits sought to direct their lines around the hills and into the valleys, at all times avoiding the rock. When it was necessary to cross a river or a deep ravine, a bridge or causeway was constructed. High Bridge, over the Harlem river, is an arched masonry viaduct differing in no essential features from the aqueducts of the Romans. When the second Croton Aqueduct was built, about the year 1890, the art of drilling rock had been so far perfected, and the use of explosives, through the invention of dynamite, had become ,so general, that this waterway was planned and executed on straight lines, following rather than avoiding the rock. The second Croton Aqueduct is a tunnel through rock, about 32 miles in length; material gneiss, almost as hard as granite. Its construction was made practicable by sinking

Jan 9, 1913

By L. C. Raymond

Valuations in the mineral industry differ from those of other enterprises because mines and oil wells have a definite life so cannot be considered a perpetuity. This requires that in any mineral-property evaluation the recovery of invested capital is necessary during the life of the property. Capital write-offs for nonextractive industries are assumed to be continuously plowed back to sustain the operation and produce yields on the capital invested. The extractive or mineral industry, however, generally attempts to return to the investor both interest and principal during the life of a property. Normally this is done currently and the dividend includes both items. Where the mineral property possesses large reserves and the life factor approximates a perpetuity, the return on investment is generally comparable to that of industrial stocks. The valuation of a mineral property, at best, is based on educated estimates and judgment factors. This is particularly true as it relates to estimating selling prices over a long term or assessing the quality of management. Also, it is possible to make various assumptions as to rapidity of working out the deposit, varying time for start-up of operations, varying earning rates, so as to obtain different results with the same basic facts. Thus it is not surprising that two engineers, irrespective of their abilities, may not agree exactly even when given the same facts, but their results should be close enough to be used in establishing a fair value for trading purposes. The valuation is no better than the source of basic data and the soundness of judgment factors. Fundamentally the basic principles of mineral valuation are similar for base metals, sulfur, oil, or any other mineral. Each mineral, however, requires an engineer to have a knowledge of such factors as its occurrence, distribution, mining and processing methods, and marketing problems in order to gather and analyze all the facts and data that have a bearing on the earning potential of the property. Present Value of a Mineral Property In essence the present value of a mineral property is a sum of money in today's dollars that future income from the property are worth. It differs from the total anticipated earnings by the amount of the interest that the unrecouped investment could be expected to earn during the period of recoupment. Thus, if one could accurately estimate what a mineral property will earn during its life, after deducting all operating, administrative, capital, interest, and tax charges, the determination of present value would be a relatively simple mathematical calculation. Normally, where the expected life of the mineral property extends beyond 20 or 25 years, the discounted value of earnings beyond this period is relatively small. The petroleum industry generally discounts the annual cash flow of an operation rather than earnings since, for tax-saving purposes, earnings are kept

Jan 1, 1976

By John E. Conley, John A. Ruppert

W. B. Mather—A minor recommendation that may be offered to improve the paper is the inclusion of a map of Oregon showing the general location of the various deposits. This is of especial importance to persons like myself who are not familiar with the various areas and counties mentioned. N. S. Wagner and R. S. Mason (authors' reply)—We agree that an index map of Oregon showing the location of the various nonmetallic deposits would add to the paper (fig. 1).

Jan 1, 1951

By John A. Ruppert, John E. Conley

W. B. Mather—A minor recommendation that may be offered to improve the paper is the inclusion of a map of Oregon showing the general location of the various deposits. This is of especial importance to persons like myself who are not familiar with the various areas and counties mentioned. N. S. Wagner and R. S. Mason (authors' reply)—We agree that an index map of Oregon showing the location of the various nonmetallic deposits would add to the paper (fig. 1).

Jan 1, 1951

By L. L. Oriard

In order to predict the influence of blasting on slopes, one must first understand the action of explosives, the manner in which rock is broken or displaced, and how seismic waves are transmitted, and the nature of these seismic waves. In this paper, the author describes the action of high explosives on rock masses, beginning at the source of the explosion, extending through the zone of rupture to a distance where only elastic waves of low energy persist. The paper describes the relationships between explosives charge quantities and distances, including the character and intensity of the seismic waves in various types of terrain. In looking at the analysis of slopes subjected to seismic waves, it has been common practice to assume a simplified model in which the anticipated acceleration is applied horizontally to the slope as an equivalent static force, or a model in which there is a rigid base subjected to mechanical shaking. Such models do not accurately portray blasting activity taking place within or near the slope in question. In dealing with blasting effects, it is important to under- stand seismic wave types, wave lengths, attenuation and transmission paths, as well as vibration intensity. In most cases, those slopes that are the least stable under static loading will also be the least stable under dynamic loading, although there may be rare exceptions. Thus, the more that is known about a slope statically, the better will be the assessment of it dynamically.

Jan 1, 1983

ASIDE from the John Fritz Medal, in which the Institute participates through its representation on the John Fritz Medal Board, the Institute itself has five major awards to make annually for excellence in technical papers, as follows: The Robert W. Hunt Medal, The Hadfield Prize, The J. E. Johnson Jr., Award, The Lewisohn Platinum Prize to senior members, and the President's Prize to junior members. ROBERT W. HUNT MEDAL The partners of Robert W. Hunt established a fund which was presented to the Institute at a fitting ceremony on May 27, 1920, to establish an annual medal and a sum of money to be awarded under the following rules: 1. The award shall consist of two prizes; first of a gold medal, second of a sum of money; a certificate to accompany each prize. The money prize shall not be awarded to. a member over 40 years of age, but under unusual circumstances, both prizes may be allotted to one person provided that he is not over 40 years of age. In general it will be understood that the Committee shall award the money prize to the younger men, rather than the medal. 2. The awards shall be made not oftener than once a year to that person or persons contributing to the Institute the best original paper or papers on iron and steel. The scope of the term "iron and steel" shall be determined by the sub-committee considering the awards. In general, papers dealing with the practical side of the subject have preference over those dealing with the theoretical side in recognition of the fact that Captain Hunt's main contributions to the industry have been in the improvement of production and quality of material. 3. A sub-committee of three to five including the Chairman of the Iron and Steel Committee, shall be appointed by the iron and Steel Committee annually to adjudge the award subject to approval. 4. The awarding committee shall submit its report to the Iron and Steel Committee at its October Meeting, and the. award be certified to the Secretary of the Institute in time to permit the presentation to be made at the Annual Meeting of the Institute. 5. The recipient of the award shall be designated "The Hunt Medallist." SIR ROBERT HADFIELD PRIZE Sir Robert Hadfield has offered an Institute prize of $1000 for researches with regard to the different forms of combination of carbon in iron and steel. Until within a few weeks no paper has been submitted which could compete for this prize. If the paper in hand should not meet the requirements, the donor has suggested that the prize be transferred and offered for: (a) the determination of the hardness in metals in connection. with super-hardness, (b) in consideration of questions of fuel economy, (c) in consideration of questions of industrial development and labor. J. E. JOHNSON, JR. AWARD This award is made from the income of a fund of $3000 donated by Mrs. Margaret Hilles Johnson in memory of her husband, J. E. Johnson, Jr., who was a prominent engineer, author of two valuable volumes on iron blast-furnace construction and practise, vice-chairman of the Institute's Iron and Steel Committee, and a frequent contributor of papers to the Institute's TRANSACTIONS.

Jan 1, 1925

By N. H. Emmons

An interesting development of copper blast-furnace construction has been brought about in adapting the blast-furnace to be a "burner" for sulphuric acid making. When the Tennessee Copper Co. first decided to construct an acid-plant, the standard type of brick-top furnace, supported by structural steel, was the only one in use at its plant. All the tests for temperature and strength of gas had been made on these furnaces, and had been satisfactory. When, however, the acid-plant was put on the flue, and the flue had to have a damper put in it to force the gas into that plant, troubles began. The furnaces were fairly tight, and for a few months the work was quite satisfactory. Fig. 1 shows the old type of furnace-top used at the start. It was soon found that this top would not stand the temperatures, particularly when dampered back, as was necessary to force the gas into the Glover towers. The structural steel, of which the furnace skeleton was constructed, warped and twisted so badly that it was not safe to use the furnaccs. This effect is shown by Fig. 2, which is a photograph of old No. 4 furnace, after the brick-work had been removed. It became apparent that a new type of top mas necessary and the engineering force was started on the design of a new furnace-top, with the result that a low top, with brick-lined flues at each end below the feed-floor, leading to the main concrete dust-chamber, was constructed. This furnace, No. 7, is shown in Fig. 3. The charging-doors are made of cast-iron sections, three sections to a door, and three doors to a side. A door to the furnace was made of east copper, but the heat was great that the copper bent readily, due to the jarring of its

Jan 1, 1911

By F. Claisse, R. Angers

Self-diffusion in iron has been measured during rapid a-r transformations using a variant of the Kryukou and Zhukhovitskii diffusion method. The study was performed by thermally cycling iron foils (1 to 6 cpm) through the transformation (=910°C). Some foils have been subjected to over 1000 cycles and some have spent more than 15 pct of their total diffusion time in the process of transformation. The experimental results show that the a-r transformation has no measurable effect on self-diffusion in iron. The study is completed by a quantitative analysis of mechanisms which can affect the diffusion rate during the transformation. The analysis confirms the experimental results. SINCE diffusion is an important factor in many solid-state transformations, it is of interest to study how it is affected by the stresses generated during these transformations. Clinard and Sherby1'2 were the first to make a study along these lines. They measured diffusion coefficients in Fe-FeCoV couples subjected to slow thermal cycling (1.5 cph) through the a-r transformation range. They found an enhancement of diffusion by a factor of about two. The purpose of the present paper is to report measurements of the self-diffusion coefficient of iron during much more rapid thermal cyclings (1 to 6 cpm) through the a-r transformation (-910°C). These more rapid cyclings produce higher strain rates during the transformation and should emphasize any possible influence of transformation upon diffusion. EXPERIMENTAL Iron foils, 25 to 35 µ thick, were cold-rolled from 99.92 pct pure iron and annealed in pure helium for 2 hr at 870°C; the resulting grain diameter was about 150 µ. Specimens 0.5 by 8 cm were cut from the foils and I7e55 was vapor deposited on one of their surfaces. A 38 gage alumel-chrome1 thermocouple was spot welded in the middle of one of the specimen long edges, Fig. 1. Two 38 gage chrome1 wires were also spot welded along the same edge on each side of the thermocouple; they were placed 2.5 cm apart and used for electrical resistance measurements. In order to prevent twisting and crumpling, the specimens were pinched between two quartz plates 0.1 by 1 by 7 cm and the assembly was close fitted into a 1 cm ID quartz tube. Four holes were drilled through the tube to let the 38 gage wires out: these were connected to the recording equipment by means of extension wires. 20-gage nickel wires fixed at both ends of the specimens were used to thermally cycle the foils by Joule heating. The above described device was placed in a 2.7 cm ID quartz tube which in turn was placed in a tubular furnace. Either a pure helium atmosphere or circulating hydrogen was used during the experiments. Specimens were subjected to thermal cycles between a minimum temperature To and a maximum temperature Tm at rates ranging from 1 to 6 cpm. This was obtained by maintaining the furnace at a constant temperature near the minimum temperature To and periodically passing an electric current through the specimen. Cooling was achieved by heat losses to the surroundings. The forms and periods of cycles were varied from one specimen to another; however, each specimen was subjected to one type of cycle only. The temperature and electrical resistance variations of the specimens were recorded as a function of time. The temperature curves were used for diffusion calculations while the electrical resistance curves were used to monitor the transformation and to determine its starting point and its approximate duration. Diffusion was measured by the method developed by Kryukov and zhukhovitskii3 and modified by Angers and Claisse.4,5 In this method a metallic foil is coated on one side with a radioactive isotope and the activity is measured periodically on both sides during the diffusion anneal. The following equation then holds: where: I1 Activity on the surface on which the deposit is made. I, Activity on the opposite surface. t Diffusion time. B Constant. D Diffusion coefficient. d Foil thickness including the deposit. G(t) A function of time; it is a second order correction term which is given graphically in Refs. 4 and 5. The diffusion coefficient D is found by plotting ln[(Il - I2)/(I1 + I,)] -G(t) against t; the resulting slope m leads to an accurate calculation of D through Eq. [2]. The effect of the a-r transformation on diffusion is expressed by the ratio DT/DU where:

Jan 1, 1970

By John T., Ryan

THE subject assigned me, "Safety in Mining," is a very broad one and only the high spots can be covered in this short paper. As this is a meeting of the Coal Division, these remarks will be directed largely to coal mine safety, although the principles of safety and effective accident prevention methods are relatively the same in every branch of mining or industrial work. The coal mining industry should take pride in the part it has played in the development of the accident prevention movement, and there is ample proof for the statement that the first real organized accident prevention, work, both abroad and in this country, was con- ducted in the coal mining industry.

Jan 1, 1930

By A. Perry Thompson

I. GENERAL DISTRIBUTIONS APPEARANCE, AND RELATIONS MINING in Butte has seldom encountered covellite in commercial quantities. The notable occurrences, extending vertically and laterally perhaps several hundred feet, presented scattered, bladed lenses of this mineral in a matrix of quartz, pyrite, enargite, bornite, and chalcocite. But under the microscope covellite is seen to be widespread in the Butte ores, though in such small quantity that megascopic examination will not discover it. In early mining operations covellite was found in the Gray Rock vein, a member of the Blue vein system. As described by Sales,1 it persisted as an occasional ore mineral, associated with quartz, pyrite, tetrahedrite, bornite, chalcocite, and minor amounts of sphalerite, from the 700-ft. to the 1,200-ft. level of the East Gray Rock and Diamond mines. Crushed quartz-monzonite and later quartz completed the vein filling between

Jan 4, 1915

By Wheeler P. Davey

In an article in the General Electric Review, January, 1915, reference was made to the X-ray examination of a steel casting 9/16 in thick. Fig. 1 shows one of the radiographs thus obtained. All these radiographs showed plainly the tool marks on the surface of the casting. All but one showed peculiar markings the shape of which strongly suggested that they were indeed the pictures of holes in the interior. A circular piece, 1 in. in diameter, was punched from the casting at a point where the radiograph shown in Fig. 1 indicated that a blow-hole should be found. (Location of sample shown by circle in Fig. l.) Fig. 2 is a photograph of the end of the punching, showing the hole that was found. Since that article was written it has seemed desirable: (1) to obtain data from which the exposure necessary for any thickness of steel could be at once calculated; (2) to find the thickness of the smallest air inclusion which could be radiographed in a given thickness of steel; (3) to determine in what direction to hope for further progress; and (4) to develop the technique of radiographing metals. In order to gain some preliminary data, several pieces of 1/2-in. (12.5-mm.) boiler plate were obtained, 5 by 7 in. (12.5 by 17.5 cm.) in size. In one of these, holes were drilled in such a way that the axis of each hole was midway between the faces of the steel and parallel to those faces. The diameters of these holes were as follows: Hole number Diameter I.........................................1/4 in. =6.3 mm 2........................................1/8 in. =3.l mm. 3................................... 1/16 in. = 1.6mm. 4....................................... 1/32 in. = 0.8 mm. 5........................................1/64 in. = 0.4 mm. Exposures were made on Seed X-ray plates at 20 in. (50 cm.) distance with Coolidge tube X-117, operated on Scheidel-Western induction coil with mercury turbine break. The X-ray plate was placed on a sheet of 1/8in. (3.1-mm.) lead. The steel was placed above this and a Iead

Jan 1, 1916

By Donald A. Dahlstrom

In 1961 it became increasingly more evident that significant technological changes must be made in minerals beneficiation. The status quo in technology in today's competitive markets will not be tolerated. Higher productivity, greater recoveries and newer and better products must be sought and incorporated with lower operating costs. In other words, "when you build a new mill, don't build an old mill." Recommended reading for proof of the vital necessity of new methods and techniques is in the September 1961 issue of MINING ENGINEERING. The article by one of MBD's cherished and true veterans, E. H. Rose, is entitled "Iron Ore: The BIG Picture". Because of new beneficiation methods for iron ores, nearly 47 million tons of plus 60% iron concentrates will be produced and another 40.1 million tons of capacity will be under construction or committed. Thus in a relatively short period, 87 million tons of this high-grade iron concentrate with record low silica will be available. As Mr. Rose also points out, "in gross tons, without allowance for better grade, this is the equivalent of almost exactly two-thirds of all iron ore used for all purposes in the U.S. and Canada in the peak years of 1953 or 1957." Needless to say, improved mineral beneficiation methods have had far more reaching effects than just the production of higher grade iron concentrate.

Jan 2, 1962

By T. P. Clendenin

THE northerly two thirds of Mexico falls into five main physiographic divisions, illustrated on the accompanying map. In form, these divisions are a series of strips, paralleling the northwest-southeast axis of the country.

Jan 10, 1951

By M. Earl Volin, M. Adnan Goksel

The hydro thermal agglomerating process described (U.S. Pat. No. 3,235,371, 1966)* is different from the cotzventional high-temperature processes. Green pellets or briquettes made with mixtures of moist iron-ore concen- trates and burned or hydrated lime fines are hardened in an azttoclave at 198°C and under steam pressure for 112 to 5 hr, with or without previous drying. Under the neutral conditiotzs, oxidation of magnetite does not occur as in the conventional processes. The resulting azzlomerates-- are hard and resistant to abrasion and weathering, and they do not disintegrate in the Under test. The equipment required for the process is not complicated, and favorable operating costs are projected because of the low temperamre and efficient heat recuperation. A low capital investment makes the process attractive even when the annual pellet production is below a million tons.

Jan 1, 1970

By R. A. Wood, R. I. Jaffee, H. R. Ogden, D. N. Williams

The tensile properties, creep resistance. and thermal stability of highly alloyed Ti-Al-Zr alloys were examined. On the basis of these studies, the Ti-7Al-1ZZr composition was selected for more complete evaluation. The alloy was found to be weldable and free from excessive directionality. In addition, it developed maximum properties without requiring heat treatment other than an annealing operation in the alpha field. The alloy was recommended for scale up and is presently being investigated on a production-level basis. One of the more attractive properties of titanium alloys is their ability to withstand stress at moderately high temperatures, and a considerable amount of effort has been devoted to increasing the maximum service temperature of titanium alloys. This work has suggested that the optimum alloys for high-temperature service will be single-phase a (close-packed hexagonal) alloys containing significant amounts of aluminum. However, the maximum amount of aluminum which can be alloyed with titanium is between 6 and 8 pct,l since at high-aluminum contents an embrittlement reaction occurs in the anticipated service temperature range, 800" to 1100°F. It has been shown that the embrittlement reaction involves decomposition of the high-aluminum a phase to one or more new phases.' Since this reaction does not occur at intermediate or low-aluminum contents, it was felt that intermediate Ti-A1 alloys might be strengthened by a-soluble ternary additions without inducing the embrittlement reaction. The first alloying addition considered was tin, which shows extensive solubility in a titanium and has moderate strengthening tendencies. Unfortunately, it was soon apparent that tin also promoted the embrittlement reaction, and that to obtain a stable alloy, the aluminum content had to be reduced as the tin content was increased. The second alloying addition considered was zirconium, which is similar to tin in its effects on titanium. This element did not contribute to the embrittlement reaction and, in fact, appeared to increase the maximum amount of aluminum which could be alloyed with titanium without inducing instability. This paper describes an investigation of the Ti-A1-Zr a alloy region. Alloys containing from 4 to 12 pct A1 and from 6 to 15 pct Zr were examined. The properties of these alloys are described and the bases for selecting an optimum composition is outlined. This composition, Ti-7A1-12Zr, is presently being scaled up in tonnage quantities, and is being evaluated extensively throughout the industry. In addition to presenting the basis for its selection, this paper presents a description of the properties developed in laboratory material as determined during the alloy investigation. These properties suggest that this alloy can fill an important position in applications requiring light weight, fabrica-bility, weldability, and strength to 1000oF or higher. EXPERIMENTAL PROCEDURES Titanium alloy ingots were prepared by inert electrode arc melting under an argon atmosphere. Alloying elements used were 110 Bhn titanium sponge, high-purity aluminum, and reactor-grade zirconium. Pancake-shaped ingots were prepared weighing approximately 300 g. The composition of the ingots was checked by weight measurements before and after melting. The pancake ingots were forged at 2000°F to approximately half their original thickness to give a flat plate roughly 1/2 in. thick. This plate was then rolled at 1800' to 1600°F to 0.250 in. thick. All of the alloys examined fabricated well. However, alloys containing 15 pct Zr tended to overheat due to exothermic oxidation, and scaling was excessive. As might be anticipated from its effect in decreasing the ß transus, increased zirconium appeared to improve fabricability somewhat, especially during rolling at lower temperatures. Except for a limited study of heat-treatment response, all alloys were examined in the a-annealed condition. Prior to heat treatment the a and ß tran-sus temperatures were determined by metallo-graphic examination of samples quenched after annealing at 50-deg intervals in the transformation region. These data are shown in Fig. 1. Recrystal-lization appeared to occur in about 1 hr in the range 1300º to 1500ºF. Therefore, alloys were annealed for 1 hr at 1550ºF (4 and 5 pct Al), 1600ºF (6 through 7-1/2 pct Al), or 1650°F (8 or more pct Al). This produced an equiaxed a grain structure. In most alloys, a "ghost" structure was visible after the a-annealing treatment, as shown in Fig. 2. This structure apparently resulted from the acicular

Jan 1, 1963

By A. U. Seybolt

The pressure-temperature relations required to maintain the existence of Si3N4 in silicon-iron of 0.44-11.7 pet Si have been partially explored. The critical data obtained have allowed the calculation of some thermodynamic quantities, and have shown evidence of an order-disorder two-phase field extending at 800°C from about l pet to 5.5 pet Si. THE presence of silicon nitride in electrical sheet, nominally about 3 1/4 pet silicon, balance iron, has been described by several authors'" but there has been some discrepancy among them regarding the identity of the nitride. Also, little has been reported on the quantitative thermodynamic prop- erties. In the work to be reported here, the nitride has been found to be more stable than described by Corney and Turkdogan." Several silicon nitrides have been described in the past, including SiN, Si3N4 and Si2N4 (see, for example, Abegg6 and Pascal7). However, the literature on nitrides other than Si,N, is all very old. No recent investigators using the more powerful tools available today have reported the presence of any nitride other than S3,N4. W. B. Hicke and L. R. Brantley8 in 1930 determined the dissociation pressure of Si3N4 which they made by reacting nitrogen

Jan 1, 1959

As a service to its readers, MINING ENGINEERING is publishing the mineral industry portion of the 1952 list of "Accredited Undergraduate Engineering Curricula in the United States." This list, revised annually, is issued by the Education Committee of the Engineers Council for Professional Development, and covers all phases of engineering education. The AIME is actively represented on ECPD, which was jointly organized by the Founder Societies and various other groups interested in the professional recognition of engineers.

Jan 4, 1953

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