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By Martin Coryell

THIS coal area, and the coal from a limited portion of it, has been known for a long time. In 1817, McClure prepared a geological map to represent the boundaries, and they are not controverted at the present date. In 1834, Richard C. Taylor made a survey and report on portions of the basin. In 1835, Prof. W. B. Rogers was appointed by the State of Virginia to make a geological survey, and made six annual reports in which this area was included; but the re¬ports and maps were not published. R. C. Taylor's Statistics of Coal, published in 1855, gave to the public the details of exploration and production, to date, very perfectly and completely. Daddow and Bannan's work, Coal, Iron, and Oil, published in 1866, repeated the details before given, and advanced some vague theories respecting the coal-field, but gave no new facts. Macfarlane's work, Coal Regions of America, published in 1873, under the head of "Triassic Coal," chapter 27, gives what is known from existing publications of the position, geology, and production of the field, making

Jan 1, 1875

By Martin Coryell

This coal area, and the coal from a limited portion of it, has been known for a long time. In 1817, McClure prepared a geological map to represent the boundaries, and they are not controverted at the present date. In 1834, Richard C. Taylor made a survey and report on portions of the basin. In 1835, Prof. W. B. Rogers was appointed by the State of Virginia to make a geological survey, and made six annual reports in which this area was included; but the reports and maps were not published. R. C. Taylor's Statistics of Coal, published in 1855, gave to the public the details of exploration and production, to date, very perfectly and completely. Daddorw and Bannan's work, Coal, Iron, and Oil, published in 1866, repeated the details before given, and advanced some vague theories respecting the coal-field, but gave no new facts. Macfarlane's work, Coal Regions of America, published in 1873, under the head of " Triassic Coal," chapter 27, gives what is known from existing publications of the position, geology, and production of the field, making

By Frank H. Macpherson

When it became apparent early in 1941 that the United States might be drawn into the war, studies were made of the bauxite situation in Arkansas, principally because 9.5 pct of the known bauxite reserves of the country were located in that State. Bauxite mining was then geared for maximum production to supply ore to meet this country's war requirements and, if necessary, to supply the needs of Canada as well. In view of the comparatively small bauxite reserves, Congress appropriated funds for an extensive exploratory drilling program to be carried out by the Bureau of Mines in cooperation with the Geological Survey. An alumina plant was erected near Bauxite and an aluminum plant near Hot Springs, Ark., by the Defence Plant Corp. The Metals Reserve Co. established a schedule of prices, arranged for stockpile sites and a buying agency. Operators cooperated to step up production and new ones came into the field. Production Record Prior to 1941, the greatest annual production in Arkansas was 562,892 long tons, dry basis in 1918. During the single month of August 1943, 693,596 long tons were mined—130,704 tons more than for the entire year of 1918. In general the Arkansas bauxite deposits are relatively small, irregular in thickness, somewhat scattered and, compared to coal, iron or open-pit copper deposits, are ill-adapted to an expansion in output. Commercial deposits range in horizontal extent from less than an acre to about 40 acres and are usually very irregular in outline. The average thickness of all known workable deposits is between 12 and 15 ft. with a maximum of about 60 ft. The ore bodies are usually somewhat undulating and nearly horizontal although locally some deposits dip as much as IS°. Types of Bauxite Three physical types of bauxite may be recognized: pisolitic, granitic and amorphous. Pisolitic ore is the most common type. It consists of small pebble-like nodules, ranging from the size of a pin head up to several inches in diameter, all set in a fine grained matrix. Transported bauxite is usually- pisolitic. Most residual bauxite is granitic. It is believed not to have moved appreciably from the location where it originally was formed. This is indicated by the fact that it appears to grade into unaltered nephelite syenite, which it overlies. Amorphous ore is the least abundant. It is nonpisolitic and resembles clay, has no characteristic texture, and can be identified definitely only by chemical analysis. Uses of Bauxite Bauxite is chiefly used for, and at the present time is substantially the only

Jan 1, 1948

By Frank H. Macpherson

When it became apparent early in 1941 that the United States might be drawn into the war, studies were made of the bauxite situation in Arkansas, principally because 9.5 pct of the known bauxite reserves of the country were located in that State. Bauxite mining was then geared for maximum production to supply ore to meet this country's war requirements and, if necessary, to supply the needs of Canada as well. In view of the comparatively small bauxite reserves, Congress appropriated funds for an extensive exploratory drilling program to be carried out by the Bureau of Mines in cooperation with the Geological Survey. An alumina plant was erected near Bauxite and an aluminum plant near Hot Springs, Ark., by the Defence Plant Corp. The Metals Reserve Co. established a schedule of prices, arranged for stockpile sites and a buying agency. Operators cooperated to step up production and new ones came into the field. Production Record Prior to 1941, the greatest annual production in Arkansas was 562,892 long tons, dry basis in 1918. During the single month of August 1943, 693,596 long tons were mined—130,704 tons more than for the entire year of 1918. In general the Arkansas bauxite deposits are relatively small, irregular in thickness, somewhat scattered and, compared to coal, iron or open-pit copper deposits, are ill-adapted to an expansion in output. Commercial deposits range in horizontal extent from less than an acre to about 40 acres and are usually very irregular in outline. The average thickness of all known workable deposits is between 12 and 15 ft. with a maximum of about 60 ft. The ore bodies are usually somewhat undulating and nearly horizontal although locally some deposits dip as much as IS°. Types of Bauxite Three physical types of bauxite may be recognized: pisolitic, granitic and amorphous. Pisolitic ore is the most common type. It consists of small pebble-like nodules, ranging from the size of a pin head up to several inches in diameter, all set in a fine grained matrix. Transported bauxite is usually- pisolitic. Most residual bauxite is granitic. It is believed not to have moved appreciably from the location where it originally was formed. This is indicated by the fact that it appears to grade into unaltered nephelite syenite, which it overlies. Amorphous ore is the least abundant. It is nonpisolitic and resembles clay, has no characteristic texture, and can be identified definitely only by chemical analysis. Uses of Bauxite Bauxite is chiefly used for, and at the present time is substantially the only

Jan 1, 1948

By David M. Cregger

The performance of the nation's first geologic repository for Commercial High Level Waste will be evaluated in a variety of ways which will involve the use of the state-of-the-art thermomechanical computer codes. Elastic properties of the host rock and the materials surrounding the repository are required for this numerical modeling effort to assess both near- and far-field effects. Only limited laboratory testing is possible, however, making it extremely beneficial to expand the data base by calculating dynamic elastic properties from available geophysical well logs. Elastic theory dictates that for an isotropic solid there are only two independent variables in addition to mass density, namely the compressional velocity, the shear velocity, and Poisson's Ratio. Compressional velocity and density are readily measured by geophysical well logs or in the lab; the crux of the solution requires measuring or determining either the shear velocity or Poisson's Ratio. Examination of acoustic propagated shear waves measured during confined compression testing demonstrates that Poisson's Ratio is a fundamental lithology-dependent parameter. Once a rock mass is appropriately classified, application of the laboratory derived dynamic Poisson's Ratio will yield a continuous and reasonable in situ modulus from acoustic and density logs. For preliminary characterization and assessment of the mechanical properties of rocks within the subsurface, and for studies of rock quality, this method is sufficiently accurate. The general availability of acoustic and density logs from wells logged for other purposes has made the application of this method desirable.

Jan 1, 1984

By J. H. Bechtold

Tensile properties of annealed molybdenum were investigated from 1000" to—200°C. In the vicinity of room temperature a well-defined transition in tensile properties occurs. Reduction in area decreases from over 80 pct to 0 pct and, simultaneously, the yield strength increases about 60,000 psi. MOLYBDENUM, tungsten, iron, and many other metals and alloys with the body-centered cubic and hexagonal close-packed crystal structures change from ductile to brittle behavior over some relatively narrow temperature range. The temperature at which this transition in ductility occurs depends on chemical composition, microstructure, and method of testing. When fine grained, completely recrystallized molybdenum of commercial purity is tested in uniaxial tension at a slow strain rate, the transition occurs at slightly below room temperature.' Iron2 and tungsten3 tested under similar conditions become brittle at temperatures close to the boiling point of nitrogen, — 195°C and at about 200°C, respectively. A sharp change in ductility is uncommon in metals with the face-centered cubic crystal structure, however, a relatively sharp transi- tion in notched bar impact properties has been observed below room temperature in a face-centered cubic copper-antimony alloy.4 A transition from ductile to brittle behavior is usually explained by the concepts originally developed by Ludwik,5 and discussed and elaborated on by others including Orowan,6 Hollomon and Jaffe,7 and Gensamer8 In brief, there are two aspects to strength, first the resistance to flow and second the resistance to fracture. Both are functions of temperature, strain, strain rate, stress system, composition, and microstructure. With decreased test temperature the flow stress required to initiate plastic deformation increases more rapidly than the fracture strength and brittle fracture occurs at that temperature where the yield strength equals or exceeds a brittle fracture strength. This investigation was conducted to determine the effects of temperature, strain, and rate of straining on the flow and fracture strengths of molybdenum above, through, and below the ductile-to-brittle transition. Other variables were held constant during testing. This information is believed to show

Jan 1, 1954

Secretary's NOTE—on page 176,of this paper, in the fourth line of the first footnote, " 4° " should, be " 1" )'; and on page 180, at the beginning of line 23, ('lined boot" should be " unlined boot." Discussion. Frank Owen, London, Eng. (communication to the Secretary) : In his very interesting and valuable paper, Prof. Snow

Jan 1, 1900

By Emil Gathmann

STEEL as it is poured, or teemed, into the mold for forming the ingot may be broadly separated into two divisions; i.e., effervescing or gassy steel, also termed evolution steel, and non-effervescing or killed steel, also termed solution steel. Between these primary divisions there are various types having the characteristics of both divisions but really not belonging to either; such steels are termed semi-piping, rising, or wild, as the type may be. True unkilled, or effervescing, steel should contain large volumes of gases, which are evolved while the metal is being teemed, or cast from the ladle nozzle into the mold, and while the temperature of the steel is being reduced prior to the solidification or freezing of the steel, the upper portion, or top, of the ingot remaining liquid due to the evolution of gases until an ingot skin of considerable thickness has been formed. These gases consist principally of hydrogen, carbon monoxide, nitrogen, and ammonia. It is generally understood that nitrogen gases are the first evolved and form the skin blowholes, at times troublesome, in the forming solidifying ingot. Ingots made of effervescing steel will always contain a large number of blowholes. Such blowholes are not deemed objectionable in various products if they occur well within the interior of the ingot where they will not be subject to oxidation upon the ingot's cooling and subsequent re-heating and rolling or forging. Very little top or bottom discard is taken from this type of ingot as pipes, or large shrinkage cavities, at the upper portion of the ingot do not usually occur, the difference in volume between the liquid and the solid steel (6 to 10 per cent.) being compensated for by the innumerable blowholes distributed throughout the body of the , ingot. Of the 40,000,000 tons of steel made in the United States during the year 1919, at least 35,000,000 tons of ingots were made of gassy or semi-gassy steel. Killed, or solution, steel is termed true piping steel from the characteristic pipe or shrinkage cavity that usually occurs in the uppermost central portion of the ingot.

Jan 8, 1920

By Nicholas J. Palethorpe

BACKGROUND Before addressing the above topic in any detail, it is pertinent to provide some background on Australia for those people who have not been there or who have a limited knowledge of our continent. Australia is approximately the size of the continental U.S.A. (excluding Alaska) covering an area of approximately 7 million square kilometres. It has a very dry climate which has led to a concentration of people in major cities scattered around the continents perimeter. Australia's population is currently approximately 15 million. Of the work force of 6.3 million, 72% work in tertiary industries, 20.2% in manufacture, 6.5% in agriculture and 1.3% in mining. Agriculture accounts for 46% of exports, mining for 31% and manufacturing for 23,. Economic activity is based on:- Agriculture This is capital intensive and covers extensive areas and is reliant on low cost farming. A.range of foods and fibres are produced with over 70% of production being exported. Such products are of course subject to the usual vagaries of world market demand and market access, particularly in regard to the operation of trade blocks such as the E.E.C. Mineral Resources A wide range of minerals and an abundance of iron ore, coal, gas and uranium resources provide an increasing volume of exports. However, Autralia's oil resources at present only supply approximately 70% of local requirements. Industry This is diverse and encompasses the processing of agricultural products and mineral ores as well as helping to supply the consumer and capital goods needs of the whole community. However, the small scale of local markets, the geographic isolation of Australia and relatively high wage costs have limited the scale of Australia's industry. Advanced technology has overcome some of these difficulties and high tariff and import quotas protect local producers from the full force of international competition. In 1980/81 Australia's Gross Domestic Product amounted to $130 billion with approximately 24% of this being devoted to investment. In the past decade Australia has experienced inflation rates ranging from 5% to 17% and only modest real growth rates ranging from 0.4% to 5% per annum. We have also experienced, as have many other industrialised nations, continuing wage and price increases. Unemployment presently stands at 6%. MINERAL DEVELOPMENT As the above figures indicate, Australia's continuing prosperity is very dependent on the mineral and agricultrual sectors of our economy. The dependence on these sectors is highlighted by the table below which indicates our position in a global context. [Australian Production of Minerals in a World Context Western World % Total Western World Position Mineral Production 1980 1st Rutile 75 Ilmenite 31 Zircon 70 Bauxite 36 Iron Ore 11 Tungsten 14 2nd Lead (Conc.) 15 3rd Manganese Ore 14 Brown Coal 11 (1979) Zinc (Conc.) 10 4thSilver (Conc.) 10 Nickel 6 5th Tin (Conc.) 5 6th Black Coal 5 Gold 2 Source: Mining Annual Review 1981] The total value of all mineral and fuel exports in 1980/81 is estimated at $5.9 billion. This prominence in the world mineral production has largely been achieved in the last 15 - 20 years. In fact, in the early 1960's, Australia had only 2 major mining export centres, Broken Hill in New South Wales and Mt. Isa in Queensland. This growth is highlighted by the fact that in 1963, for example, we exported only 9 tonnes of iron ore and less than 4 million tonnes of coal. In 1980/81 we exported 75m. tonnes ',of iron ore (valued at $1,117m.) and 47m. tonnes of coal valued at $1,965m.). The growth in our mineral industry has come about because of a number of factors. Abundance of Mineral Resources We are particularly well endowed with mineral resources, as indicated below.

Jan 1, 1982

Institute of Metals Division Iron and Steel Division Extractive Metallurgy Division Council J H Scaff (IMD) Chairman, Robert W Shearman, Secretary, J S Smart, (IMD), P T Stroup, (EMD), A W Schlechten, (EMD), J S Marsh, (ISD), A W Thornton, (ISD), M E Violin, (MED), D S Eppelsheimer, (MIED) Journal of Metals Editorial Advisory Committee J S Smart, Jr, Chairman, W A Dean, J C Kinnear, Jr, T D Jones, Evan Just, John Marsh, M Tenenbaum Pacific Northwest Regional Conference A Y Bethune, General Chairman, Frank N Marr, Chairman, General Arrangements, R J Lapee, Chairman, C P Love, (EMD Program), W M Armstrong, Chairman, Physical Metallurgy Program, L W Heinzinger, Chairman (ISD Program), J P Spielman, Chairman, (MIED Program) New England Regional Conference K H Mairs, Chairman, W A Backofen, Vice-Chair¬man, Delmar E Trout, Secretary, G W Coleman, Treasurer, F H Wilson, Past Chairman, Members at Large Sidney Siegel, Boston, G F Donahue, Connecti¬cut Representatives from Connecticut Frank Chudy, J E Chafey Representa¬tives from Boston N L Reed, E Gordon

Jan 1, 1955

By E. I. Alessandrini, A. U. Seybolt

Selective oxidation (preferential oxidation of a single alloy component) can be an important oxidation mode in the case of alloys such as Si-Fe, Al-Fe, and so on, when heat-treating in atmospheres of low oxygen potential. It was the purpose of this work to identify the oxide films formed on iron containing 31/4 pct Si at low oxygen potentials, and to make some observations on the H2O/H2 ratios required to form them. EXPERIMENTAL METHOD HYDROGEN of varying water content offers a very convenient method of establishing a wide range of oxidizing power, or oxygen potential. The method chosen to provide a desired H2O/H2 ratio was to nearly saturate hydrogen at room temperature by bubbling the gas through water at room temperature, and then to wring out the excess water by passing the wet gas through a long glass spiral immersed in a refrigerated liquid at a desired dew point. After oxidation, the samples were examined by electron diffraction in order to identify any film which might be present. PREPARATION AND TREATMENT OF SAMPLES The samples were prepared from a Si-Fe alloy made in the laboratory using electrolytic iron and 96 pct ferro-silico11, vacuum-induction melted, hot-rolled then cold-rolled to 0.015-in. thickness. After the cold-rolling the samples were annealed at 1000°C. Transmission Laue X-ray patterns showed very little evidence of preferred orientation, but it is likely that a weak texture could have escaped notice. The chemical analysis was as follows: 3.34 Si, 0.01 Al, 0.001 0, 0.006 C, 0.002 N. Before each sample was oxidized, it was polished through 4/0 emery paper, cleaned and dried using benzene, carbon tetrachloride, acetone, absolute alcohol, and ether. The method of oxidizing the samples was as follows: Samples about 1/2 by 1 by 0.015 in. were held in the upper, cool part of a vertical vacuum furnace until the desired temperature was established in the furnace, Fig. 1. The sample was then lowered into the uniform hot zone where it was heated quickly to the desired temperature, and subjected to hydrogen of controlled moisture content (dew point) as mentioned previously. Temperatures from 400" to 1000°C were used, and dew points from room temperature to —78°C were explored. In general, the runs lasted about 6 hr, but a few runs were of different duration, as will be indicated later. After the predetermined period of time had elapsed, the specimens were withdrawn by the hollow stainless steel-quartz holder to a cool zone at the top of the furnace. EXPERIMENTAL RESULTS The results are summarized in Table I. Most of the electron-diffraction patterns were obtained by glancing-angle reflection, but in a few cases it was possible to strip the oxide films from the surface by a total immersion in a 3 pct bromine-methanol solution. Some of the thinner stripped films yielded quite satisfactory transmission patterns. However, both diffraction techniques yielded the same results; the patterns while most frequently showing a (low) tridymite, also showed a (low) cristobalite in some cases. A few patterns showed evidence of both phases. Because of the known nonequilibrium behavior of silica, it is not surprising that both forms of silica could coexist on one sample. It was noted that at fairly low dew points such as —40°C, there was a tendency for diffuse diffraction rings, suggesting a very small crystallite size. Also some subsequent experiments to be reported later show that thin silica films can be amorphous.

Jan 1, 1959

By Oliver B. Hopkins

Peru produced approximately 17,466,620 bbl., of oil during 1937, or slightly less than the record high of 17,593,700 bbl. established during 1936. As in 1936, the entire output of the country was derived from the La Brea-Parinas, Lobitos-Restin and Zorritos fields in the northwestern part of the country. Outside of the proven areas, drilling was 'continued by the Peruvian Government in the northern province of Tumbes on the reserved zone at Zorritos. Drilling was carried out on three locations, two of which are understood to have been abandoned during the year. In southern Peru, further attention was given by Government engineers to the Pusi and Saman districts and plans are being worked out for the commencement of drilling operations in the near future in the vicinity of Pirin. Activities in the montaiia region in eastern Peru were continued by the Compafiia Petrolera El Ganso Azul. This company acquired the interest of the Selden Breck Co., and holds some 90,000 acres along the Pachitea River a few miles above its confluence with the Ucayali. During the year, the preparation of a landing place, the cutting of a 12-km. (71/2-mile) road from the river to the drill site, and the construction of a camp were undertaken. Equipment for drilling on this company's concessions has already arrived in South America. La Brea-Parinas Estate.—Production of crude oil on the La Brea-Parinas Estate of the International Petroleum Company Limited amounted to 14,722,754 bbl. during 1937, a decrease of 403,736 bbl. from the all-time high reached during 1936. The total production from 1890 to Dec. 31,1937, was 178,390,767 bbl. During 1937, a total of 141,653 ft. was drilled, 129,516 ft. in new wells and 12,137 in deepening existing wells. In all, 57 wells were completed, 47 of which produced oil, 2 were gas wells and 8 dry. holes. Twenty-nine wells were cleaned out or deepened during the year. The average depth of new wells completed during 1937 was 2367 ft. compared with 1984 ft. for the new wells completed during 1936. There was an increased use of rotary tools during the year and this method is now used to a greater extent than the cable-tool method, which formerly predominated. Of the 57 wells completed during the year, 31 were

Jan 1, 1938

By Homer N. Mead

This report develops equations for decline curve analysis based upon the premise that the rate of change of the reciprocal of decline for succeeding time intervals is constant when the reservoir is produced under a fixed set of conditions. A method is shown for predicting maximum production rate against cumulative production for any reservoir. A method is also presented for predicting future production rate by an analysis of past production performance after decline has been esrahlished. INTRODUCTION No significant contribution to the analysis of decline curves by the loss-ratio method has been made since J. J. Arps paper1. The concept of loss-ratio that was developed by Arps and his contemporaries has been redefined in another way and the concept of instantaneous loss-ratio at time zero has been added. In the mathematical developmerit by Arps, production rate was related as a continuous function with time and his equatlons were developed on that basis. In this paper, production is considered to be a series of segments for equal time intervals and equations have been developed based upon these finite differences. It is realized that decline curve analysis is not the answer to all predictions of reservoir behavior. However, as production must decline from an initial maximum rate to zero in any reservoir, if such decline can be expressed as an infinite series, this series should accurately predict production. Decline curve analysis should be considered a valuable tool that may be used in conjunction with predictions of future recoveries by other methods. Various uses of the decline curve method will be discussed in this paper. Equations predicting production rate at any time and cumulative production by exponential and hyperbolic decline will be developed. Characteristic values of b related to various types of drive will be discussed. After that a hypothetical reservoir will be studied and ultimate recovery by natural depletion and pressure maintenance compared, then actual field examples will be shown and discussed. The rate-cumulative curve introduced by H. N. Marshs in 1928 is an important one for use in estimating future production rate and ultimate recovery. This graphical method is the one that is used in conjunction with the equations to be developed for predicting production behavior. EXPONENTIAL DECLINE In exponential decline each succeeding production rate per unit of time is a constant percentage of the production rate just before it. Since (1 — r) is the common ratio, where r is the constant decline rate, this condition may be expressed as a geometrical progression; thus Pn = P (1 - r)n-1 . ......(1) Where r is less than unity, r Since P1 (1 - r)n = Pn+1 P1 - Pn+1 C =P1-Pn+1/r........(2) LOSS-RATIO In this paper the calculation for loss-ratio has been changed from the method presented by Johnson and Bollens2. The first loss-ratio to be calculated is a,; it is the initial production per unit of time after decline has set in divided by the difference between the initial and the second production rate. This loss-ratio is for the first time interval. After b (which is the constant change

Jan 1, 1957

By J. Chipman, G. G. Hatch

T. ROSENQVIST*—It is a pleasure to see the excellent way in which the experimental part of this work has been handled. There seems to be little doubt that the distribution data obtained corresponds most closely to thermodynamic equilibrium under the prevailing reducing conditions, namely equilibrium with graphite and one atmosphere CO pressure. The desulphurization curves in Fig 10 show the same general feature as the curves given by Holbrook and Joseph, but the distribution ratios are from 20 to 40 times greater—undoubtedly due to a closer approach to true equilibrium. In the theoretical discussion, the authors calculate a theoretical distribution (S) ration -jg-. which they find to be about 50 times greater than the experimental. The deviation is so great that the basis for their calculation needs a more thorough examination. The authors base their thermodynamic calculation on free energy expressions where diluted solutions of FeS and CaS are used as standard states. (The activity coefficient in diluted solutions is taken to equal unity.) Such a standard state will change when the nature of the solvent is changed. Taking the free energy of the reaction [FeS] ? (FeS), Eq 2, which is derived from the distribution of sulphur between an iron and a FeO-melt, it is very unlikely that the free energy of this reaction will be the same for a distribution between pig iron and a calcium silicate slag. Therefore a more fundamental basis for the thermodyuamic calculations seems needed, where all thermodynamic equations are referred to unambiguously defined standard states. The most natural standard states for CaO and CaS are the pure solid substances at the same temperature. As standard state for sulphur in iron, pure liquid FeS can be used. This rules out Eq 2 [FeS] ;=s (FeS) because ?F° = 0. The standard equation will then be: FeS, + CaO6 + Cgraph ?Fei + CaS8 + CO. vFo1773 = 25,000 cal It would be more universal and also simpler to refer the escaping tendency of sulphur in liquid iron to the corresponding H2S/H2 ratio which can readily be determined experimentally. As standard state a gas mixture H2S/H2 = 1/1 can be used. (This corresponds at the temperature of liquid iron closely to one atmosphere S2 vapor.) Thus the standard equation for the sulphur reaction can be formulated as follows: H2S0 + CaO3 + Cgraph ?H2o + CaS8 + COg The standard free energy of this reaction has been calculated from the best available data to AF°m3 = —35,000 cal. This gives for the equilibrium constant at 1500°C Now, the solubility of CaS in blast furnace slags has been determined by McCafferey and Oesterle* and corresponds at 1500°C to about 10 pet S (varying somewhat with the composition of the slag.) If the activity of CaS is assumed linear between 0-10 pet as curve 1, (see Fig 11), then acaO = 0.1 (S); (S) being wt. pet sulphur in the slag. For a diluted solution of sulphur in an iron melt saturated with carbon, the ratio H2S/H2 is, according to Kitchener, Bockris and Liberman,f about 0.01 [S], [S] being wt. pet sulphur in iron. Substituting these values in the expression for Kp we find The value 2.103 is only 4 times greater than the experimental coefficient found by Hatch and Chipman, but the value is very sensitive to a small error in AF°. A better agreement with the experimental distribution coefficient can be obtained if one assumes the activity of CaS to run like curve 2 (Fig 11). This (S) will give a lower theoretical W, value, a value which varies with (S) exactly as Hatch and Chipman learned. Such a shape of the activity curve, which corresponds to a positive deviation from Raoult's law, is actually to be expected from the fact that liquid silicate and sulphide phases usually show incomplete miscibility. A closer agreement between experimental and theoretical data can not be expected before we have more complete data for the individual activities of CaS and CaO in the slag. The activities acaS and Ocao referred to the solid phases as standard states, are exact defined quantities contrary to the somewhat undefined expression "free lime," and they are independent of any theory for the constitution of liquid slag. J. CHIPMAN (authors' reply)—The authors wish to thank Mr. Rosenqvist for his very interesting and useful thermodynamic addition. Curve 2 of his figure offers the needed basis for explaining the increase in the ratio (S)/[S] with increasing sulphur content. Attention is called to an error in the printed paper: Fig 2 and 3 are reversed. M. TENENBAUM*—In the figures showing the relationship between excess base and sulphur distribution (Fig 6, 7 and 9) the slope of the curve tapers off in the negative basicity range. Somewhat the same thing is observed with open hearth slags. In that case, the fact that some sulphur distribution between slag and metal is obtained with negative basicity is interpreted as indicating some dissociation of the lime silicate compounds whose existence in oxidizing basic slags has been used to explain various observed phenomena with regard to other slag-metal reactions. In the case of the blast furnace slags, the reduced slope of the sulphur distribution curve with decreasing excess base is attributed to the amphoteric effect of alumina. Has the possibility of other explanations been investigated ?

Jan 1, 1950

By John W. Cabot

In the manufacture by the Bessemer process of soft steel suitable for rolling into fine sheets, tubes and 60 forth, a difficulty is sometimes met with, in the tendency of this kind of metal to rise violently and boil in the moulds while being cast; this results in hollow-topped ingots, and consequently in an undue amount of scrap in the subsequent rolling. It has been noticed that this peculiarity does not pertain to all pig-irons, some grades producing a blown metal which pours quietly, while others, in whatever way the blow may have been conducted, give a metal which rises in the moulds, accompanied by the evolution of large quantities of hydrogen and carbonic oxide gases, and requiring a long time to solidify. This difference in behavior has been some-

Jan 1, 1891

By P. E. Busby, C. Wells

FURTHER study of data used in determinations of 1—rates of diffusion of boron in austenite and 2—solubilities of boron in the a and phases of iron and steel' has provided an equation for the diffusion of boron in a iron. In brief, the previously published data were accumulated from the results of deboron-izing (and decarburizing) experiments carried out in the range of 700° to 1300°C. Diffusion coefficients (D?) for boron in austenite were calculated using the Grube solution of Fick's law. However, only solubility values were estimated from the discontinuous concentration-penetration curves, Fig. 1, which are characteristic of diffusion in two phases. Dr. Carl Wagner' has recently provided a solution for calculating D values from penetration curves of this type as follows: Cl1.1 —C8/C8- C11.1 = vp ? e ? erf (?) and D = ?/4?2 t where C11,12, C8, C11, and E have the values shown in Fig. 1. D is the diffusion coefficient, sq cm per sec; t is time of deboronizing anneal, see; and ? is a di-mensionless parameter. For a given diffusion experiment, the value of ? can be readily obtained by graphical solution from a plot of y vs the right-hand part of Eq. 1. D may then be evaluated from Eq. 2. The avplication of this solution to previously re-ported results, of which excerpts are given in Table I, permits the calculation of diffusion coefficients for boron in a iron. On the basis of these meager data, it is tentatively concluded that the diffusion of boron in a may be represented by the equation Da = 1011 e-92,900/RT where R is the gas constant, cal X 0C-1 X mol-1; and T is the absolute temperature, OK. Although the frequency factor, 106 sq cm per sec, is admittedly several orders of magnitude higher than expected, the value of Q, 62,000 cal per mol, appears reasonable and is, in fact, very similar to that for the self-diffusion of iron. It is pertinent to mention at this point that the value of Q obtained for the diffusion of boron in austenite by means of the Wagner solution is 19,000 cal per mol and is in excellent agreement with the value previously reported1 in the equation DT = 2xl0-3 e-21,000/RT [4] which was determined by the application of the Grube solution to other data. The fact that determined constants A and Q in the equation D? = A e-Q/RT were practically the same, independent of whether the Wagner or Grube solutions were used in determinations of D values, strengthened the authors' belief that the computed values of D (Table I) using the Wagner solution are reliable. The relative values in Eqs. 3 and 4 for the diffusion of boron in the a and ? phases, respectively, suggest that boron forms a substitutional solid solution in a iron and an interstitial solid solution in ? iron. The same tentative conclusion has been reached by McBride et al.3 on the basis of relative solubilities, atom diameter, and the size of the interstitial hole in a and ? iron. In connection with the data for test 14 listed in Table I, it is of interest to calculate the solubility of boron in a iron using the D value given by Eq. 3. As might be anticipated from the small movement of the interface in test 14, proper substitutions in Eqs. 2 and 1 give a low value, approximately 0.0004 pct B, at 850°C. Apparently at 835°C (test 13) it is possible to obtain 0.0018 pct B, and at 850°C only 0.0004 pct B into solution in the a phase before a second phase appears. These observations are consistent with the Fe-B constitution diagram proposed by McBride, Spretnak, and Speiser.3 References P. E. Busby, M. E. Warga, and C. Wells: Diffusion and Solubility of Boron in Iron and Steel. Trans. AIME (1953) 197, p. 1463; Journal of Metals (November 1953). 'W. Jost: Diffusion in Solids, Liquids, Gases. (1952) pp. 69-71. New York. Academic Press Inc. "C. C. McBride, J. W. Spretnak, and R. Speiser: A Study of the Fe-Fe2B System. Trans. ASM (1954) 46, p. 499.

Jan 1, 1955

By Gordon G. Bentle, W. P. Fishel

GREINER, Marsh, and Stoughton1 have reviewed the literature in a monograph on the iron-silicon system. The lack of agreement among the various studies may be due to the difference in the purity of materials in some cases. The results of the X-ray method indicate only a general rather than a specific limit of the y loop. The iron-titanium system was investigated by Roe and Fishel,' whose results are used in determining the iron-silicon-titanium y loop. The literature indicates that no study has been made thus far of the iron-silicon-titanium system in the y loop region. Experimental Procedure The alloys were made from Armco iron, 99.86 pct Si, and 98.5 pct Ti. The titanium contains 1.07 pct Fe. The Armco iron contains 0.01 pct C, 0.005 pct Si, 0.02 pct Mn, 0.006 pct P, 0.01 pct S, and 0.04 pct Cu. A dilatation sample of Armco iron was prepared in the same manner as were the other samples. Several dilatation runs indicated that Ac3 begins at 905°C and ends at 910°C, which compares favorably with the study of Wells, Ackley, and Mehl' employing specially purified iron. All alloys were melted in an induction furnace in Alundum crucibles and were top poured into baked core sand molds. The ingots weighed about 600 g as cast. Dilatation samples of 4 in. by % in. diam were taken from the bottom end of the ingot, from which turnings for analysis were taken. Turnings from each end of two of the samples indicated that the alloys possessed uniform silicon content. A hole was drilled halfway through each end of a 4 in, dilatation sample. A chromel-alumel thermocouple was inserted in each hole and the surrounding metal peened in to hold the thermocouple in place. Fig. 1 represents the dilatation apparatus. The heating unit is an Alundum tube wound with resistance wire; the dilatation tube is a McDanel combustion tube; the push rod is zircon; the dial gage is graduated in 0.0001 in. and was vibrated to prevent sticking. A blank run over the temperature range of interest gave no significant dilatation. The thermocouples were attached to a multiple recording micromax which indicated the temperature at each end of the sample at 35 sec intervals. A Lindberg control unit governed the rate of heating of the furnace, and lowering or raising the

Jan 1, 1957

By F. E. Pawlek, J. K. Gerlach

The chloridizing roasting of ores is applied when metal sulfides and oxides are to be converted into soluble or volatile compounds. The chlorine required is either obtained from the admixed chlorides of sodium or calcium or added in the gaseous state. In the first part of the investigations the reaction rate of the chlorides of sodium or calcium with gas mixtures of SO,-0, or SO ,-O2 ,-SO , was measured. The rate for reactions with gas mixtures SO2-O2 is ThE chloridizing roasting of ores is applied when metal sulfides and oxides are to be converted into soluble or volatile compounds. At present the process is mainly applied to produce nonferrous metals which occur in pyrite cinders in small concentrations. Thereby the nonferrous metals are converted into water-soluble, acid-soluble, or volatile compounds whereas all the iron remains as insoluble oxide. The chlorine required is either obtained from the admixed chlorides of sodium or calcium or added in the gaseous state. The reactions occurring during the roasting process can be divided into two groups: solid-solid reaction and gas-solid reaction. The reactions between solids proceed by means of solid-state diffusion and are therefore of low velocity. The heterogeneous reactions between solids and gases of the roasting atmosphere5 are high-velocity processes and determine the velocity of the chloridizing roasting. These gas-solid reactions shall be the subject of the paper presented. In order to investigate the still little-known processes which occur during the chloridizing roasting 6-' the complex reaction is split into several partial steps. First the reactions of NaCl and CaCl, with gas mixtures of SO2 and 0, have been investigated at temperatures between 500" and 600°C by measuring the weight increase of the samples. The gas mixtures used in this series of experiments had first variable compositions, then the amount of SO 2 had been increased. Furthermore the influence of Fe 2 O3 admixtures upon these reactions, the behavior of pure Fe 2 O3 with the gaseous reactants, and the chlorination of the sulfides of lead, copper, nickel, and zinc have been investigated. FORMATION OF GASEOUS CHLORINE Pyrite cinders are never completely roasted and therefore contain still a small amount of sulfide sulfur. When heated again in air, this sulfur is converted into SO,. Accordingly the formation of chlorine can first be described by the reactions: dependent on the composition of the gas phase. If more than 1 pct SO 3 is added to the roasting gas, the reaction rate is determined only by the concentrations of the SO,. In the second part the reactions between chlorine and metal sulfides are discussed. The rate of formation of gaseous chlorine is higher by me order of magnitude than is the reaction rate between ZnS and chlorine. The reaction rate of NiS and PbS lies considerably below that of ZnS. The conversion rate of both pure Fe 2 O 3 and Fe 2 O 3 containing NaCl or CaCl2 when reacting with SO2-O2, mixtures with and without SO3 portions was measured at temperatures of 500", 550°, and 600°C. The weight increase of pressings was determined by means of a spiral balanceg and the reaction rate calculated therefrom according to Eqs. [ll to [31 and [5] to [7]. The prepared samples were suspended on a platinum filament in a vertically mounted tube of mullite (ID 4 cm, length 110 cm) which could be heated by a resistance tube furnace. The platinum filament was tied to the lower end of the spiral balance. A supremax glass tube (length 70 cm) was mounted gas-tight on top of the reaction tube. The unit was sealed up at its top by a ground-in stopper which was holding the spiral balance with the sample. The spiral balance therefore hung outside the high-temperature region of the furnace. Fig. 2 shows the experimental arrangement schematically. While lowering the sample into the reaction tube pure nitrogen was flowing through the reaction zone providing a protective atmosphere. After the sample had reached the reaction temperature within approximately 1 min, the protective gas was replaced by the sulfur dioxide-oxygen reaction mixture. It took about 30 sec until the mixture filled the tube homogeneously. A Ni/NiCr thermocouple placed in the center of the furnace where the sample hung during the measure-

Jan 1, 1968

By K. L. Fetters, F. M. Walters

ALL previous records were broken by the Iron and Steel Division, in the number of sessions, the number of papers, and the attendance. In addition to ten papers (all preprinted) on properties, structure, aid hardenability of, carbon and alloy steels, eight formal papers were presented on one or more phases of steelmaklng, and a symposium on the determination of hydrogen and nitrogen in steel. This last started at 2 p.m. and was going strong with more than a third of the audience still present at 6 p.m.

Jan 1, 1944

By Arthur F. Taggart

In 1900, Elmore found that if an acidulated pulp was stirred up with an oil which was relatively insoluble in and lighter than water, and the mixture was allowed to stratify, much of the sulfide would be found hanging to the lower surface of the floating body of oil and could be skimmed off or overflowed with it. The action of the flotation agent here is twofold, first to select the sulfide from the gangue—what today is called collection—and second, to buoy the collected sulfide away from the gangue. The action in collecting is illustrated by Fig. 1: which contrasts the behavior of drops of oil brought, under water, to the surfaces of gangue and sulfide particles, respectively. The oil displaces water from the surface of the sulfide; the water displaces oil from the gangue surface. If, instead of considering the solid particles the fixed parts of the system of oil, water and solids. we consider the oil and water fixed and the solids presented to the surface of contact, the condition will be as shown in Fig. 2; the sulfide tends to be drawn into the interface and the gangue to be excluded. The sulfide particles are held in the oil-water surface by the tension of this surface. The buoyant effect is supplied by the oil droplets in bringing the sulfides to the water surface, but not in holding them there. Gas as Buoyant Medium of Flotation In 1906 Sulman. Picard and Ballot discovered a practical and substantially fool-proof method of doing what Everson, in 1886, and Fro-nlcnt. DeBavay Bessel and Elmore had been doing in the intervening years, viz.: using gas in place of oil as the buoyant medium for flotation, but retaining oil as the agent. To all of these inventors "oil," with no qualification as to its kind and no true understanding of its function, was the important thing. Hut they placed on the oil an additional burden viz.: froth-making, and it soon became apparent that not all oils were suitable for the dual purpose. As a matter of fact, it is probable that each of these inventors knew only one suitable oil at the time he wrote his patent, but used the generic term in the patent with the usual idea

Jan 1, 1928