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By J. Chipman, H. Towers, M. Paris

A simple radioactive tracer technique is used to measure the diffusion coefficient of calcium ion in molten slags. In a slag of 40 pct Ca0-40 pct Si0,-20 pct Al203, Dc " at 1450°C is 1.3x10-6 cm' sec-'. THE application of the principles of thermodynamics to steel and iron making problems has proved so fruitful that the kinetic approach has tended to be neglected. It seems probable that in some reactions the rate-determining step is the dif-fusivity of the reactants or of the products. But knowledge of the diffusion coefficients of the constituents of liquid slag and metal is singularly lacking. The present work was undertaken as a first step toward supplying such data for slags. Furthermore, any additional information on the physical properties of liquid slags might be expected to help in elucidating their structure. It is essentially a preliminary investigation, the course of which was determined more by the necessity of establishing a method than by the immediate intrinsic interest of the results. For example, the selection of calcium ion to be studied was dictated by the suitability of the isotope Ca45 in that it is a simple emitter with a long half-life. Of the other ions commonly encountered in slags, the isotopes of iron and manganese have relatively complex radiations as well as the normal disadvantage of requiring control of the oxygen potential of the atmosphere; Mg27 and Al29 have half-lives measured only in minutes; Si3' has a simple decay process but its half-life of 2.8 hr is too short for preliminary studies; the only useful oxygen isotope is the stable O18; and there remain only sulphur and phosphorus both of which have suitable isotopes but were rejected as being of less fundamental interest than calcium. Similarly a lime-alumina- silica slag was used in preference to calcium silicate primarily because of its low melting point and its capacity to form a glass on fairly rapid cooling. Literature Review Very few studies of diffusion in liquid silicate systems have been reported. In order to determine the origin of diopside inclusions in felspathic rocks, Bowen1 investigated the diffusion between diopside and various mixtures of albite and anorthite. Platinum crucibles were used with diopside, the heavier of the two liquids, forming the lower half of the cell and diffusion taking place against gravity. Change in concentration along the diffusion path was found by measuring the refractive index of the quenched glass. Nearly thirty years later McCallum and Barrett2 used essentially the same method to determine the diffusion coefficient of lime in lime-alumina-silica slags. In this case the interest was to find the rate-determining step in the process of slag attack on refractory materials. In an investigation of the kinetics of the sulphur reaction, Derge, Philbrook, and Goldman8 determined the diffusion coefficient of sulphur in a typical blast furnace slag by the simple procedure of melting a slag containing 2 pct S over an identical slag sulphur-free. They make no claim to a high degree of accuracy but suggest that D, is of the order of 10-6 cm2 sec-l. Other high temperature liquid diffusion studies have been concerned with metals. Holbrook, Furnas, and Joseph4 determined the diffusion coefficients of silicon, phosphorus, sulphur, manganese, and carbon in liquid iron by immersing a small carbon crucible containing pure iron-carbon alloy in a large vessel containing iron with a high concentration of the particular element. Their results were confirmed by Paschke and Hauttmann5 using a similar method. Diffusion coefficients in silicates in the glassy state have been studied by Johnson, Bristow, and Blau6 Both Na24 and Ca45 were used as tracers but only the

Jan 1, 1954

By A. T. Shurick

THE NRA Administrator's casual reference to the coal code as the next "pineapple" to be fixed was a conservative estimate of his job. This thorny and adamantine morsel now looms as a critical test of NRA. A failure in coal supplies would have the gravest potentialities in the Administration's program at this time. And the loss of prestige from a breakdown of the enforcement machinery in this initial large-scale test of strength would accentuate the incipient indications of insurrection in other directions. General Johnson has had a difficult task. It involves problems festering for a quarter of a century. A succes¬sion of Presidents have been glad to tide over their respective regimens with inconclusive expedients; they have been baffled by the complexities of the technical angles and hopelessly irreconcilable concepts of powerful conflicting interests with large issues at stake.

Jan 1, 1933

By Raymond M. Howe

Some time ago, a prominent engineer asked a representative of the firebrick industry to prepare a comprehensive paper on blast-furnace refractories. It was to have been the purpose of this paper to gather practical experiences from widely different sources, in the hope of determining what kind or kinds of firebrick were best adapted for certain uses. This engineer sent questionnaires to the large consumers of blast-furrace linings and stovebrick and received very detailed replies as to their experiences. These replies are conflicting, but, having been turned over to the writer, form the basis of this attempt to meet the request. Because of the impossibility of making final recommendations at this time, a few of the more interesting and commonly known methods of studying refractories are also discussed, as well as the more recent developments in this field. The first reply to the questionnaire stated that good service was being secured from the linings. This satisfactory condition was attributed to the use of a very good distributor. The writer believed that manufacturers try to and do produce a good product and that the proper handling of equipment is of the utmost importance, if good results are to be secured. The type of bricks used was not mentioned. The second reply stated that good life was secured from the furnace linings, but that the writer had had soft-fired stovebrick crumble and, for that reason, preferred a hard-fired product for use in this position. The type of bricks used was not mentioned. The third reply stated that firebrick had crumbled from the mantle up; the cause was not known. The fourth reply stated that the stove linings were satisfactory. Hand-made furnace linings failed after.4 years' service so a steam-pressed lining- was installed which was still good after 4 years of service. Consequently, a second steam-pressed lining was installed but this disintegrated at the top after the furnace had been in blast 7 months. The firebrick manufacturer attributed this failure to the expansion of iron blocks that had been installed at the stock line to prevent erosion. The fifth reply stated that the present "hard-burned" hand-made furnace lining had worn away very uniformly to the depth of only 5 in.

Jan 1, 1920

By H. E. Hawkes, D. A. Barr

Time variations in the copper content of the sediments of streams draining mineralized areas were studied in two areas of contrasting climatic environment, one in northern and one in southern British Columbia. In each area, samples were collected and observations made of rainfall, stream discharge and air and water temperature at intervals throughout the summer season. Samples were analyzed for total and cold-extractable copper. Results showed a weak inverse relation between cold-extractable copper and discharge in two out of the three test sites in the southern area, and a decrease in ratio of COld-extractable to total copper over the duration of the test period at a highly anomalous site in the northern area. In suspended rock flour resulting from glacial erosion of mineralized rock in the northern area, virtually all the copper was found to be soluble in cold, dilute hydrochloric acid. None of the variations observed is sufficient to cause serious problems in geochemical sediment surveys. Systematic collection and trace analysis of stream sediments has seen wide application in recent years as a method of primary prospecting in primitive areas. Common practice is to collect fine-grained samples of sediment either from the active channel or from the flood plain near the channel. Samples are dried, sieved and the -80-mesh fraction analyzed after breakdown of the sample by a relatively strong attack, such as by fusion or by treatment with hot perchloric acid. Drying, sieving and rigorous chemical attack requires established facilities, either in a well equipped central laboratory or in base camp. Thus analysis for total metal involves a substantial delay from the time the samples are collected until the analytical data can be reported. An alternative system uses a cold aqueous extrac-tant in place of the hot acid or flux.4 Advantages of the cold-extraction techniques are that kits can be prepared for use directly at the sample site and that, in some problems, the patterns in cold-extractable metal, usually abbreviated cxMe, are more useful as ore guides than the patterns in total metal.' In the course of operational geochemical sediment surveys, a problem that has come up repeatedly is failure to reproduce anomalous values or patterns by resampling the same areas. The mystery of the vanishing anomaly has led to speculation as to whether there is a significant variation in the metal content of sediment samples with the weather or with the time of year. Review of the published literature shows that a number of experiments have been carried out on time variations in the metal content of stream water.1,2,5,7-9 The only published report on time variations in stream sediments that has come to the authors' attention, however, is by Govett,3 working in Northern Rhodesia.

Jan 1, 1963

By N. A. Gokcen

The construction and operation of a simple and accurate vacuum-fusion apparatus are described in detail. Absolute accuracy of the oxygen analysis has been determined by the reduction of oxides weighed to 20.01 mg. The Bureau of Standards steel samples have been analyzed repeatedly, and their inadequacy for the acceptable range of oxygen is presented. The limits of interference of manganese, aluminum, and titanium, and the effects of tin and water-cooling of the furnace tube have been investigated in detail. ANALYSIS by the vacuum-fusion method consists of melting a sample in a degassed graphite crucible under high vacuum and extracting oxygen as carbon monoxide, and nitrogen and hydrogen as gaseous elements. The resulting gas mixture is analyzed for its constituents, from which oxygen, nitrogen, and frequently hydrogen may be determined within 1/2 hr or less. The history and summary of methods1-4 and extensive reviews of literature'.' for the determination of gases in metals have been published in detail. The foundation of the modern vacuum-fusion method of analysis was laid by Jordan and Eckman,11 and Oberhoffer and his associates.1, 10 Diergarten,11, 12 Meyer,13 Thanheiser et al.,14, 15 Ericson and Benedicks,16 Ziegler,17, 18 Sloman,16-23 Thompson et al.,24 and later many others contributed to the improvement, accuracy, and limitations of the method. In some investigations, however, the limitations of the procedure and the errors involved in the analysis require further critical examination and evaluation. In many apparatuses, lunnecessarily complicated and cumbersome features and elaborate precautionary measures do not have conclusive advantages. The purpose of this invest:igation was, therefore, a) to construct a very simple and accurate apparatus, b) to determine the absolute accuracy of results, c) to establish the limits of interference of manganese. aluminum, and titanium, d) to reexamine critically the reduction and recovery of oxygen from oxide powders of various sizes, and e) to evaluate critically the eight steels of the Bureau of Standards."' Apparatus The apparatus used in this investigation is shown in Fig. 1. It has been used for over three years, during which several modifications were made. A brief description of the apparatus is as follows. The transparent silica or Vycor tube, E, is joined to the Pyrex head, B, by mean of a face to face ground joint sealed with mercury. A similarly sealed ball and socket joint would also have been satisfactory. A standard tapered ground joint, successfully used by some investigators, was tried, but in the absence of grease or vacuum cement it was very difficult to disassemble the joint. The graphite crucible, G, 15/16 or l 1/8 in. OD, 2 1/2 or 3 in. high, 1/10 in. wall, shown enlarged in Fig. 3a, is made from the rods containing less than 0.08 pet ash. Two baffles, overlapping sufficiently to prevent spattering, are inserted in two opposite slots cut on a band saw. Two small holes in the baffles permit the temperature measurement of the melt. A second type of crucible, Fig. 2, G, shown enlarged in Fig. 3b, is also satisfactory, though not as convenient as the crucible shown in Fig. 3a. Somewhat similar but more elaborate crucibles with baffles were first tried by Ericson and Benedicks,'" but were abandoned in favor of a crucible with a stopper and a peripheral graphite powder filter. Various versions of their crucible with a stopper have later been used by other analysts, 10-27, 27-30 The crucible is packed directly in E, Figs. 1 and 2, with —35 + 48 graphite powder for shielding and insulation. A minimum layer of 7 mm of powder is necessary for keeping E cool and minimizing the blank. The first use of graphite powder was made by Sloman,10-23 Who found that —200 mesh was the most satisfactory. The author tried various size powders from +20 to —100 mesh and found that a) particles of 28 mesh or larger were not sufficiently insulating and were heated by the induction current, b) the powder finer than 60 mesh packed too much and did not readily permit the escape of gases even when the crucible was heated very slowly; hence, the powder was occasionally blown out of the side in the crucible and in the mercury pump. The optimum size powder is, therefore, 35 to 48 mesh size or 0.4 mm in average diameter. The furnace is designed to eliminate excessive amounts of

Jan 1, 1959

By M. R. J. Wyllie

Eight laboratory-prepared aqueous base drilling muds representing common mud types, and 15 aqueous base drilling muds sampled in the field, have been used in an experimental investigation of the relationship between the streaming potential developed across a mud filter cake and the differential pressure causing filtrate flow. It has been established that the relationship is of the form, ES = kPy, where Es is the streaming potential, P the differential pressure and k and y are constants for any particular mud system at constant temperature. Beyond a certain minimum thickness this relationship is independent of filter cake thickness. Experiment has shown that both k and y are temperature dependent parameters and that in certain mud systems there is a critical value of P above which the simple relationship Es = kPY ceases to hold. The constant k tends to be a function of the mud resistivity at 77ºF, but the exponent y has not been found to be related to any commonly measured mud property. Certain field experiments are described which serve to demonstrate that the total SP (self potential) developed opposite a formation may be quantitatively accounted for as the algebraic sum of an electrochemical potential and an electrokinetic potential. A chart to permit the simple use of mean solution activities in the interpretation of electrochemical SP data is given and its use described. Various field methods for computing the electrokinetic SP component of the total SP are considered and rejected as being unduly complicated and inaccurate. It is shown that the employment of low resistivity drilling muds is essential if optimum accuracy is desired in the use of the S.P. curve for the purpose of computing connate water salinities by the electrochemical SP method. The use of such low resistivity drilling muds is accordingly recommended. INTRODUCTION In a previous paper' a quantitative analysis of the electrochemical compovent of the SP (self potential) curve was made and it was shown that the electrochemical* emf, E, could be expressed as E = ZtRT/F In a,/a,, where t is the transference number of the chloride ion, R is the gas constant, T the absolute temperature of the formation water and mud, a, the mean activity of the connate water (assumed to be sodium chloride) and a, the mean activity of the mud (as sodium chloride). The essential accuracy of this expression was confirmed by an investigation 2 of the SP kicks opposite sands of known water salinity. The logs examined had been routine runs in oil wells in a number of Mid-Continent states. Further confirmation of the original analysis of the electrochemical SP is implicit in the paper by Tixier3 wherein a relationship between the SP and the ratio of connate water and mud resistivities, based only on field data, is given. Allowing for the fact that mud and connate water resistivities were used instead of activities, and that electrokinetic effects were ignored, the constant reported by Tixier is essentially 2tRT/F. The error involved in the universal substitution of resistivities for activities will receive further reference below. Possible reasons for the fact that the electrochemical properties of shales do not appear to be significantly dependent upon either the nature or the quantity of cation exchange materials, such as clays, they contain has been considered at some length by Wyllie and Patnode.4 In the same paper, the probable effects of shale thickness and compaction on electrochemical efficiency, and hence the inherent difficulty of obtaining reliable laboratory-scale data, were also pointed out. However, it is

Jan 1, 1951

By M. R. J. Wyllie

Eight laboratory-prepared aqueous base drilling muds representing common mud types, and 15 aqueous base drilling muds sampled in the field, have been used in an experimental investigation of the relationship between the streaming potential developed across a mud filter cake and the differential pressure causing filtrate flow. It has been established that the relationship is of the form, ES = kPy, where Es is the streaming potential, P the differential pressure and k and y are constants for any particular mud system at constant temperature. Beyond a certain minimum thickness this relationship is independent of filter cake thickness. Experiment has shown that both k and y are temperature dependent parameters and that in certain mud systems there is a critical value of P above which the simple relationship Es = kPY ceases to hold. The constant k tends to be a function of the mud resistivity at 77ºF, but the exponent y has not been found to be related to any commonly measured mud property. Certain field experiments are described which serve to demonstrate that the total SP (self potential) developed opposite a formation may be quantitatively accounted for as the algebraic sum of an electrochemical potential and an electrokinetic potential. A chart to permit the simple use of mean solution activities in the interpretation of electrochemical SP data is given and its use described. Various field methods for computing the electrokinetic SP component of the total SP are considered and rejected as being unduly complicated and inaccurate. It is shown that the employment of low resistivity drilling muds is essential if optimum accuracy is desired in the use of the S.P. curve for the purpose of computing connate water salinities by the electrochemical SP method. The use of such low resistivity drilling muds is accordingly recommended. INTRODUCTION In a previous paper' a quantitative analysis of the electrochemical compovent of the SP (self potential) curve was made and it was shown that the electrochemical* emf, E, could be expressed as E = ZtRT/F In a,/a,, where t is the transference number of the chloride ion, R is the gas constant, T the absolute temperature of the formation water and mud, a, the mean activity of the connate water (assumed to be sodium chloride) and a, the mean activity of the mud (as sodium chloride). The essential accuracy of this expression was confirmed by an investigation 2 of the SP kicks opposite sands of known water salinity. The logs examined had been routine runs in oil wells in a number of Mid-Continent states. Further confirmation of the original analysis of the electrochemical SP is implicit in the paper by Tixier3 wherein a relationship between the SP and the ratio of connate water and mud resistivities, based only on field data, is given. Allowing for the fact that mud and connate water resistivities were used instead of activities, and that electrokinetic effects were ignored, the constant reported by Tixier is essentially 2tRT/F. The error involved in the universal substitution of resistivities for activities will receive further reference below. Possible reasons for the fact that the electrochemical properties of shales do not appear to be significantly dependent upon either the nature or the quantity of cation exchange materials, such as clays, they contain has been considered at some length by Wyllie and Patnode.4 In the same paper, the probable effects of shale thickness and compaction on electrochemical efficiency, and hence the inherent difficulty of obtaining reliable laboratory-scale data, were also pointed out. However, it is

Jan 1, 1951

By F. W. Schaller

TETRAGONALITY is an important aspect of the models of transformation, strengthening, and tempering of ferrous martensite. When the c/a

Jan 1, 1963

By Reinhardt Schuhmann JR

Metallurgical Engineering Volume I, by Reinhardt Schuhmann, Jr. Addison-Wesley Press. $7.50, 390 pp., 1952. -This first volume, engineering principles, of a two volume work, is intended by the author to meet a need for reorganization of instruction in extractive metallurgy. Its three main objectives are to organize the subject matter according to basic principles and unit processes; to integrate the underlying science of physical chemistry with metallurgical engineering; and to put greater emphasis on analysis and quantitative solution of engineering problems. Vol. I deals with unit processes, stoichiometry, thermodynamics, fuels, fluid flow, heat transfer, pyrometallurgical systems and refractories. Vol. II will take up the individual unit processes. Initiation and Growth of Explosion in Liquids and Solids, by F. P. Bowden and A. D. Yoffe. Cambridge University Press. $4.50, 104 pp., 1952.-The book is a study of decomposition by impact and by friction of explosive substances and deals mainly with the work of the authors and their collaborators. Research is still in progress but results thus far indicate that the mechanism of initiation is relatively simple. Findings are thoroughly discussed, and the latter part of the monograph describes the way in which a small nucleus of decomposition can grow into a large scale explosion.

Jan 1, 1952

By T. B. Counselman

Probably the earliest concentration of iron ore in this country was carried on in the northeastern magnetite areas. Magnetic concentration was relatively simple and gave a concentrate that, after agglomeration, and in spite of being high in phosphorus because of the dry concentrating methods then in use, was satisfactory blast-furnace feed. Production from the northeastern magnetite area languished after the discovery and development of the Lake Superior ores, where there was seemingly an unlimited tonnage of high-grade ore, first the Michigan ores, and subsequently the still larger deposits of Minnesota. For years only the higher grade, direct shipping ores of the Lake Superior district were mined. Those of Michigan, and of the Vermilion Range in Minnesota, were hard ores and came principally from underground mines. The softer ores of the Mesabi came partly from underground mines, but mostly from the enormous deposits that could be worked by open-pit methods. The costs of ore from these open-pit deposits, even with the high initial cost of stripping, were so low that the underground mines of the Mesabi could hardly compete. The so-called Old Range ores, of Michigan and of the Vermilion. Range of Minnesota, were hard and lumpy, and opened UP the burden in the blast furnace, therefore making possible harder driving with greater output. Also, some of these ores were of such grade and physical characteristics that they were suitable for charge ore in the open hearth. These ores, therefore, commanded a price premium, and could compete with the softer, finer, but cheaper, Mesabi ores. The big tonnage reserves, however, are on the Mesabi. and it is these big open-pit deposits that constitute our stock pile of iron ore, from which we are drawing so heavily during this war period. On the western end of the Mesabi the ore was found to be high in silica, and not suitable as furnace feed. As early as 1902, attempts were made to concentrate this so-called wash ore and by 1910 the first washing plant was put into operation. The Process was very simple, consisting essentially of a sizing and washing operation, with scalping screens, logwashers, and tables, which later were replaced by classifiers. Ore particles finer than 100 mesh were deliberately wasted, because these fines were undesirable in the furnace. Fortunately, these tailings were impounded, and already are being reworked. Before long some of the low-grade ores began to require more elaborate treatment than the simple washing operation and, tables having been discarded because of their low capacity, in favor of classifiers, jigs were next introduced. These were able to discard coarser pieces of tailing than classifiers. jigs are in active use today, various improvements having been made in their design and application. Various other machines and methods of concentration have been tried from time to time, and have in turn been discarded for more improved processes. The latest and most important process that has been

Jan 1, 1947

By T. B. Counselman

Probably the earliest concentration of iron ore in this country was carried on in the northeastern magnetite areas. Magnetic concentration was relatively simple and gave a concentrate that, after agglomeration, and in spite of being high in phosphorus because of the dry concentrating methods then in use, was satisfactory blast-furnace feed. Production from the northeastern magnetite area languished after the discovery and development of the Lake Superior ores, where there was seemingly an unlimited tonnage of high-grade ore, first the Michigan ores, and subsequently the still larger deposits of Minnesota. For years only the higher grade, direct shipping ores of the Lake Superior district were mined. Those of Michigan, and of the Vermilion Range in Minnesota, were hard ores and came principally from underground mines. The softer ores of the Mesabi came partly from underground mines, but mostly from the enormous deposits that could be worked by open-pit methods. The costs of ore from these open-pit deposits, even with the high initial cost of stripping, were so low that the underground mines of the Mesabi could hardly compete. The so-called Old Range ores, of Michigan and of the Vermilion. Range of Minnesota, were hard and lumpy, and opened UP the burden in the blast furnace, therefore making possible harder driving with greater output. Also, some of these ores were of such grade and physical characteristics that they were suitable for charge ore in the open hearth. These ores, therefore, commanded a price premium, and could compete with the softer, finer, but cheaper, Mesabi ores. The big tonnage reserves, however, are on the Mesabi. and it is these big open-pit deposits that constitute our stock pile of iron ore, from which we are drawing so heavily during this war period. On the western end of the Mesabi the ore was found to be high in silica, and not suitable as furnace feed. As early as 1902, attempts were made to concentrate this so-called wash ore and by 1910 the first washing plant was put into operation. The Process was very simple, consisting essentially of a sizing and washing operation, with scalping screens, logwashers, and tables, which later were replaced by classifiers. Ore particles finer than 100 mesh were deliberately wasted, because these fines were undesirable in the furnace. Fortunately, these tailings were impounded, and already are being reworked. Before long some of the low-grade ores began to require more elaborate treatment than the simple washing operation and, tables having been discarded because of their low capacity, in favor of classifiers, jigs were next introduced. These were able to discard coarser pieces of tailing than classifiers. jigs are in active use today, various improvements having been made in their design and application. Various other machines and methods of concentration have been tried from time to time, and have in turn been discarded for more improved processes. The latest and most important process that has been

Jan 1, 1947

By H. B. Menardi

The history, geology, ore deposits and current mining operations of the Huitzuco district have been described by C. W. Vaupelll and the current mill operations by David Segura.2 This paper completes the story of Huitzuco with a description of the reduction of the flotation concentrates. The predominant ore mineral in the Huitzuco deposit is livingstonite, a rare, mercury-antimony sulphide (HgS.2Sb2S3). Other associated minerals include cinnabar, stibnite and elemental sulphur. The gangue is largely limestone and gypsum. Former operators mined a selected grade of ore, from which the mercury was recovered by an expensive, inefficient operation. A considerable tonnage of rejects and fills, carrying mercury and antimony, was left in the mine. In order to recover both mercury and antimony from these fills and also from newly developed ore, a combination method has been developed, by means of which the livingstonite is concentrated by flotation and the flotation concentrates subsequently reduced to metallic mercury and antimony. An essential part of the flotation treatment, as developed by Segura, is the use of copper sulphate as an activating agent. A typical analysis of concentrates now being produced at the property is as follows: Hg, 7.73 per cent; Sb, 26.40; Fe, 1.20; S, 29.68; CaO, 11.50; MgO, 7.25; SiOz, 1.63; A1203, 0.65. PRocess foR Treatment op Concentrates In the development of a process for treatment of these concentrates, three different methods were investigated: (1) roasting in a Dwight-Lloyd sintering machine with an excess of air; (2) separation of mercury and antimony by distillation in a reducing atmosphere; (3) a third method, which ultimately developed into the present process. The third method involved a slow calcination at a closely regulated temperature with a limited admission of air, which separated the mercury and antimony, the raeroury passing out of the kiln with the furnace gases and the antimony remaining in the calcine or "sinter."

Jan 1, 1944

By R. G. Hudson, H. W. Paxton

The activities of iron and chromium in their binary system have been measured by the Knudsen orifice technique. The system is close to ideal at 1200- 1250 C with slight positive deviations. The effect of this on the liquidus and solidus is discussed and these are calculated for two limiting assumptions. The vapor pressure of pure iron, pure chromium, and one alloy is compared with that obtained by the Langmuir free-evaporation technique. The results agree, indicating a vaporization coefficient close to 1. HERE are no reported data on the thermody-A namic activity of iron and chromium in the solid portions of the phase diagram. It is generally assumed'.' that the liquid solutions of iron and chromium obey Raoult's law. Chen and Chipman" have inferred that the liquid solution obeys Raoult's law. The minimum' in the solidus-liquidus curves for the iron-chromium system shows that there are deviations from ideality in either the solid or liquid or both. Because of the importance of developing reliable techniques for obtaining activity data in alloy systems at high temperatures and of the data so obtained, an investigation of the activity of iron and chromium in the binary at 1200-1250 C was undertaken using the Knudsen cell. Experimental The apparatus and experimental procedures used in this investigation were described in a previous paper." The various materials used for the construction of the Knudsen cell are listed in Table I. The metal used for the determination of the vapor pressure of chromium was 99.9 pet pure, obtained from A. D. Mackay, Inc. The iron was obtained as electrolytic grade from Fisher Scientific Company. The Fe-Cr alloys used are shown in Table 11. The largest error and controlling factor in the accuracy in the experiments reported here are introduced because of temperature uncertainty, which is estimated to be ±3 deg C. This introduces an uncertainty of 26 pet in the measured pressure. Experimental Results and Calculations The vapor pressures of pure iron and pure chromium were calculated from the measurements by the Knudsen equation3 on the assumption that only Cr or Fe atoms were present in the gas phase. For metal vapors, at the high temperatures and low pressures involved in these measurements this should be a reasonable assumption. Whitman" corrections for the cells were made. The data and results of pressure calculations are presented in Table I, and are plotted in Fig. 1. In addition the heat of vaporization at the absolute zero, ?E°°, has been calculated for chromium. These calculations are summarized in Table 111. The data used in these calculations are as follows kelley13 (F° - E°°/T ) Speiser, et al H (F° - E°°/T ) 010 where F" — standard free energy at temperature T It was necessary to calculate the total pressure above the alloys from the total weight loss W of the cell during a run, because of the fact that all attempts to collect and analyze the chromium and iron vapor effusing from the cell in the apparatus available failed. The failure resulted from the re-

Jan 1, 1959

By W. A. Alexander, L. M. Pidgeon

Metallic magnesium and similar meta!s near the top of the electromotive series have been commercially produced by the electrolysis of a suitable molten salt. Despite the success of electrolysis, sufficient inherent objections exist to justify the search for a direct reduction method. Such a method would widen the choice of raw materials, relax the rigid electrolytic requirements of raw-material purity, and, by obviating direct current, over simplicity of plant equipment. This paper describes the pilot-plant development of one such method, which has subsequently formed the basis of operation of six commercial plants-—one in Canada and five in the United States. Unlike aluminum, magnesium is volatile at relatively low temperatures. This physical property, which produces its greater inflammability, also offers possibilities of direct reduction that are not available with aluminum. In the basic reaction MgO + X = XO + Mg if X is nonvolatile, the reaction may be forced to the right at high temperatures by the evolution of magnesium vapor, despite the large negative value of the heat of reaction which is almost bound to follow the use of any available commercial reducing agent. The cheapest X, of course, is carbon, but this notable advantage is modified by the production of a volatile oxide CO, so that both Mg and CO are evolved simultaneously. Elaborate devices are required to shock-cool the equilibrium mixture in order to prevent back reaction. At best, a pyrophoric powder is produced, requiring redistillation to provide marketable metal. The practical development of this process, is due to F. Hansgirg, and his methods have recently been given a trial on a grand scale in the plant at Permanente, California, and smaller plants were previously built in Austria, England and Japan. A second class of reducing agents is available, those which produce nonvolatile oxides. When XO and X are relatively nonvolatile, magnesium is the only volatile member of the system. It may be evolved in a simple distillation step and condensed without the formation of powder. Two basic requirements must bc fulfilled in order that such a reaction may proceed: I. The reducing agent when heated to a reasonable temperature in presence of MgO must cause the production of an appreciable equilibrium vapor pressure of magnesium. This magnesium must be removed continuously. z. A supply of heat must be maintained. In order to fulfill the first requirement, operations must be conducted in vacuo or in a stream of Hz. Owing to its greater efficacy and relative safety, vacuum has been employed in the work to be described. The choice of a suitable reducing agent formed the subject of an extensive series

Jan 1, 1944

By W. C. J. van Rensburg

Exploration of unconventional mineral resources is stimulated by uncertainties about the cost and security of conventional resource sup- plies. Costs of the latter are likely to increase as a result of inflation, higher energy costs declining productivity, a lack of sufficient investment in politically volatile areas, or through cartel-like action. Exploration of unconventional resources is likely to be delayed by these same factors, insufficient research and development facilities, and a decline in capital formation. World economic growth is likely to be slow, so there will be more emphasis on material conservation. Therefore, the incentive to explore for unconventional resources may be reduced.

Jan 1, 1983

Jan 1, 1965

By George C. Gibbons

ALMOST everyone in any of the five counties embracing the great East Texas field depends heavily upon oil for his living whether or not he actually owns a well or piece of royalty himself. Oil is a natural resource that, when utilized, spreads its benefits over a vast area and into many channels. Depending then almost entirely upon agriculture: what is now known as the East Texas oil field a decade ago had a scattered farming population. For many of its people, tomatoes and other vegetable crops coupled with the old southern stand-by of cotton, furnished an adequate living and a small cash surplus. Some farm families on the red hills, however, were not far re- moved from the sowbelly and black- eyed peas, or cornpone and potlikker, standard of living. Kilgore of that day, was a village of less than 850 per- sons. Longview, with just over 5000, apparently had reached the limit of its growth. Tyler was an overgrown farming town of around 17,000 persons, de- pending largely upon the agricultural income of Smith County and surrounding territory for which it was a trading center.

Jan 1, 1941

R. 8. MACPHERRAN, Milwaukee, Wis. (communication to the Secretary): The importance of carbon in pig-iron, as well as the desirability of buying, for some purposes, irons which are high in carbon, has always been recognized. Mr. Summers, I think, has given undue weight to the carbon-determinations. The combined carbon often decreases materially as the center of the pig is approached, with a corresponding increase in the graphite. Even the determination of total carbon, to be of service, must he supplemented by that of other elements. By it alone, the softness of a foundry-iron cannot be determined. Car-wheels and No. 5 iron, for instance, frequently contain 3.75 per cent. of carbon. This is the percentage specified by Mr. Summers for his No. 1 iron, " with the silicon about anywhere the furnace-man wants it." It is true that, other things being equal, the higher the carbon the softer the iron for foundry-use. But to introduce any given percentages of graphitic and total carbon into a pig-iron specification would but make the specification more complicated, without increasing its value in a commensurate degree. Mr. Summers does not believe in the governing of mixtures by the silicon, and, in support of his views, gives several tables. It seems to me that both his conclusions and his tables are somewhat unsatisfactory. He comments on the irregularity in carbon, but fails to note the significance of the irregularity in silicon..The variation of 0.7 per cent. in silicon, for example, is too great to be accounted for by difference in blast. It might better be attributed to bad grading at the furnace, unsystematic sampling, or irregular charging. Deductions drawn under such conditions are of little value. In ordinary work the castings from the same mixture should

Jan 1, 1899

By John Chipman, Peter J. Koros

The distribution of copper between liquid silver and liquid iron, Fe-C, and Fe-C-Si alloys was studied at 1600°C. From the data and the activity of copper in silver obtained from the phase diagrams, the activity coefficients of copper in iron up to 3 atomic pct are log y, = 0.90 — 2.4 N, and y": = 8.0. The effect of carbon up to saturation is expressed as log y = 1.8 Ni. The effect of silicon up to 11 atomic pct is insignificant. SLOWLY rising copper content of steel being produced is focusing attention on the lack of information on the behavior of copper in liquid steel. Chou' measured the activity coefficient of copper in liquid iron through its distribution between liquid silver and iron. He obtained a value of 9.12 at infinite dilution. Chipman' calculated the activity coefficient of copper in liquid iron at 1600°C from the phase diagram and obtained a value of 12. Ameiln and Pfeiffer- investigated the possibility of removing copper from liquid steel through the use of lead, silver, and bismuth as solvents. They also calculated that the activity coefficient of copper in liquid iron would be increased five or sixfold by addition of 4 pct C. Langenberg and Lindsay' are investigating the effectiveness of lead and sodium sulfide in removing copper from liquid iron. The experimental method was similar to that used by Chou' and Chipman and Floridis." Silver, copper, and iron were melted together, the copper distributing itself between the two layers so that at equilibrium a,.,, (in Ag) - a,.,, (inFe) and N,.,, (in Ag) yc,, (inFe) (in Ag). [21 N,.,, (inFe) Thus, from the concentration of copper in each layer and the activity coefficient of copper in liquid silver, the activity coefficient of copper in liquid iron can be calculated. The effect of an alloying element such as carbon on the activity coefficient of copper can also be determined from its effect on the distribution, provided the new element is essentially insoluble in silver. The one serious limitation of this method is the increasing mutual solubility of silver and iron in the presence of a third component. The mutual solubilities of pure iron and silver are negligible, but increase with increasing copper concentration beyond the range investigated. Ag-Cu System—The activity coefficient of copper in silver at 1600°C had to be estimated, since direct experimental data are not available. Kawakami" measured the heat of mixing of Ag-Cu alloys at 1200°C by a calorimetric technique. Scheil' calculated the heat of mixing in this system by use of the phase diagram, assuming that the solution is random and that the heat of mixing is independent of temperature. The terminal solid solution may be assumed to obey Raoult's law within the requirements

Jan 1, 1957

By W. C. Ellis, M. E. Fine

WHEN certain binary Fe-Ni alloys are worked cold and then stabilized by a stress-relief anneal, their Young's moduli are nearly invariant over a substantial temperature range determined by composition and work-anneal history.' In the present investigation addition of molybdenum to such alloys (besides increasing the yield strength) was found to diminish the sensitivity of the thermal coefficient of Young's modulus to composition changes. Such alloys are of interest for applications requiring 1 a metal with controlled, low temperature coefficient of Young's modulus and substantial magnetic permeability.' Young's modulus ordinarily decreases with rising temperature. In ferromagnetic alloys a change in modulus on heating due to loss of ferromagnetism modifies the .temperature dependence. Far below the Curie temperature ferromagnetism alters the modulus in two ways: a—Addition of the energy of magnetization, a function of interatomic distance, changes the relation between interatomic energy and distance.' This lowers the modulus in the Fe-Ni and Fe-Ni-Mo alloys of this investigation. b—An applied stress changes the ferromagnetic domain arrangement so that linear magnetostriction contributes to the strain and further lowers the modulUs.~ Since in the alloys of this investigation both effects lower the modulus, loss of ferromagnetism on heating changes the slope of the modulus-temperature curve in a positive direction. With increasing temperature the slope of the modulus-temperature curve, due to progressive loss of ferromagnetism, becomes less negative, goes through zero (the modulus is minimum), becomes positive, and resumes its normal negative value above the Curie temperature.' The increase in modulus and decrease in curvature in the modulus-temperature curve occurring on work hardening have been attributed to a reduction in effect (b).'. Vn the absence of ferromagnetism work hardening through introduction of residual strains would be expected to decrease the modulus.' Alloy Preparation—Test Methods Four series of alloys having nominal molybdenum contents of 5, 7, 9, and 10 pct and containing 47 to 58 pct Fe (the analyzed compositions are given in Table I) were melted in air and cast as bars weighing from 2 to 6 lb. The charge consisted of electrolytic nickel, Armco iron, molybdenum (99+ pct) or ferromolybdenum (62 pct Mo), manganese, and aluminum as a deoxidizer. The bars were swaged cold to the desired diameters with intermediate anneals. Alloys in this composition range are reported" to be face-centered cubic and ferromagnetic at room temperature. The Curie temperatures" decrease with molybdenum. For example, keeping the Ni/Fe ratio at unity and increasing the molybdenum from 0 to 17 pct decreases the Curie tempera- ture from approximately 500°C to room temperature. (The 17 pct Mo alloy requires quenching to retain a single phase.~) Young's modulus at a series of temperatures from —50" to 100°C was determined by a dynamic method previously described.', " In this method Young's modulus is calculated from the resonant frequency (in this case approximately 50,000 cycles per second) of a rod sample (approximately 2 in. long) vibrating longitudinally in the first mode. The densities of the samples at room temperature, Table I, were determined by the standard method of weighing in air and reweighing in redistilled bromobenzene. The linear coefficients of expansion, Table I, needed to calculate the sample length and density at the temperature of measurement, were obtained by observing the change in length (22" to 100°C) of an 8 in. gage distance with a two microscope cathetometer. The values of density and coefficient of expansion in the few samples checked are independent of treatment to the accuracy reported. This was assumed to be general for all the samples. The modulus values are accurate to &0.05x101' dynes per sq cm. However, values of thermal change in modulus are accurate to 20.005~ 10" dynes per sq cm. Young's Modulus Values at 25°C: The modulus values of O', 5, and 10 pct Mo alloys at 25 °C are plotted in Fig. 1 as functions of nickel. After working cold, the samples were either recrystallized at 950" to 1000°C or given a low temperature stabilizing anneal at 400° C. The 400°C anneal does not reduce the hardness nor cause recrystallization. Annealing at 400 °C does

Jan 1, 1952