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By Robert D. Pehlke, Arden L. Bement

A mass transfer coefficient for the removal of hydrogen from liquid aluminum by inert flush degassing has been determined experimentally at 700°C. A mathematical model has been derived, assuming transport control, which adequately describes the experimental data. The removal of hydrogen is shown to increase with decreasing bubble size, and with increasing flow of flushing gas. The presence of hydrogen in liquid metals in amounts which exceed the solid solubility at one atmosphere hydrogen pressure is highly undesirable, causing unsound ingots or castings, or resulting in difficulties during further fabrication. The removal of hydrogen from liquid metals can be accomplished by several methods, the principal two being vacuum treating and inert flush degassing. The design of a process involving either of these techniques is based on the mass transfer coefficient for hydrogen between the liquid metal and a hydrogen-dilute gas phase. In an effort to extend our knowledge in this area, an investigation of the rate of removal of hydrogen from liquid metals by inert gas flushing was undertaken. In view of the difficulties encountered with gas porosity in the casting of aluminum and aluminum alloys, and because of certain experimental advantages, liquid aluminum was selected for the study. PREVIOUS INVESTIGATIONS The removal of gases from liquid metals, particularly steel, has received considerable attention in recent years, The first definitive work of a theoretical nature was presented by Geller1 who considered the case where equilibrium exists between purging gases and metal bath during flushing, and also deviations from this ideal case. Hulme2 has surveyed a number of experimental studies and discussed some of the practical limitations of removing dissolved gases from molten metals. More recently a number of studies have been reported on degassing of steel melts by flushing with an inert gas.3'4 Considerable work has also been reported on aqueous and organic liquid-gas systems, and an excellent summary prepared by Hovis.5 The treatment of liquid aluminum by a flushing gas to remove dissolved hydrogen has been known for several decades.6 A number of gases have been used for this purpose, including nitrogen, argon, and chlorine, or mixtures of these gases. Tikkanen and Erkko7 have studied the relative density changes of aluminum castings poured from melts degassed with chlorine, nitrogen, and mixtures of the two gases. Their

Jan 1, 1962

By T. R. Ingraham

The thermal decomposition of Nickel (II) sulfate was examined by determining the total pressure of SO3, SO2, and O2 developed over a sample when it was heated in an evacuated system fitted with a Pyrex-bellows mercury manometer. The equilibrium pressures were combined with previously published data on the oxide and sulfide systems to establish a predominance volume diagranz for the Ni-S-O system over the normal range of roasting temperature and gas composition used in the treatment of nickel minerals. The protective coating of NiSO4 which forms on the oxide during roasting, and which causes the sulfation reaction to almost cease, may be disengaged readily by temperature cycling. When nickel sulfide is roasted in air, either nickel sulfate or nickel oxide may be formed by altering the experimental conditions. Because of the differing stabilities of various metal sulfates and oxides, possibilities exist for separating some of the constituents of mineral mixtures by the technique of selective sulfation and oxidation roasting. The experimental information required to make reasonable predictions of the possibilities of this technique is incomplete and, in some cases, in conflict. As part of a general program of providing some of the required information, a study EXPERIMENTAL Materials, Apparatus, and Procedure. Fisher certified reagent-grade nickel sulfate hexahydrate was used in the source material for both nickel sulfate and nickel oxide. The manufacturer's analysis indicated: 0.001 pct Fe, 0.005 pct Cu, 0.003 pct Co, 0.001 pct C1, other 0.15 pct. The material was dehydrated, before use, by heating at 420°C for 5 hr. The oxide was prepared by roasting the sulfate in an open tray in a muffle furnace for 10 hr at950°C. Preliminary experiments which were made by thermogravimetric analysis and X-ray diffraction analysis established that only one crystal form of nickel oxide and one of nickel sulfate were involved in the equilibrium shown in Eq. [I]. The apparatus used in the experiments was described previously.1,3 The main feature is a corrosion-resistant, flexible Pyrex bellows which is used to protect the mercury in a u-tube manometer. Before a run was begun, the apparatus was washed thoroughly with hot hydrochloric acid and water and dried by heating under vacuum. The mixed sulfate -oxide sample was contained in a platinum bat rest-

Jan 1, 1967

By Charles S. Barrett, Robert F. Mehl, Shueling Woo

WHEN one solid phase is generated from another, fixed and rational orientation relationships are observed to subsist between the parent and the new crystal. The principle has been proposed' that the relationships obtaining between the same two phases are identical whatever the type of phase change involved, or whichever of the phases may act as parent. Many types of phase changes have been studied: allotropic transformations in pure metals, precipitation from solid solutions, eutectoid decompositions, peritectic reactions, the formation of oxide layers, and others.2 Phase layers generated by diffusion of one metal into another constitute an additional type of reaction. This report provides new data on the orientation relationships occurring between , phase layers formed by diffusion, in the Cu-Zn system, § and furnishes further evidence in support of the principle. MATERIALS AND METHODS The Cu-Zn system is especially suitable for these studies since the high vapor pressure of Zn provides an opportunity readily to create one phase poorer in Zn upon a parent phase richer in Zn by removing Zn by vaporization, or to reverse this process by adding Zn from Zn vapor; e.g., the beta phase can be found as a layer upon gamma by dezincing, or gamma can be found on beta by addition of Zn from Zn vapor. Since orientation relationships are to be sought, requiring crystals large enough for orientation determinations, it is convenient to prepare single crystals or large grains of the parent phase. The samples were prepared from oxygen-free high-conductivity copper and Horse Head zinc by melting under a borax flux in a graphite crucible. Large crystals of beta brass were grown by the strain-anneal method, in plates sectioned from the cast ingots, by the following procedure. Rockwell-hardness indents were made at I cm. intervals-and with various loads, then the plates were annealed for .4 days at 700°C. in Nichrome boxes packed with beta-brass chips and graphite. Surface layers were removed by grinding and etching to a depth of about 1.0 mm., and individual grains were cut out. Crystals of alpha and gamma brass were prepared by freezing, by lowering a graphite crucible at speeds less than one inch per hour through a furnace held at a constant temperature above the melting point. Single crystals were cut out with a jeweler's saw, ground, polished and etched. Care was taken to remove cold worked layers from the finished crystals

Jan 1, 1944

By Frederick C. Hull, Robert F. Mehl, Robert A. Colton

IT is known that pearlite forms from austenite by a process of nucleation and growth, and that the rate of formation of pearlite may be described by a rate of nucleation and a rate of growth.1,2 The manner in which these two quantities operate to produce the observed isothermal reaction curve has been analyzed in a paper published in 1939.3 Two types of process were described: (1) that in which nucleation occurs at the grain boundaries of the parent phase, with the nodules growing toward the centers of the grains, initially as hemi¬spheres and then after impingement as roughly radial-columnar structures; and (2) that in which nucleation occurs generally, with the nodules growing to full spheres until impingement with other growing nodules restricts growth. Both cases are met in the formation of pearlite from austenite (Fig. 1);2.4 the former, occurring near the knee of the S-curve has been named "grain-boundary transformation," and the latter, occurring at temperatures near Ae1, has been named "group-nodule transformation." In developing our knowledge of the factors that determine the rate of formation of pearlite from austenite, it is important 1,2 to obtain data on the rate of nucleation and the rate of growth of pearlite. Such data, when obtained near the knee of the S-curve, will furnish information of use in understanding the factors that affect hardenability; when obtained at higher temperatures, such data will be useful in understanding the behavior of steels that during heat-treatment react to pearlite.2 It is the purpose of this paper to present data on the rate of nucleation and the rate of growth of pearlite in dependence upon composition, grain size, temperature, and the degree of homogeneity of the parent austenite. The studies are restricted chiefly to plain carbon commercial steels.* PREVIOUS DATA ON RATE OF NUCLEATION AND RATE OF GROWTH Data on the rate of nucleation and the rate of growth of pearlite have been published by Scheil and Lange-Weise,5 by Mirkin and Blanter,6,7 by Mehl,1 and by Dorn, De Garmo and Flanigan.2 It is difficult to interpret the data, for in most cases too little information is given on austenitizing temperatures and times, the state of homogeneity of the austenite (presence or absence of carbide, etc.), austenite grain size, and mode of formation of pearlite at the temperatures given.

Jan 1, 1942

THIS chapter and the one following deal with the heat quantities involved in open-hearth steelmaking, including the thermal efficiency of the furnace as a generator of high-temperature heat, the heat storage in the steel and slag produced and in the furnace walls, and the heats of the various chemical reactions involved in combustion, in the formation of slag, and the refining of steel. The fundamental laws to be considered are the simplification of the first two ' laws of thermodynamics as applied to problems involving sensible and potential (or latent) heat only 1. Heat input equals heat outflow plus storage. 2. Heat may be transferred only from a hotter body to a colder one. The first of these laws relates to the various heat quantities or the "heat balance" of the process. No one has as yet made an open-hearth heat balance that came out almost exactly balanced, and we assume that the cause lies in the difficulties of accurate temperature and flow-rate measurements at the high temperatures involved and the inherent complexities of flow distribution, air leakage, etc., present in any real, open-hearth furnace system. Some idea of the magnitude of the heat quantities involved can be obtained- by a brief, crude outline of the heat balance of a 90-ton heat of steel. We will assume a 60 to 70 per cent hot-metal charge in a fairly fast working and only moderately efficient furnace, burning fuel oil, with a fuel consumption of around 4 million B.t.u. per net ton. of ingots produced. The time from start of charge to tap is 9 hr. During this period, the oil burned represents 360 million B.t.u., and the sensible heat in the preheated air at the port ends is 117 million B.t.u. so that the total heat input at the ports is 477 million B.t.u. Heat stored in the steel and slag at the end of the heat, plus the various amounts absorbed by certain bath reactions, amounts to a total of 195 million B.t.u., but 120 million of this is supplied by the heat in the hot metal and by various heat--evolving reactions in the bath, so that only 75 million B.t.u. need be supplied to the bath by the flame.

Jan 1, 1944

By J. T. Berling, J. B. Conway

MANY studies have been devoted to the correlation of low-cycle fatigue behavior. Several of these have also been concerned with the identification of an effective approach to the prediction of low-cycle fatigue behavior from short-term tensile data. Perhaps the first such approach was that reported by coffin1 in the form: where is the plastic strain range, Nf is the number of cycles to failure, and c is a constant characteristic of a material. In this analysis by Coffin it was reasoned that in a short-term tensile test the value of Nf could be considered as equal to a , in which case the value of c is interpreted as the tensile ductility, f, measured in such a test. If, therefore, the Coffin equation is assumed to be applicable to a given material, it is a simple matter to predict the low-cycle fatigue behavior. Once the tensile ductility is known, this point is located at Nf = 1/4 on a log-log plot of vs Nf and a line is drawn through this point with a slope of to yield a prediction for the fatigue life. Actually, while this equation is quite useful it is not generally applicable, for experiment has shown that the value of —$ does not reflect the relationship between and Nf for all materials or even for a given material over all temperature ranges. An equation similar to the Coffin equation was prepared almost simultaneously by Manson.2 This expression had the form: In this case the exponent on Nf was not assigned any particular numerical value in accord with the various values of this exponent which had been observed for different materials and at different test conditions. Because of this characteristic it will be recognized that little use can be made of this expression in predicting low-cycle fatigue results. A fairly effective expression for use in predicting fatigue behavior was proposed by Manson3 based on a study of numerous sets of experimental results. This relation (Method of Universal Slopes) makes use of modulus of elasticity, ultimate strength, and tensile ductility, and assumes an exponent on Nf equal to 0.6 in representing the plastic strain range contribution to total strain range. While this equation of Man-Son does not yield completely accurate results it must be recognized as being the best means available at

Jan 1, 1970

By H. W. Mead, C. E. Birchenall

SELF-DIFFUSION of iron in austenite is a process which may play a significant role in some of the practically important reactions which occur in solid irons and steels. It also provides a system in which the interaction of vacancies on substitutional sites and atoms in interstitial positions may be investigated. For both purposes, accurate values of the diffusivities are required. Two sets of previous measurements exist, each containing features which require checking. In the course of an investigation to determine the rate of diffusion of iron in certain steels, Garwick and Rosenqvist' measured the self-diffusion coefficient of iron in a 0.10 pct* C steel and obtained a dicated that while at lower temperatures D increased with increasing carbon content, at the higher temperatures it first increased and then decreased. At the same time the activation energy decreased linearly from a value of 69,000 cal per g-atom for pure iron to 33,000 cal per g-atom at 1.06 pct C. This rapid decrease in activation energy implies that iron at higher temperatures within the austenite range would diffuse more slowly in high carbon steels than in steels of lower carbon content. Experimental Procedure The radioactive iron used in this work was obtained from Oak Ridge National Laboratory. The unit consisted of about 1 microcurie each of Fe7 and Fe It was allowed to decay for two years. At the end of this time most of the Fe with a half-life of 46.3 days, had decayed, while most of the original Fe(half-life 2.91 years) still remained. The iron as chloride was extracted into an ether layer, using the method of Ashley and M~rray. After evaporation of the ether the iron chloride was dissolved in 250 ml of aqueous solution containing 2.4 gpl Fe. The compositions of the steels used are listed in Table I. Disks of ¾ in. diam and about ¼ in. thick were machined from these steels for use in diffusion couples. The disks were surface ground on both sides to ensure parallel opposite faces. One face of each disk was polished through 000 emery paper. Half of the prepared disks were plated with radioactive iron. For this, 1 ml of the radioactive iron

Jan 1, 1957

By B. Chalmers, Stefan Wojciechowski

Rotary oscillation of the mold has been used to produce mechanical stirring of the melt during unidirectional solidification. Al-Cu alloys (1 to 4 wt pct Cu) were solidified to study the influence of alloy composition, temperature at which intensive cooling was initiated, and intensity of stirring on the temperature distribution in the sample, the resulting structure, and the copper microsegregation at the columnar to equiaxed transition. The Proposed explanation for the equiaxed solidification in stirred castings consists of the melting off of dendrite fragments, their partial remelting in hotter liquid, and the subsequent growth of the surviving part when the temperature of the melt is lowered. This may result in the formation of a crystal network, which can stop the growth of the columnar crystals and produce the equiaxed zone. It has long been known and many times affirmed that ultrasonic vibrations or relative motion of liquid and solid can significantly reduce the length of the columnar zone and refine the grains in the equiaxed zone in ingots and castings. Because of the technological importance of these phenomena many investigations have been conducted in which ultrasonic energy or mechanical vibration,1-6 electromagnetic stirring,7"10'17 magnetic stirring,"'12 or mechanical stirring13'14 were used to produce the relative liquid-solid motion. More recently, the question of the importance of natural (or thermal) convection has been raised.15-l7 Several possible mechanisms have been suggested.l,8,18-20 They can be divided into two main groups. The first group includes such nucleation hypotheses as nucleation frequency enhancement due to cavitation at the mold wall or other surfaces; cavita-tion in the body of the liquid resulting from the pressure wave, or an agglomeration mechanism, which involves the formation of nuclei by the accretion of subcritical nuclei. The second group considers the grain-refining action to be due to crystal multiplication phenomena such as the removal of the dendrite fragments by viscous forces or by a high-pressure cycle following cavitation or by a melting-off process. Sbme recent investigations give good experimental support to the melting-off proposa1.21-23 The purpose of the present study was to examine the effect of mechanical stirring during the unidirectional solidification on the structure of alloy samples and on the solidification variables. The motion of the liquid was produced by rotary oscillation of the mold around its vertical axis.

Jan 1, 1969

By John F. Elliott

STAFF: Editor, Gerhard Derge Acting Editor, Poul G. Shewmon Carnegie lnstitute of Technology Schenley Pork Pittsburgh 13, PO. Editorial Assistant, M. A. Redmerski Production Editor, Otto T. Johnson THE METALLURGICAL SOCIETY: Rich-ard C. Cole, President; Karl L. Fetters, Past-President; J. H. Scoff, Vice President; R. L. Henneboch, Treasurer, R. W. Shearman, Secretary. PUBLICATIONS COMMITTEE OF THE METALLURGICAL SOCIETY: R. E. Lund, Chairmon; T. E. Dancy, P. R. Gouwens, W. A. Krivsky, F. C. Longenberg, E. R. Morgan, R.R. Nosh, Poul Queneou, W.O. Philbrook, J. H. Scoff, L. L. Seigle, and M. E. Wadsworth. Review and selection of manuscripts is under the supervision of the following Publications Committees: Extractive Metallurgy Division: M. E. Wadsworth, Chairmon; R. E. Grace, Vice Chairman; D. H. Baker, Jr., G. M. Bell, D. H. Bridges, J. M. Cigon, G. W. Healy, R. A. Lewis, C. E. O'Neill, A. W. Schlechten, R. E. Shinkoskey, and W. W. Stephens. Iron and Steel Division: T. E. Dancy, Chairman; A. Muan, D.W. Murphy, R. D. Pehlke, J. M. Uys, J. 5. Wagstoff, and R. G. Word. lnstitute of Metals Division: R. R. Nash, Chairman, H. H. Johnson, Jr., Vice Chairman; M. R. Achter, P. A. Beck, J. J. Becker, G. F. Bolling, J. 0. Brittain, J. 8. Clark, R. 5. Davis, A. E. Dwight, R. W. Fountain, L. A. Girifalco, E. L. Harmon, J. J. Heger, A. A. Hendrickson, L. Himmel, J. P. Hirth, R. H. Richmao, H.C.Rogers, W. Rostoker, 0. D. Sherby. E. A. Steigawald, R. Steinitz, H. C. Stumpf, R. A. Swalin, W. A. Tiller, W. R. Upthegrove, D. Walton, H.W. Weart, and D. Wilsdorf. Published bimonthly by the American lnstitute of Mining, Metallurgical, and Petroleum Engineers, Inc 345 East 47th Street, New York 17. N. Y. Telephone PLaza 2-6800. Subscription $30 per year for non-AIME members in United States and North, South, and Central America; $32, foreign;$30per $7 50 for AlME members. Single copies, $6.00, single copies foreign, $6.50. The AlME is not responsible for any statement made or opinion expressed in its publications ... Copyright 1963 by the American lnstitute of Mining, Metallurgical, and Petroleum Engineers, Inc....Registered cable address, AlME New York . .. Indexed in Engineering Index, Industrial Arts Index, and Chemical Abstracts . . Second class postage paid ot New York, N. Y., and Ann Arbor, Mich. Volume 227, Number 4.

Jan 1, 1963

By W. J. Skewes, C. T. Holland

Properly constructed stopes are necessary underground for proper ventilation and safe, healthful working conditions. Mining companies are concerned with providing the best possible stoppings at an economic cost. It is important to consider 1) proper materials, 2) construction that ensures maximum performance from the material used, and 3) keeping costs within reasonable limits for the unit operation—stopping—involved. The authors investigated all aspects of the problem and have attempted to layout a study program to provide information on all phases. Mining companies every year purchase huge amounts of material for the construction of ventilation stoppings. This material by the time it is in place in the stoppings will cost the company many thousands of dollars. In addition and more importantly these stoppings are supposed to confine air travel along certain well defined paths into areas where it is needed to provide safe and healthful atmospheres for workmen. The cost of forcing this air through the mine is large and in general increases as the total quantity increases. Consequently, if the stoppings leak, increased cost results and in addition unsatisfactory ventilation may prevail in the mine. Therefore, it is essentia1 to provide the best possible stoppings at an economic cost. When attempting to provide the best stoppings possible at an economic cost, three aspects of the problem must be considered. These are 1) getting the most suitable material for stopping constructions, 2) constructing the stopping so as to get the best performance from the material used, and 3) keeping the cost of stopping construction to a minimum for a suitable stopping. This investigation is concerned with all phases of the problem and has attempted to lay out a study to provide information on all of them. In order to develop information on the best stopping material available it seemed wise, after con- sidering the job a stopping must do, to investigate the following aspects of material used for stoppings: 1) strength in compression, 2) compressibility or yield under load, 3) porosity, and 4) permeability. To provide information on the best manner of construction the following aspects of air leakage through the stopping were investigated: 1) when the stopping is built of dry stacked materials—i.e., the joints are not mortar-laid (See Fig. 1); 2) when the stopping is built of dry stacked material and then plastered on one side (see Fig. 2); 3) when the

Jan 1, 1961

By W. B. Boggs, J. N. Anderson

An account of the operation of the Noranda smelter covering the period from December, 1927, when the smelter started, until December, 1929, was given in a paper published by the Canadian Institute of Mining and Metallurgy early in 1930.' The object of the present paper is to review matters of interest in the original paper and to describe the present construction and operation of the smelter, with particular reference to the reverberatory-furnace practice. The Noranda smelter was built by Noranda Mines, Ltd., from the designs of A. E. Wheeler, consulting metallurgist of New York, for the reduction of ores and concentrates from the Horne mine and to treat, on a custom basis, ores and concentrates from other mines in the Rouyn district. The smelter is at Noranda, about 330 miles directly north of Toronto. Construction work was started in June, 1926, and copper was first produced in December, 1927. The smelter was built throughout as two duplicate units, each with a rated capacity of 500 tons of ore per day. Operations were started with one unit and after several months it was found that one unit alone could smelt 1000 tons of ore a day. At that time there was only one hoisting shaft, No. 3, and its hoisting capacity and the capacity of the original crushing plant were insufficient to supply ore for the two units at the increased tonnage. Accordingly No. 4 shaft was sunk and a new crushing plant provided to handle the ore hoisted there. Operating two units at capacity also required the installation of two more converters to treat the additional quantity of matte produced. This work was completed in the latter part of November, 1929, and since then both smelter units have been operating continuously. In 1928, a mill to treat 500 tons a day of concentrating ore was completed. Since then the concentrator capacity has been increased twice, and at present 2000 tons a day of ore are being concentrated. The layout of the surface plant of the mine, concentrator and smelter is shown in Fig. 1 and the general plan in Fig. 2. The smelter is shown in more detail in Fig. 3. The original hoisting shaft, No. 3, is now used only for handling men, supplies and waste rock, and the original crushing

Jan 1, 1934

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

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

Jan 1, 1920

By F. N. Rhines, A. H. Grobe

At elevated temperatures the oxide of silver is unstable in the air at atmospheric pressure, consequently no external oxide scale forms upon pure silver under conditions of high-temperature annealing. When small quantities of certain alloying elements are present in the silver, the formation of a thin external scale is possible1 and in addition there may form a subscale composed of the oxide of the solute element precipitated within the body of the silver. Norbury2 and Leroux and Raub3 have reported internal oxidation (subscaleiormation) in alloys of silver with 2, 7.5, and 30 per cent of copper. The presence of the subscale is believed to be responsible, at least in part, for the objectionable "fire mark" in Sterling silver.4 Several other alloys of silver, after oxidizing heat-treatments, are known to exhibit undesirable polishing characteristics that may be the result of internal oxidation. Except for the absence of an external scale of silver oxide, it is to be anticipated that silver alloys will prove to be very similar in their oxidation behavior to the alloys of copper, the oxidation characteristics of which have been studied in some detai1.5,6 The present research confirms this anticipation. The oxidation of a series of 20 dilute alloys of silver has been studied metallographically; some types of subscale not encountered among the copper alloys have been found. Instances of internal oxidation in alloys of most of the metals of the 1-6 and VIII groups of the periodic system are on record, but evidence of this type of oxidation in alloys of the metals of the intermediate groups is lacking. A number of the metals of the intermediate group, among them cadmium, lead, tin, and zinc, appear to provide the conditions essential to subscale formation; i.e., they form oxides with a relatively low negative free energy of formation, they dissolve other metals that form more stable oxides, and, presumably, oxygen will diffuse through them. In a study of 40 alloys of these white metals only a few cases of internal oxidation have been found. The probable reasons for this difference in behavior will be discussed presently. Experimental Procedure Silver.—The silver alloys employed in the oxidation studies were prepared in heats of 30 grams each from high-purity silver (99.993 per cent Ag)* and the purest avail-

Jan 1, 1942

By A. H. Grobe, F. N. Rhines

At elevated temperatures the oxide of silver is unstable in the air at atmospheric pressure, consequently no external oxide scale forms upon pure silver under conditions of high-temperature annealing. When small quantities of certain alloying elements are present in the silver, the formation of a thin external scale is possible1 and in addition there may form a subscale composed of the oxide of the solute element precipitated within the body of the silver. Norbury2 and Leroux and Raub3 have reported internal oxidation (subscaleiormation) in alloys of silver with 2, 7.5, and 30 per cent of copper. The presence of the subscale is believed to be responsible, at least in part, for the objectionable "fire mark" in Sterling silver.4 Several other alloys of silver, after oxidizing heat-treatments, are known to exhibit undesirable polishing characteristics that may be the result of internal oxidation. Except for the absence of an external scale of silver oxide, it is to be anticipated that silver alloys will prove to be very similar in their oxidation behavior to the alloys of copper, the oxidation characteristics of which have been studied in some detai1.5,6 The present research confirms this anticipation. The oxidation of a series of 20 dilute alloys of silver has been studied metallographically; some types of subscale not encountered among the copper alloys have been found. Instances of internal oxidation in alloys of most of the metals of the 1-6 and VIII groups of the periodic system are on record, but evidence of this type of oxidation in alloys of the metals of the intermediate groups is lacking. A number of the metals of the intermediate group, among them cadmium, lead, tin, and zinc, appear to provide the conditions essential to subscale formation; i.e., they form oxides with a relatively low negative free energy of formation, they dissolve other metals that form more stable oxides, and, presumably, oxygen will diffuse through them. In a study of 40 alloys of these white metals only a few cases of internal oxidation have been found. The probable reasons for this difference in behavior will be discussed presently. Experimental Procedure Silver.—The silver alloys employed in the oxidation studies were prepared in heats of 30 grams each from high-purity silver (99.993 per cent Ag)* and the purest avail-

Jan 1, 1942

By John H. Hollomon

IN recent papers, O'Neill,1 Vivian,2 and Zener and Hollomon3 have reviewed some of the information concerning the relations between stress and strain during plastic deformation. Since further information has been obtained since these reviews were published, this paper attempts to further coordinate and amplify the knowledge concerning the plastic deformation of metals in simple tension. Ordinarily the results of tensile tests of metals are presented as graphs in which the load divided by the original area is plotted as a function of the percentage of elongation measured over some specified gauge length. The interpretation of graphs of this sort is limited, since the stress required to deform the metal at any stage of the deformation is actually the load divided by the instantaneous rather than the original area. Furthermore, each increment of the deformation is performed on metal that has been previously deformed, and, as pointed out by Ludwik,4 the strain could be more effectively defined: [e = In A t][I] where a is the strain and Ao and A are, respectively, the original and instantaneous areas. The results of the tensile tests can be more effectively presented and interpreted if the stress* (load divided by actual area) is plotted as a function of the strain as defined above. A schematic curve of this type is presented as Fig. I. In a previous paper,6 the concept of Ludwik7 concerning the flow and fracture of metals was successfully employed to explain some of the puzzling results of notched-bar impact tests of steel. It appears that the use of this concept is very fruitful and should be kept in mind in any study of the deformation characteristics of metals. Ludwik considered that a flow stress-strain curve of a metal was essentially a locus of points that described the stress required for plastic flow of an infinite number of specimens, each with a different strain history determined by the preceding part of the flow curve. Each of these specimens can also be considered to have a fracture strength. Unfortunately (or fortunately depending upon the point of view), all the specimens, except the one deformed to the fracture strain, flow and do not fracture. Even though the metals do not fracture, the concept of a fracture-strength curve seems

Jan 1, 1945

By W. B. Triplett, H. I. Aaronson, G. M. Andes

A detailed morphological study has been made of the pro-eutectoid TiCr, and the eutectoid reactions in a Ti-17.42 pct Cr alloy isothermally transformed at temperatures from 775° through 5561°C. The morphologies of proeute,ctoid TiCr2 were found to be subject to description by the Dube morphological classification system. Grain boundary allotriomo.lphs are the dominant plpoeutectoid morphology throughout the temperature range investigated. lntragranular plates, and especially Widmanstatten sideplates, form only in small numbers. This morphological pattern differs markedly from that of the proeutectoid a reaction in hypoeutectoid Ti-Cr alloys (AIME Trans., 1957, vol. 209, p. 1227; 1958, vol. 212, p. 624), in which plates form prolifically throughout wide ranges of temperature. The eutectoid reaction is nonlamellar in character at 675°C. An increasingly prominent lamellar component develops at lower temperatures. The proeutectoid TiCr 2 and the eutectoid transformations have been studied metallographically in a hypereutectoid titanium-chromium alloy. This investigation was undertaken with the immediate objective of comparing these transformations with their counterparts in hypoeutectoid titanium-chromium alloys, studies of which have been recently completed.1,2 It was also intended, however, to contribute to the general literature on transformations of these types. Especially in the proeutectoid case, this literature is still sufficiently sparse to make difficult the testing of generalizations on the mechanisms of these transformations. TiCr, is the only intermetallic compound in the titanium-chromium system.3-5 The TiCr2 phase field extends to a maximum temperature of 1350°C) and encompasses the approximate composition range of 62 to 68 pct Cr at lower temperatures.3'4 At temperatures below 1000°C, TiCr2 has a MgCu,-type fcc structure, with 24 atoms comprising a unit cell.6,7 Only fragmentary observations on the morphology of proeutectoid TiCr2 have been previously reported. An observation which is of considerable importance with respect to the results obtained during the present investigation was made, however, on anisother-mally transformed alloys with high chromium (48 to 70 pct Cr) contents.3"8 Despite the occurrence of extensive impingement, it is apparent that a substantial proportion of the proeutectoid TiCr, which precipitated in these alloys grew in the form of Widmanstatten plates. Several observations have been made on the eutectoid reaction in hypereutectoid alloys during investigations of the titanium-chromium phase di-

Jan 1, 1961

By David White

In these days, when detailed investigations of stratigraphy, structure, and sand conditions so frequently result in the discovery of new oil fields, and applause from oil companies and the public, geologists do well to walk humbly, and punctiliously to admit that the geologic principles controlling the distribution of oil and gas have as yet been discovered only in part, and that what remains yet to be learned is probably vastly more than what is already known. The few experiments already attempted have been fragmentary, and somewhat desultory, and however positive each of us may be with respect to certain theoretical conclusions, many of the fundamental questions as to the origin and mode of occurrence of petroleum are subject to radical disagreement. Of the chemical changes attending the generation of petroleum from organic matter, little is actually known. Most of the postulated formulas are liable to be misleading, through ignorance of essential factors. Open-minded-ness is therefore a prime essential at the present stage of our science. Nevertheless, adopting the hypothesis that oil originates in some manner fundamentally connected with the organic theory, and in possible departure from such open-mindedness, the writer will pay no attention to the so-called inorganic theory, since every attempt to apply this theory to the study of old oil fields, or to the discovery of new ones, affords cumulative evidence of its inadequacy. In this paper, some of the factors affecting the occurrence of petroleum that the writer believes worthy of consideration by the prospector for oil in any new region will be discussed. Some of these, which arc less generaLly understood, will be considercd somewhat in detail. Other points, the significance of which cannot now be determined, require more field study, and for that reason are here brought to the attention of the field geologist. On the other hand, certain theoretical points which do not bear especially on the oil possibilities of a new region will be given little or no attention. The main topics that will be discussed are: (1) sufficiency of carbonaceous detritus and residues in the oil-forming rocks; (2) stage of carbonization of the organic matter in the oil-bearing formations; (3) folding of the strata; (4) thickness of sedimentary formations; (5) conditions of deposition.

Jan 1, 1921

By J. Spotts McDowell

Preparation and Use.-Magnesite is an important refractory in open-hearth, heating, and electric furnaces for steel-making and in many of those employed in the metallurgy of copper and lead. It is sold in the form of brick, finely ground "furnace magnesite" for brick-laying, and dead-burned grains for making and repairing furnace bottoms. The latter are a mixture of granules varying in size from pieces of about 5/8 in. (1.6 cm.) diameter to very fine but sandy particles. Dead-burned magnesite results from calcining 'the crude or lightly burned mineral at a temperature that will not merely drive off practically all the CO2, but will also cause sintering of the particles. During this process the pieces shrink considerably and become hard, dense, and inert to atmospheric moisture and C02; under-burned material, on the other hand, will hydrate on exposure to the air. A small percentage of ferric oxide seems to be necessary for the production of a satisfactory sinter; from 4.5 to 8 per cent. in the dead-burned grains is considered the most desirable amount. Dolomite has been little used for brick-making in the United States, but it is prepared for use in the granular condition calcined or "double-burned" and is the principal ingredient of several materials offered for sale under various trade names for refractory purposes. Dolomitic refractories are almost wholly confined to the open-hearth and electric furnaces, where they are used for fettling and as substitutes for magnesite. Much more magnesite and dolomite are used for basic open-hearth steel-making than for all other refractory purposes. The hearth of the furnace is usually built up of magnesite brick and dead-burned grain magnesite so laid that the brick base is protected by a working bottom of the granular material. The latter is sintered into place in layers 1 to 2 in. (2.5 to 5 cm.) thick to a total depth of 12 to 18 in. (30 to 45 cm.) at the center of the furnace. After each heat, burned dolomite is thrown against the banks as high as it will stick, and all holes in the bottom are filled. At most plants such holes, at the end of each week, are also

Jan 2, 1919

By P. W. Rainier

THE Chivor emerald field is situated on the eastern slope of the Andes in the Department of Boyacá, at an elevation of about 8000 ft. above sea level. It overlooks the Llanos (plains) of the Orinoco and is watered by many streams flowing into the Rio Meta, the Orinoco's largest tributary. The Rio Meta is navigable from the Orinoco to a point within about 50 miles of the Chivor district and may eventually prove to be the reasonable outlet for the future development of this part of the country. The topography of the district is extremely rugged and mountainous (Fig. 1), the difference in elevation between two points on a mining claim 1 km. square being sometimes as much as 4000 ft. The ground is covered with dense forest growth and the available timber is suitable and sufficient for mining purposes, but it is becoming gradually depleted by Indian clearings as the country around the mines becomes settled. The many streams combined with the rough topography give good possi-bilities for hydroelectric power. The center of population nearest to Chivor is Bogota, the capital of the republic and a city of some 300,000 inhabitants; the distance is two and one-half days' travel. The first stage of the journey from Bogota, is accomplished by rail to Chocontá, some 4 hr. travel. From Chocontá the journey is made in the saddle, one night being spent in Guateque. The latter is a small town and the nearest post office to the mines, being some 10 hr. ride distant. The roads are mere bridle paths, in parts hazardous and almost impassable in the wet season. All supplies brought to the mines, other than those produced locally, are carried by pack mule; mule freight from Chocontá costs 3 centavos1 per pound. The climate of the Chivor district is healthful and bracing. The wet season begins in March and concludes in November, the remaining months being dry. The annual precipitation is about 150 in. The temperature throughout the year is nearly constant, varying from about 45° F. to about 65° F. shade temperature. The rains are cold and unpleasant, and for the greater part of each day in the wet season the country is shrouded in dense mist. A fire can with comfort be kept burning in a living room all the year round. There are a few slight

Jan 1, 1929

AN intermetallic compound, Ni3A1, has an ordered fcc structure of type Ll2, and shows peculiar dependence of the yield stress upon temperature; i.e., the yield stress increases by a factor of six upon raising the temperature from 77" to 900K1, 2 This compound is technologically important, since many nickel-base superalloys owe their high-temperature strength to the peculiar yield stress behavior of Ni3Al. The only study of the elastic behavior of this compound was made by Davies and Stoloff,1 who determined Young's modulus of poly crystalline Ni3A1 between 300" and 730°K. The determination of single-crystal elastic constants of Ni3A1 is therefore of interest in connection with dislocation dynamics and is reported in this paper. A single-crystal specimen, 1 by 1 by 3 cm, was cut from an ingot generously supplied by Dr. B. H. Kear of Pratt & Whitney Aircraft. Following initial machining with a Servomet and a surface grinder, the specimen was etched and annealed at 1100°C for 5 hr in vacuum followed by furnace cooling. Two parallel faces were oriented normal to within ±l deg of a [I101 crystallographic axis by the back-reflection Laue technique. The parallel faces were hand-lapped, etched, and polished by the usual metallographic procedures. Final thickness along the [I101 axis was (0.9325 * 0.0005) cm. Chemical analysis gave an average composition of 87.35 pct Ni. Total impurity content is esimated to be no more than 0.1 pct. The elastic constants were calculated from measurements of ultrasonic waves which were propagated along the [110] axis. A longitudinal wave and two shear waves whose displacements are aligned along the [ 110], [li~], and [001] directions, respectively, are necessary in order to completely specify the three elastic constants. Two 3/6-in. quartz transducers were bonded to the parallel faces of the sample with ~ac-seal.3 Although this bond was sensitive to thermal shock, it performed satisfactorily over the entire temperature range for both longitudinal and shear wave propagation. A frequency of 5 mHz was employed in the method of Williams and Lamb4 in order to measure the absolute value of the ultrasonic velocity. The pulse-overlap technique of Mcskimin5 was also used at this frequency in order to determine the shift in the ultrasonic velocity

Jan 1, 1970