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By Philip D. Anderson, Ralph Hultgren

Heat contents of extremely pure iron were measured over the range 300"to 1433"K, using a diphenyl ether calorimeter. Results from three samples containing widely differing impurities agreed with one another and with Previously reported results at higher temperatures (1184 ° to 1809°K) by Olette and Ferrier. From these data a table of heat contents of iron has been Prepared which is believed to be more accurate than those previously available. CP values have been derived which are consistent with these heat contents, with the best experimental Cp data, and with the thermodynamic conditions of equilibrium between bcc and fcc iron. The opinion is expressed that low-temperature extrapolations of presently known Cp values for y-Fe are not reliable. It would seem that the thermodynamic properties of iron, which is by far our most important metal, should have been well established long ago. This is not the case, however. As discussed by Olette and Ferrier,' there is objection to every earlier heat content measurement. While the best true Cp determinations agree well at temperatures below the Curie point, there is wide divergence at higher temperatures. Several investigators have examined available data and attempted to calculate thermodynamic functions for iron that are consistent with the two equilibrium temperatures of bcc and fcc iron. The two primary efforts were those of Austin' in 1930 and Darken and smith3 in 1948. The recommended values differ considerably; integration of Austin's Cp values leads to a heat content at 1100°K which is 300 cal per g-atom higher than the value recommended by Darken and Smith. The compilation of Fisher4 in 1949 was based on the selection of Austin. In 1956, Weiss and Tauer obtained yet another set of values by resolving Cp values into components due to dilation, lattice vibration, electronic excitation, and magnetism. The magnitude of contribution by each component and its dependence on temperature was estimated by semiempirical means. Their values are not self-consistent in that they do not form smooth curves when plotted vs temperature; moreover, their calculations cannot easily be repeated since they do not give the values of some of the parameters used. Clearly, experimental values for iron were in a most unsatisfactory state. The presently described measurements of the heat content of iron were therefore undertaken, covering temperatures as high as 1433°K. While the work was in progress, the high-temperature (1193" to 1789"K) heat content measurements of Olette and Ferrier' were published; in the region of temperature overlap the present results agree with Olette and Ferrier well within experimental accuracy. It is believed that the present results, combined with those of Olette and Ferrier, provide for the first time a reliable set of heat contents of iron from room temperature to the melting point. From these data, guided by available Cp measurements, it proved possible to derive Cp, entropy, and free energy function values for @-iron from room temperature to the melting point, and for y- iron in the temperature region of its stability. Exhaustive study led to the conclusion that extrapolations of y-iron functions to room temperature were not reliable enough to be useful; hence these have been omitted from the tables. EXPERIMENTAL Materials. Three samples of extremely high purity iron from different sources, containing widely different impurities, were measured. The first of these, designated "Chipman", was kindly supplied by Dr. K. K. Kelley of the U. S. Bureau of Mines from a lot which was made many years ago by Dr. John Chipman of the Massachusetts Institute of Technology. The second, designated6'Teddington", was supplied by the National Physical Laboratory, Teddington, England, from a lot zone-refined by them. The third sample, designated "Irsid", was supplied by the Institute de Recherches de la

Jan 1, 1962

By E. T. Turkdogan

This is a compilation and a critical review of the data on the Fe-Ca-0 ternary system. Using the results on the reductiorz-equilibria, an oxygen potential diagram is drawn for the greater part of the system. A number of univariant systems and invariant points, not determined experimentally, are evaluated by making use of the theorem on univariant curves intersecting at an invariant point. The formation of solid solutions and ternary compounds and the crystal structures of some of the phases in the composition-diagram are given for a feu! temperatures. DURING the past thirty years there has been a continued interest in the study of the Fe-Ca-0 system. A detailed literature survey made by white1 in 1943 indicated that further work was required to clarify the phase relationships; in fact, the work carried out in the subsequent years, reviewed by Burdese2 in 1954, made a valuable contribution to a better understanding of this subject. Most of the data were obtained by the step-wise reduction of mixtures of iron oxides and calcium ferrites. However, there is some uncertainty about the phase relationships in this system, arising mainly from insufficient use of thermodynamic concepts in the construction of phase diagrams. In this paper an attempt is made to establish the invariant points from the available data. OXYGEN POTENTIAL DIAGRAM Schenck and coworkers3,4 were the early investigators who studied part of this system by the step- wise reduction method and suggested the formation of two ternary compounds, CaO.FeO.Fe2O3 and 2Ca0.5Fe0.2Fez03, the latter being referred to as point X. They also deduced from their results that the phases Y (8.74Ca0.32.5Fe0.8.74Fe2O3 and Z (2.02CaO-97.98FeO) were formed near the w?stite corner of the system. Martin and voge15 postulated the existence of the compounds CaO.9FeO and 4Ca0.3Fe3O4; the former is very close to the composition of point Z and the latter to that of CaO.FeO-Fe2O3. The most valuable contribution to the presen knowledge on this system was made by Cirilli and Burdese6-8 who showed by X-ray and chemical anal yses that there were two ternary compounds, CaO-Fe0.Fe2O3 and CaO.3FeO-FezO3; the former is the same as that suggested by Schenck et al. and the latter is close to their point X. The results of Cirilli and Burdese show that the phases Y and Z postulated by Schenk et al. are solid solutions of calcium oxide in w?stite. In most of the above-mentioned reduction-equilibria measurements carbon monoxide-carbon dioxide mixtures were used and in a few cases hydrogen-water vapor mixtures were employed. Using the

Jan 1, 1962

By Richard F. Hinds, F. O. Reudelhuber

Application of the conventional depletion drive calculation methods to volatile oil reservoirs results in erroneous estimates of ultimate recovery. In view of the increasing number and importance of volatile oil reservoirs, a special technique has been developed which will result in more realistic predictions using laboratory data obtained from reservoir fluid studies of a specific type. The experimental data are designed to permit continuous material accounting and, therefrom, provide the hy-clrocarbon composition of both the flowing oil and gas phases. The resultant well-stream composition data are then used directly in surface recovery calculations utilizing equilibrium ratios. A step by step procedure, specifically designed for routine use by the practicing reservoir engineer, is presented in an appendix. An actual study performed on a deep Mid-Continent reservoir is used ay an il-lustrathe example. INTRODUCTION It has been a practice for many years to utilize the conventional ma- terial balance methods in conjunction with relative permeability concepts for the prediction of recovery from solution gas drive reservoirs.' Those who have performed such calculations recognize that compromises of several types are necessary in order to reduce the calculations to a reasonable degree of complexity. The most serious assumption involved results from the necessity of treating the produced oil and gas as separate fluids, independent of each other in their behavior. It is further assumed that the gas which is evolved in the reservoir as a result of pressure decline will not yield liquid upon the reduction of pressure and temperature resulting from production through surface equipment. Although these shortcomings have been recognized,' it has been difficult to attempt refinement of calculation procedures since the laboratory data available normally were not of the proper type or extent to permit such calculations. Three general procedures have been available for depletion drive calculations when laboratory fluid data are of the conventional type. Differential Procedure The most simple, and most widely used, method requires use of the formation volume factor and gas sol- ubility data obtained from a differential liberation performed at reservoir temperature. This procedure ignores the differences existing between the fluid behavior in the reservoir and its behavior as it is produced through surface separation equipment. The errors introduced are not serious when dealing with very low volatility fluids and this method may be utilized if the laboratory data indicate only slight differences between the differential data and the flash data obtained from separator tests. Modified Differential Procedure This method was developed when it became apparent that medium volatility fluids evidenced a wide difference between the flash and differential data. The differential data are adjusted by changing from a residual oil basis to a stock tank oil basis. All that is required is multiplication of the differential data by the ratio of residual oil to stock tank oil relative volumes existing for the original reservoir fluid at the determined saturation pressure. This procedure generally results in increased calculated ul-timate recovery; however, such results should be viewed critically. Upon examination it may become apparent that the results are influenced by errors in reservoir liquid

Jan 1, 1958

By Don C. Blackmar

The production of non-ferrous secondary metals has become a large and important industry in the United States, and deals with practically cvery type of manufacturing concern. Its business is unique in that it generally buys frorn its customers as well as sells to them, whether they are individuals, cities, corporations, or the United States government. Its operations are of vital importance to the success and prosperity of nlany of the nation's most important manufacturers; yet there are few industries about which less is generally known by those outside it, whether concerning the rliagnitude of its operations or the details of its actual technique. The industry itself is to blame for this meager publicity, because its technical men have made few attempts to openly exchange ideas, in spite of the excellent examples set by the iron and steel or the copper and brass industries. Whether this is due to the ancient shroud of secrecy generally supposed to cover smelting operations, or because its technical men actually felt that the industry was too puny to be interesting, is hard to say. This paper will consider its subject in a general way, attenlpting to show something of the size and importance of the industry, as well as its fitness to do its work well. Attention will be called to the sound economic reasons for the handling of non-ferrous wastes by specialists, and to the often unseen losses of metals and labor which occur when manufacturc~rs rcclairn thrir own metallic wastes. Magnitude of the Modern Industry No particular thought is given to the kitchen accident whereby a ruined saucepan is sorrowfully tossed into the ash can, yet it is a fairly safe guess that within a month this saucepan, together with hundreds of its follows, will again be in service, perhaps in an autonlobile crankcase, or in an electric vacuum sweeper. It is by this conversion of the useless into the useful, whether from home or large manufacturer, that the secondary tonnage is built up.

The following delegates were appointed to the National Conservation Congress on May 2, 3, and 4, 1916, in Washington, D. C. HENRY S.. DRINKER, a GEORGE OTIS SMITH, A. F. Lucas, - W. L. SAUNDERS, VAN H. MANNING. President Ricketts was appointed delegate to the dedication ceremonies of the new buildings of the Massachusetts Institute of Technology in June. W. L. Saunders was appointed delegate to the ceremonies in celebration of the 150th Anniversary of the founding of Rutgers College to be held in October. George C. Stone was appointed delegate to the meeting on Standard Screen Scale of the U. S. Bureau of Standards. George D. Barron and Thomas T. Read were appointed delegates to the Second National Exposition of Chemical Industries to be held in New York in September. It was resolved, that the Institute shall pay the transportation of the Secretaries of the Local Sections to and from the Arizona Meeting. It was resolved that certain general topics' should be selected for discussion at the next meeting of the Institute and a session devoted to each.

Jan 6, 1916

William Kent, New York City: I regret that I have not had the time since the Cincinnati meeting to make as complete a study of Mr. Salom's paper as I wished. I regard it as one of the most important papers that have been presented on this subject, and worthy of complete study. I started out, on the limited time I had, on a system of study which I would recommend to any one else who has leisure to complete the investigation. I took the original report presented at the Cincinnati meeting, and selected from it' such tests as had the analyses reported along with the physical tests, giving the amounts of carbon, phosphorus, manganese, etc., taking only those in which all these elements are given.

Jan 1, 1885

By G. M. Ritcey

Sulphuric acid leaching has been up to the present, the most popular of the leaching routes. Oxide ores are usually leached with sulphuric acid directly by dump leaching, as practiced at the Bagdad or Bluebird Mines in Arizona, or by vat leaching as done at Inspiration Mining in Arizona. Upgrading of the low-grade oxide ores by dump leaching followed by cementation of the copper from solution by scrap iron has been replaced by the leaching-solvent extraction-electrowinning route which results in a high purity product at the mill site at reduced production costs compared to previous practice. High-grade oxide ores, vat leached with H2SO4, can contain, for example, 25 g Cu/l and 25 g H2S04/,l, or higher concentrations of both, and are presently fed directly to electrorefining plants. Advantages of coupling solvent extraction-electrowinning with the low cost dump leaching instead of using cementation, are as follows (1): a) the production of high purity electrolytic copper rather than cement copper;

Jan 1, 1978

By A. S. Malicsi, I. Iwasaki

The removal of hydrophobic coatings of flotation collectors from iron ores becomes of interest when a duplex flotation process is considered for upgrading, when a pelletizing process is considered for a concentrate floated with a fatty acid or a soap collector, or when a disposal of froth products from cationic silica flotation is of environmental concern. Ozone can oxidize organic compounds rapidly, thereby removing the hydrophobic coatings of flotation collectors. Ozone is widely used for treating and purifying drinking water, waste water treatment, and for chemicals processing (Murphy and Orr, 1975; Rice et al., 1980). Its uses in metallurgical operations, however, are very sparse (Allegrini et al., 1970; Chernobrov and Rozinoyer, 1975; Ishii et al., 1970; Iwasaki and Malicsi, 1985; Matsubara et al., 1978). Yet, its high reactivity and the absence of potentially hazardous byproducts become of interest in destroying flotation reagents adsorbed on mineral surfaces or remaining in mill water for recycle or for discharge. Duplex Flotation A duplex flotation process, as applied to oxidized iron ores, would involve a fatty acid flotation of iron minerals followed by an amine flotation of the siliceous gangue from the rougher iron concentrate. Such a process has been used in the Florida phosphate fields. Fatty acid coatings cannot be removed as readily with a simple acid or alkali treatment from iron oxide surfaces as from Florida phosphates. A combination of reagents, such as lime and quebracho, lime and alkali phosphate, or sulfuric acid and oxalic acid, has therefore been proposed. In a previous article (Iwasaki et al., 1967) , the use of activated carbon was found to be effective in removing fatty acid coatings both in the duplex flotation and the pelletizing processes. The use of ozone offers another approach to the removal of fatty acid coatings from iron oxide surfaces. To investigate the possible application of the duplex flotation process, a specularite ore from Michigan analyzing 36.5% iron was used. A 600-g (1.3-1b) sample was ground in a laboratory rod mill together with 250 g/t (0.5 lb per st) of sodium silicate to -150 µm (-100 mesh). This was transferred to a Fagergren laboratory flotation cell, and deslimed four times at 20 µm (quartz equivalent). The deslimed pulp was transferred to a laboratory conditioner, diluted to 40% solids, and conditioned with 250 g/t (0.5 lb per st) of soda ash and 250 g/t (0.5 lb per st) of oleic acid. The conditioned pulp was then transferred back to the Fagergren cell, floated until barren of froth, and the rougher froth product was returned to the cell and cleaned. The results are presented in Table 1. The cleaner concentrate at this point analyzed 45.3% Fe. The cleaner concentrate coated with fatty acid was transferred to a 2-L (0.53-gal) beaker. While the pulp was agitated with a glass T-stirrer, ozone was bubbled into the agitated pulp for 15 minutes at a rate of 10 mg/min (0.00035 oz per min) ozone (250 g/t or 0.5 lb per st 03 feed). It was observed that the pulp ceased to froth after about 10 minutes. The amine flotation of siliceous gangue from the ozonated pulp was carried out first by conditioning with a dextrin, a commonly used starch depressant for iron oxides. This was followed by flotation with a stage addition of an ether amine at increments of 100 g/t (0.2 lb per st). Three stages were required to float the siliceous gangue to near completion. The three froth products were combined and cleaned twice. When the cationic flotation Rougher, Cleaner 1 and Cleaner 2 cell products were combined, an iron concentrate analyzing 64.5% iron was obtained at an overall iron recovery of 72.8%. Pelletizing Fatty acid flotation concentrates have been pelletized successfully in northern Michigan mills. But at other locations, fatty acid coatings on iron flotation concentrates proved so undesirable in agglomeration that other methods of concentration had to be sought. For example, a sinter mix containing iron ore concentrates upgraded by fatty acid flotation resulted in decreased productivity. This occurred because the micropellets of particles with the hydrophobic coating are less tolerant of moisture. Thus, the bed permeability is lost (Beebe, 1965). The agglomeration of concentrates obtained by the fatty acid flotation alone, and the hydrophobic coatings destroyed by ozonation or by the duplex flotation process, is not expected to cause any difficulty since the surfaces of the concentrates would be hydrophilic. Removal of the fatty acid coating with activated carbon, indicated by the loss of floatability, was shown to restore the decrepitation temperature of wet balls during drying cycle (Iwasaki et al., 1967). Disposal of Cationic Silica Flotation Froths Recent demands of iron blast furnaces place the silica content of the magnetic taconite pellets at about 5%. Conventional process for magnetic taconite involving fine grinding and magnetic separation often produces magnetic concentrates analyzing in excess of 5% silica. This is due to the presence of the middling grains of siliceous gangue and magnetite. Cationic silica flotation of magnetic taconite concentrates (DeVaney, 1949) may be used to reduce the silica content. But the amine coating on siliceous gangue becomes of environmental concern when the flotation tailings are discarded in tailing ponds.

Jan 1, 1986

By C. W. Handy

ONE LAW cannot he evaded, the economic law of supply and demand. Silver, like any other commodity, is subject to this law; and its price in the long run is determined by existing conditions. I say "in the lone run because at times silver has appeared to mope contra to basic coalitions. Such movements, however, are, occasioned by the market's attempt to anticipate changes in these governing conditions. If the expected changes materialize then the new market level is justified, but if they do not then the market will revert to its previous status, A striking example of such a move occurred in November when the price advanced over 70, in ten days and then in the next two weeks lost more than it had gained. The reasons for this advance were that the speculative element interpreted certain events as favorable to silver namely, England suspension of the gold standard, higher shat prices, and the Chinese-Japanese crisis. When these expectations proved unjustified the inevitably, elapse followed became the governing conditions had not channel.

Jan 1, 1932

(Members are urged to send in for this column any notes of interest concerning themselves or their fellow-members) The following is a partial list of members and guests who called at Institute headquarters during the period May 10,1917, to June 10, 1917. F. J. Anderson, Cali, Colombia. W. F. Jahn, Kirkland Lake, Ont., Canada. George J. Bancroft, Denver, Colo. W. McA. Johnson, Hartford, Conn. W. F. B. Berger, Denver, Colo. J. E. Jopling, Marquette, Mich. F. J. Brulé, Toronto, Ont., Canada. William Kelley, Vulcan, Mich. J. Murray Clark, Toronto, Ont., Canada. H. M. LaFollette, La Follette, Tenn. Will L. Clark, Jerome, Ariz.. Dorsey A. Lyon, Washington, D. C. G. H. Clevenger, Palo Alto, Cal. James F. Magee, Lancaster, Pa. Paul S. Couldrey, Sound Beach, Conn. M. Ortin, Nijni-Novgorod, Russia. C. W. Crispell, Kingston, N. Y. - C. H. Palmer, Jr., Los Angeles, Cal. George A. Easley, La Paz, Bolivia. Edison S. Pettis, ?Mill Valley, Cal. Bancroft Gore, Butte, Mont. Mortimer A. Sears, Paintsville, Ky. John B. Guernsey, Roanoke, Va. W. J. Uren, Houghton, Mich. Rush M. Hess, St. Louis, Mo. C. E. Visel, New Haven, Conn. E. Hibbert, Nickelton, Ont., Canada. Percy E. Barbour, has resigned his position as managing editor of the Engineering & Mining Journal, to accept the appointment of Deputy Superintendent of the New York State Troopers, with headquarters at Albany, N. Y., with the rank of captain.. He has also been commissioned as captain in the 22nd Regiment, N: Y. N. G., having been formerly 1st Lieutenant.

Jan 7, 1917

By AIME AIME

0 N March 5, at Carnegie Hall, Cleveland, the Ohio Section held a joint meeting with the Cleveland Engineering Society, and the local sections of the American Chemical Society, American Society of Mechanical Engineers, and the American Society for Steel Treating. Prior to the meeting there was an informal dinner attended by 50 men. Then followed an address, "The Principles of Corrosion Protection," by Ulick R. Evans, the well-known British specialist in this problem. There were 266 present, presided over by Zay Jeffries, president of the American Society for Steel Treating and a member of the Cleveland Engineering Society. The address was well received and some discussion followed

Jan 1, 1929

By Edward W. Parker

One of the most important features of the coal-mining industry of the present day is one that is common to the majority of industrial enterprises—the substitution of mechanical methods for hand-labor.

Jan 1, 1900

By P. S. Bagga, P. T. Luckie

Liberation (the process of destroying the interlock between unwanted materials, such as mineral matter and pyrite, and coal) is one of the most important precursors to the benefication of raw coal in order to produce high grade marketable coals at economical recovery levels. Liberation is achieved usually by comminuting the raw coal. However, because of the significant interaction between the production of fine particles to achieve liberation and the cost of separating fine particles, the coal industry needs a method projecting the change in washability with size reduction. Such a projection can be combined with size reduction and separation simulators in order to examine completely beneficiation circuitry to produce coals of stringent specification. This paper presents the development of an appropriate liberation model for coal and its solution by Monte Carlo simulation to predict the expected washability of the raw coal as a function of comminution. It includes model validation with a known binary mixture as well as with a known teritary mixture.

Jan 1, 1983

THE following employment items are made available to AIME on a non-profit basis by the Engineering Societies Personnel Service, Inc., operating in cooperation with the Four Founder Societies. Local offices of the Personnel Service are at 8 W. 40th St., New York 18; 100 Farnswarth Ave., Detroit; 57 Past St., San-Francisco; 84 E. Randalph St., Chicago 1. Applicants should address all mail to the proper key numbers in care of the New York Office and include 6c in stamps far forwarding and returning application. The applicant agrees, if placed in a position by means of the Service, to pay the placement fee listed by the Service. AIME members may secure a weekly bulletin of positions available far $3.50 a quarter, $12 a year. MEN AVAILABLE Graduate Mining Engineer, 38; married, two children, Dutch nationality. Experience bauxite open-pit dragline, stripping and mining, nickel silicateous ore exploration, tin lode mining and dredging, ore dressing research, administrative. work, all in responsible positions. Read, write and/or speak seven languages. Desires responsible position. Presently located Netherlands. M-655. Mining Geologist, 35, married, 3 children, Canadian citizen. Eight years' experience Canadian gold mines as geologist, chief engineer, shift boss, 3 years in western U. S. as surveyor, junior geologist, etc. Desires position of responsibility. Prefer western United States. M-656-478-E-3-San Francisco. Mining Engineer, 30 years' experience open-pit and underground coal and iron mines. Held positions engineer to manager. Desire position of responsibility in foreign field. M-659.

Jan 1, 1952

By W. Rall, A. J. Birkle

The effect of fast-neutron irradiation on the micvo strcture of a common reactor pressure-vessel steel, A212 Grade B, was studied using thin-foil transmission electron microscopy. The dislocation density of the irradiated material is considerably greater than that of the nonirradiated control material. Annealing studies indicated that dislocations and hardness ill the irradiated material annealed out—as docs the radiation-induced embrittlement according to other- investigators— at temperatures STEELS in nuclear reactors are affected by neutron irradiation. In the American Society for Testing Materials (ASTM) A302B and A212B steels commonly specified by designers for reactor vessels, between 650° and 800°F. However, the dislocations and hardness in control samples cold-worked to 9 and 70 pct did not anneal out readily, and a high dis -location density was observed, even after a 1-hr anneal at 850°F. Based on the hypothesis that cllrster defects, rather than the increased dislocation density, are primarily responsible for mdicltiotz-iudziced e)nbriftlen7ent, reconzmendations are made for reducing the susceptibility to such ernbrittlement. exposures at a temperature of 550°F or lower to neutron dosages encountered during a 20- to 30-year life (-3 X 10'' nvt, >1 mev) may increase the nil-ductility transition temperature (NDT) as much as 300" or 400".'9 Therefore, to prevent brittle failures in reactor structures, extreme caution is required to reduce thermally induced stresses during all reactor shutdowns and startups when the temperature is below the NDT of the pressure vessel.

Jan 1, 1964

By A. B. Stevens

IN the calculation of oil and gas reserves by volumetric methods, it is necessary to know the volume of the reservoir available for the storage of the oil or gas. To obtain this information, a number of methods for determining both total and effective porosity of reservoir rocks are used. For the determination of the total porosity, or the porosity that considers all of the pore spaces, connected and isolated, the Russell7,8,9 and the Melcher-Nutting1-6 methods are the best known and most- widely used in the petroleum industry. These methods have disadvantages in that they give the total porosity of the samples and in that the samples are reduced to grain size in the determination. In many sands there may be little or no difference between total and effective porosity but in other sands there may be considerable difference between the two. For the estimation of oil-and gas reserves the effective porosity of the reservoir rock always should be used. Of the methods that have been developed for the determination of the effective porosity of reservoir rocks, or the porosity that considers only those pore spaces that are connected, the best known are the so-called Boyle's law6,10-13, and the Washburn-Buntings.5,6,11 methods. The Wash-burn-Bunting method is probably the most widely used because it gives effective porosity, it is rapid, and the apparatus is inexpensive. This method employs a special porosimeter in which the core sample is placed in direct contact with mercury. This method has disadvantages in that, as a result of the high vacuum created in the pore spaces, mercury is drawn into the openings, making it impossible to use the sample for a check determination and also ruining the sample for any further test, such as permeability. The purpose of this paper is to describe an appa-ratus employing the same principle as the Washburn-Bunting method but so designed that the core sample does not come in contact with the mercury in the porosimeter.

Jan 1, 1939

Jan 1, 1968

By Joseph T. Singewald

AMONG the genetically interesting iron ores of the United States are those of the St. Francis Mountains near Ironton and Iron Mountain, Missouri. They are specular hematite in porphyry. The Iron Mountain and Shepherd Mountain deposits are generally spoken of as veins and those of Pilot Knob, Cedar Hill, and Russell Mountain as bedded deposits. Iron Mountain has produced nearly 4,000,000 tons of ore and Pilot Knob about 1,500,000 tons. The output of the other three localities has been insignificant. Pilot Knob is no longer worked as an iron mine, but the rock is now being crushed for use as road metal. Iron Mountain has continued as an active producer. In 1927, the property was acquired by the M. A. Hanna Co. and an extensive prospecting and exploration campaign was undertaken, so that the ultimate production of Iron Mountain will doubtless greatly exceed the figures mentioned. Previous Theories of Origin Descriptions of the deposits and theories of their origin have been concerned mainly with Iron Mountain and Pilot Knob, which represent the two contrasting types of occurrence. The Iron Mountain deposits have been considered of close magmatic origin by Whitney' in 18.54, Geijer2 in 1915, and Spurr3 in 1927. Whitney referred to them as of eruptive origin. Geijer considered them fissure fillings at magmatic temperatures. Spurr called them vein dikes formed from ore magma which was essentially fluid iron oxide. Schmidt4 in 1872 ascribed them to fissure filling by thermal chalybeate waters of meteoric origin. Nason5 in 1892 advanced essentially the same explanation. One of the best

Jan 1, 1929

By Robert Mehl

THE purpose of this investigation was to prepare high-purity iron-carbon alloys, to determine as precisely as possible the A3(GOS), the Acm(SE), and the A1(PSK) transformation temperatures in the meta-stable iron-iron carbide system (up to 1.4 per cent C), and to study the influence of carefully controlled and constant rates of heating and cooling (1/8 to 2° C. per minute) upon the transformation temperature and upon the resulting microstructure. Apart from the general metallurgical importance attending the completion of such a task, it will be noted that highly precise transformation temperatures are of interest and importance in the thermodynamic study of this system1. Several determinations of the iron-iron carbide diagram have been made. These suffer generally from the low purity of the alloys used, and from the application of methods of investigation of low sensitivity. Attempts to compare and weight the many data available in an effort to construct as accurate a diagram as possible have, in the main, been unsuccessful. In general, the wide differences in the results of different workers, the lack of complete analytical data, the omission of important details relating to the heat-treatment of the alloys, and the meager description of the methods of investigation applied, render such a process of averaging nearly meaningless. It may be seen from the summaries by Epstein2 and Körber and Oelsen1 that variations as great as 30° C. exist in the reported data on the A3 temperatures in iron-carbon alloys. For-tunately, the A3 temperature in pure iron is now known to be 910° C. ± 1° C.3 The best recent work on iron-carbon alloys is that of Esser4 on hypoeutectoid steels and that of Sato' on both hypoeutectoid and hyper-eutectoid steels.

Jan 1, 1937

By Louis E. Toth, Alan W. Searcy

A modification of Le Claire's microscopic model for self-diffusion is developed in a form suitable for prediction of activation energies for diffusion in disordered substitutional solutions as well as in pure metals Bonding is considered as a localized interaction, and the energy of bonding between atoms of different types is taken as the arithmetic mean of the energies in the pure elements. The activation energies for vacancy formation and migration in substitutional alloys are shown to depend on the empirical constants developed for self-diffusion when the equations are adjusted for the mole fractions of the two elements. The differences in activation energies between alloys and pure metals are calculated and compared with the experimental differences. MaNY different correlations have been proposed for use in predicting activation energies for self-diffusion or diffusion in dilute alloys. Usually theories for self-diffusion cannot be applied to alloys nor can theories for dilute alloys be satisfactorily adapted to self-diffusion. We present here a correlation scheme which can approximate activation energies for diffusion, vacancy formation, and atom migration in substitutional-alloy systems of any concentration. The activation energy for self-diffusion QD has been correlated to the melting temperature Tm,1, 2 the sublimation energy L,,l the heat of fusion Lf,3 crystal structure, and valence.4 Working with mechanical parameters Le claire5 proposed that the activation energy for vacancy migration Qm could be related to appropriate shear moduli. He also proposed that the activation energy for vacancy formation 62, is proportional to Ls. THEORY We consider that Le Claire's expression for 4, is satisfactory. But an alternate expression for Qm in terms of the bulk modulus is just as satisfactory from a theoretical point of view for the prediction of the energy of vacancy migration in pure metals and can more easily be used for alloys. In order for Qm to be a minimum, not only the moving atom but also adjacent and nearby atoms must undergo distortions. These distortions are neither isotropic as is implied by a correlation with the bulk modulus nor unidirectional as implied by a correlation with a shear modulus, but are complex and multidirectional. A complete analysis in terms of the bulk modulus and all the shear moduli is not yet available. In a first approximation in which only one parameter is used, there is no obvious theoretical reason to prefer the shear modulus over the bulk modulus. The bulk modulus is a much more convenient parameter for use in predicting Qm. Shear moduli are known for less than half of the metallic elements while bulk moduli are usually available. Furthermore, because of the directional dependence of shear moduli, their estimation for alloys appears inherently more difficult than is the estimation of bulk moduli. We assume that the bulk modulus Bs reflects an average value of the shear moduli such that the strain energy at the point of maximum distortion of the lattice during vacancy migration can be expressed as

Jan 1, 1964