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By R. W. Gurry

Thermodynamic calculations indicate that boron is a better deoxidizer than silicon but probably is not quite as effective as aluminum. Boron should, therefore, be readily oxidized out of the open-hearth bath, which implies that it is not recovered in significant concentration from any scrap charged; also that, if added in the ladle, it tends to oxidize out during teeming unless protected by the presence of a better deoxidizing agent. These conclusions do not apply to liquid cast iron, in which the oxygen content is much lower than in liquid steel. The possibility of conserving certain strategic alloying elements widely used in steelmaking, notably manganese, chromium and molybdenum, by the use of boron, which in small concentration appears to be extraordinarily effective in promoting hardenability, raises a question as to what extent any boron present in the scrap charged into the open hearth is oxidized out during melting and subsequent refining. This question is significant because the optimum concentration of boron in the finished steel, which is fairly critical, would be very difficult to attain if the boron in the charge were largely retained in the metal. Moreover, unless boron is substantially eliminated in the open-hearth process its use on a large scale would eventually make it impossible to produce boron-free steel except by restricting the charge to virgin material. There is at present, unfortunately, virtually no satisfactory direct evidence to provide an answer to this question; but there are indications from practice that boron is oxidized out in the open hearth in the production of medium or low-carbon steel, although it may be retained if the carbon content remains fairly high; that is, if the oxygen is kept fairly low. In the absence of direct data, it is necessary to rely upon the indications of indirect evidence, the best approach now available being a thermodynamic calculation of the deoxidizing power of boron in liquid steel by the general method used so successfully by Chipman1 in his study of the reactions in the open-hearth process. The thermal data for boron, upon which such a calculation must be based, are reasonably satisfactory; the only quantities not directly determined are the entropy of melting of boron, the activity coefficient of boron in liquid steel, and the activity coefficient of B2O3in an open-hearth slag; but these values may be estimated with ample accuracy. The results of this calculation, which is presented later, are given in Table I, together with corresponding data for other deoxidizing elements. This table shows the calculated residual content of oxygen in equilibrium with different residual concentrations of the deoxidizer in the metal;

Jan 1, 1944

By Arthur Knapp

Oil-well depletion curves, to be of value, should show when a well or lease may no longer be operated at a profit. The difference, at any time, between the total expenditures and the total income of a lease or well may be called the lease status. Plotting this lease status against time will give a curve subject to more accurate and different interpretations than the barrels-time curves. According to the hypothetical barrels-time curves shown in Fig. 1, well A, at the end of 16 mo., is producing twice as much oil as well B and will continue to produce for another year whereas well B will cease producing in about 6 months. Data fob Lease Status-time or Dollars-timb Curve Time Lease Months Status Lease purchased for $3000.............................. 0 — $ 3,000 No expenses chargeable to lease for 3 mo................. 2 — 3,000 Well A is started; cost of drilling for month is $16,000..... 3 — 19,000 Well is completed at additional cost of $10,000............ 4 - 29,000 Well A is brought in and flows 10,000 bbl. first month (we Fig. 1). Necessary to invest in tanks, boilers, pipe lines, etc.; difference between expenditures and receipts gives profit for month of $5,000............................ 5 — 24,000 Investment is small, cost of operating well A is small, so profits are $15,000................................... 6 — 9,000 Well ceases to flow so there is additional investment for pumping equipment and additional operating expense; net earnings from 6,000 bbl. of oil produced is $4,000. 7 ... Lease operation nor becomes normal and curve becomes smooth........................................... 8 — 500 9 2,000 10 4,500 11 6,000 12 7,700 13 8,700 14 9,000 15 9,500 16 10,000 A hypothetical lease status-time, or dollars-time, curve of this lease is shown in Fig. 2. At zero time, the lease is purchased for $3000, which is plotted below the zero dollar line, All subsequent entries are plotted

Jan 1, 1921

For the year ending February, 1919 PRESIDENT SIDNEY J. JENNINGS NEW YORK, N. Y. PAST PRESIDENTS L. D. RICKETTS NEW YORK, N. Y. PHILIP N. MOORE ST Louis, Mo. FIRST VICE-PRESIDENT C. W. GOODALE BUTTE, MONT. TREASURER GEORGE C. STONE, NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND, NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON NEW YORK, N. Y.

Jan 7, 1918

For the year ending February, 1919 PRESIDENT SIDNEY .J. JENNINGS NEW YORK, N. Y. PAST PRESIDENTS L. D. RICKETTS, NEW YORK, N. Y. PHILIP N. MOORE, ST.Louis, Mo. FIRST VICE-PRESIDENT C. W. GOODALE BUTTE, MONT. TREASURER GEORGE C. STONE, : NEW YORK, N. Y. SECRETARY' EMERITUS ROSSITER W. RAYMOND NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON, NEW YORK, N. Y.

Jan 10, 1918

For the year ending February, 1918 PRESIDENT SIDNEY J. JENNINGS, NEW YORK, N. Y. PAST PRESIDENTS L. D: RICKETTS, ; . , . NEW YORK, N. Y. PHILIP N. MOORE, , ST. Louis, Mo FIRST VICE-PRESIDENT C. W. GOODALE, . . . . BUTTE, MONT. TREASURER GEORGE C. STONE NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND,. NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON NEW YORK, N. Y.

Jan 3, 1918

For. the year ending February, 1919 PRESIDENT SIDNEY J. JENNINGS NEW YORK, N. Y. PAST PRESIDENTS L. D. RICKETTS NEW YORK, N. Y. PHILIP N. MOORE, ST. LOUIS, M.O. FIRST VICE-PRESIDENT C. W. GOODALE, BUTTE, MONT. TREASURER GEORGE C. STONE, NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND, NEW YORK, N.Y. SECRETARY BRADLEY STOUGHTON NEW YORK, N. Y.

Jan 8, 1918

By R. F. Mehl, J. T. Ransom

For many years the Metals Research Laboratory of Carnegie Institute of Technology has been concerned with the statistical nature of the engineering properties of steel from an experimental viewpoint, particularly those properties representing ductility.' In the past three years new work has been directed toward evaluating the statistical nature of the endurance properties. It has been shown that both the fracture curve and the endurance limit in fatigue are markedly statistical in nature. The S-N curve (and the endurance limit) of ferrous materials is often determined with specimens which number as few as ten. The common procedure is to test the first specimen at a stress well above the expected endurance hmit. Each succeeding specimen is then tested at a progressively lower stress, until, after five or six tests, a specimen runs ten million or so cycles without failing. Two or three more specimens are then used to find the highest stress at which failure will not occur; the limiting stress determined in this way is called the endurance limit. It has now been found, however, that the variability in the fracture curve and in the endurance limit in heat-treated alloy forging steels is so great that S-N curves must be drawn on the basis of distribution curves which can be appraised only by statistical methods. Two methods have been adopted in this study: (1) straightforward statistical studies of cycles to fracture of a number of specimens at each of a series of stress levels, and (2) a new abbreviated statistical method, known as "staircase testing."2 The latter corisists in testing a series of specimens, one by one, with the test stress for any given specimen automatically

Jan 1, 1950

By W. O. Philbrook, A. E. El-Mehairy

The reduction by hydrogen of individual particles of dense hematite implanted in beds of inert spheres is controlled by single-particle kinetics. No evidence of reagent starvation was found down to low flow rates established by pressure gradients as low as 0.01 in. H2O per- in. of depth in beds of spheres as small as 3/16 in. diam. The optimum size for most rapid reduction of beds of homogeneous ores results from the effect on reducing potential of the gas of competing factors of supply and consumption. A recent publication1 presented the results of a study of the rate of reduction of iron ore in a fixed bed by hydrogen introduced at constant pressure differential. Under these conditions the reagent flow rate varied directly with the bed permeability, which was a function of particle size and shape and bed voidage, and inversely with the temperature-dependent viscosity of the gas. The present note adds data from supplementary experiments designed to reveal whether or not any partial reagent starvation arising from a flow-dependent transport resistance in the gas phase might have been operative. Kinetic studies were made of the reduction of individual spheres of iron oxide inserted into beds of inert spheres, so that the reagent flow rate and aerodynamic conditions were again determined by bed characteristics and temperature. The experimental techniques and apparatus were similar to those previously described.' The synthetic iron ore spheres were wet-rolled by hand from powdered, reagent-grade* Fe2O3 and subsequently dried and then fired in air at 1250°C. The indurated pellets has almost no porosity as indicated by their specific gravity of 5.10. The beds were made of dense alumina spheres, closely sized to the same dimension as the iron oxide spheres, in the following diameters: 3/16, 1/4, 5/16, and 3/8 in. Each bed was hand-packed of particles of a single size to a controlled voidage of 0.32 and depth of 3 in. within a capsule having an internal diameter at least 10 times the particle diameter. A few weighed iron oxide spheres were individually planted in the central plane of the bed of inert spheres at points away from the wall. Reduction was carried out at atmospheric pressure by purified hydrogen at 670°, 800°, and 985°c. The reagent was supplied at precisely controlled pressure differentials of 0.01, 0.02, and 0.03 in. of water per in. of bed depth. This gave a range of flow rates similar to that used in the study of beds of ore and comparable with blast-furnace practice in terms of mols of reducing gas per hr per sq ft of cross-section. Viscous flow prevailed in all beds under the experimental conditions of this study. The reduced particles were checked for loss in weight and then sectioned for metallographic examination. Occasional particles were found to have contained minute internal cracks that interfered with the concentricity of the reduction interfaces, and data for such particles were rejected. An experimental rate constant for the reduction of the imbedded Fe2O3 spheres was calculated on the assumption that the rate was proportional to the metal-oxide interface area by an equation that has been found by McKewan2 to describe the reduction of single spheres

Jan 1, 1962

By George S. Rice

THE wide scope of the causes and effects of ground movement and their interrelation to various kinds of mining and geological conditions are not always understood. Minimizing of roof movement by selection of suitable mining methods is closely allied to the problem of obtaining maximum safety in mining, but there are other questions involved: for example, mechanical developments which increase the production of ore and other minerals per shift or unit of labor but which, though highly ingenious, may increase hazards. More- over, the newer mobile loaders need much space for operation with longer protecting roof spans. Another problem emphasized by mechanization is the incompleteness of extraction of mineral, as there is no governmental requirement (except for limited leases on the public domain) in this country, as in European countries, and loss of coal in pillars is accepted by mine operators rather than risking the loss of an ex- pensive loading machine from a heavy roof fall. The extent to which losses of coal in mining are now being incurred is conjectural, for it has been fifteen years since there has been a comprehensive survey. In that study a loss of slightly over one-third of the coal in both anthracite and bituminous mining was indicated.

Jan 1, 1939

By R. C. Weed

LEACHING in place at Cananea began in the 1920's on a limited scale. The first plants were small wooden boxes located underground in the Capote and Oversight mines, and output was low. Scrap iron was used as precipitant. Later several other small plants were started up. Leaching was limited entirely to underground areas, and production remained low. The Veta precipitating plant, the first on a larger scale, was put into operation in the late 1920's. After a period of intermittent service it was rebuilt in 1946 and has since been running continuously. In 1943 work on the Colorada open pit was started. This produced 40 million tons of waste, which averaged 0.20 pct capper. When these dumps had aged a few years it was decided to leach them on a large scale, and after considerable research and investigation a leaching system of pumps and pipelines was laid out and installed. At the same time the Ron-quillo precipitation plant was built to treat the copper solutions from the pit dumps. This plant started operation in March 1953. Leaching areas consist of the Colorada pit dumps and various mined out and caved underground stopes. The principal mineral, chalcocite, leaches readily in a weak sulfuric acid solution containing ferric iron. Enough pyrite is contained in the areas to produce an acid-ferric iron solution strong enough to dissolve the copper. Each area is studied to determine the best method of distributing the water over it and the best method of collecting the copper-bearing solutions after leaching has taken place. Water is generally distributed by means of ponds, ditches, and sprays. Spraying has proved the best method of spreading the water evenly; however, in a dry climate some water is lost through evaporation. After passing through the leachable material the solution is collected underground by dams and bulkheads and on surface by dams. An effort is made to give the maximum storage capacity practicable.

Jan 1, 1957

By Henry B. Kaeding

This paper presents the results of experiments in the treatnient of the gold-bearing ores of the Pis Pis district, near the Atlantic coast of Nicaragua, C. A. Up to the present time, the methods in use in this section of the country for the extraction of the values from the ores have been of the crudest, and the waste has been criminal in its enormity. The transportation of heavy machinery being difficult and costly, recourse has been had to flimsy and inadequate installations, involving great wastes in operation. In some places $15 ore is considered the lowest workable grade. One mine that came under my observation had a 7-ft. vein of $23 ore when examined for purchase; it has been running for years and is now deeply in debt. The future metallurgy of these ores must depend upon chemical, mechanical, and economical considerations—the last being, of course, a resultant of the two former, discussed in the light of prevailing or realizable commercial and industrial conditions. I. Chemical. The ores consist principally of quartz, carrying galena, pyrite, marcasite, and chalcopyrite, and occasionally magnetite, hematite, pyromorphite, and sphalerite, in which minerals the gold lies. The quartz veins occur between malls of andesite, " porphyry," or dioritic rocks, occasionally limestone and dacite. Often the dacite itself is heavily ribbed and filled with auriferous quartz, and is mined as ore. Owing to the excessive rainfall of the country, the ores above water-level have been oxidized and leached of their sulphides, and have become in that operation highly acid and free from

Jan 1, 1912

By W. M. McKewan

Magnetite pellets were reduced in flowing hydrogen at pressures up to 40 atm over a temperature range of 350° to 500°C. The rate of weight loss of oxygen per unit area of the reaction surface was found to be constant with time at each temperature and pressure. The reaction rate was found to be directly proportional to hydrogen pressure up to 1 atm and to approach a maximum rate at high pressures. The results can be explained by considering the reaction surface to be sparsely occupied by adsorbed hydrogen at low pressures and saturated at high pressures. PREVIOUS investigation1,2 have shown that the reduction of iron oxides in hydrogen is controlled at the reaction interface. Under fixed conditions of temperature, hydrogen pressure, and gas composition, the reduction rate is constant with time, per unit surface area of residual oxide, and is directly proportional to the hydrogen pressure up to one atmosphere. The reduction rate of a sphere of iron oxide can be described3 by the following equation which takes into account the changing reaction surface area: where ro and do are the initial radius and density of the sphere; t is time; R is the fractional reduction; and R, is the reduction rate constant with units mass per area per time. The quantityis actually the fractional thickness of the reduced layer in terms of fractional reduction R. It was found in a previous investigation2 of the reduction of magnetite pellets in H2-H,O-N, mixtures, that the reaction rate was directly proportional to the hydrogen partial pressure up to 1 atm at a constant ratio of water vapor to hydrogen. Water vapor poisoned the oxide surface by an oxidizing reaction and markedly slowed the reduction. The enthalpy of activation was found to be + 13,600 cal per mole. It was also found that the magnetite reduced to meta-stable wüstite before proceeding to iron metal. The following equation was derived from absolute reaction-rate theory4,8 to expfain the experimental data: where Ro is the reduction rate in mg cm-2 min-'; KO contains the conversion units; Ph2 and PH2O are the hydrogen and water vapor partial pressures in atmospheres; Ke is the equilibrium constant for the Fe,O,/FeO equilibrium; Kp is the equilibrium constant for the poisoning reaction of water vapor; L is the total number of active sites; k and h are Boltzmann's and Planck's constants; and AF is the free energy of activation. Tenenbaum zind Joseph5 studied the reduction of iron ore by hydrogen at pressures over 1 atm. They showed that increasing the hydrogen pressure materially increased the rate of reduction. This is in accordance with the work of Diepschlag,6 who found that the rate of reduction of iron ores by either carbon monoxide or hydrogen was much greater at higher pressures. He used pressures as high as 7 atm. In order to further understand the mechanism of the reduction of iron oxide by hydrogen it was decided to study the effect of increasing the hydrogen pressure on rebduction rates of magnetite pellets. EXPERIMENTAL PROCEDURE The dense magnetite pellets used in these experiments were made in the following manner. Reagent-grade ferric oxide was moistened with water and hand-rolled into spherical pellets. The pellets were heated slowly to 550°C in an atmosphere of 10 pct H2-90 pct CO, and held for 1 hr. They were then heated slowly to 1370°C in an atmosphere of 2 pct H2-98 pct CO, then cooled slowly in the same atmosphere. The sintered pellets were crystalline magnetite with an apparent density of about 4.9 gm per cm3. They were about 0.9 cm in diam. The porosity of the pellets, which was discontinuous in nature, was akrout 6 pct. The pellets were suspended from a quartz spring balance in a vertical tube furnace. The equipment is shown in Fig. 1. Essentially the furnace consists of a 12-in. OD stainless steel outer shell and a 3-in. ID inconel inner shell. The kanthal wound 22 in. long, 1 1/2, in. ID alumina reaction tube is inside the inconel inner shell. Prepurified hydrogen sweeps the reaction tube to remove the water vapor formed during the reaction. The hydrogen is static in the rest of the furnace. The sample is placed at the bottom of the furnace in a nickel wire mesh basket suspended by nickel wire from the quartz spring. The furnace is then sealed, evacuated, and refilled with argon several times to remove all traces of oxygen. It is then evacuated, filled with

Jan 1, 1962

By E. T. Turkdogan, Klaus Schwerdtfeger, P. Grieveson

The rate of growth of "Fe4N" on a iron was measured by nitriding purified iron strips in flowing am -monia -hydrogen gas mixtures at 504" and 554°C. It is shown that a dense nitride layer is formed when a zone -refined iron is used in the experiments. With less pure iron, the nitride layer is found to be porous. Through theoretical treatment, the self-diffusivity of nitrogen is evaluated porn the parabolic rate constant, and found to be essentially independent of nitrogen actirlity, e.g., D* = 3.2 x l0-12 and 7.9x l0-12 sq cm per sec at 504" and 554?C. Some consideration is given to the mechanism of diffusion in the nitride phase. THERE is a great deal of background knowledge on the solubility and diffusivity of nitrogen in iron, and on the thermodynamics and crystallography of several phases in the Fe-N system. Although case-nitrided steels have many applications in practice, no work seems to have been done on the diffusivity of nitrogen in the iron nitride, ?', phase. The only work reported on the related subject of which the authors are aware is an investigation by Prenosil,1 who measured the growth rate of the e phase on iron by nitriding in ammonia-hydrogen gas mixtures. EXPERIMENTS Purified iron plates of approximate dimensions 1 by 0.5 by 0.03 cm were nitrided in flowing mixtures of ammonia and hydrogen, in a vertical furnace fitted with a gas-tight recrystallized alumina tube. After a specified time of reaction, the sample was cooled to room temperature by withdrawal to the water cooled top of the reaction tube. The furnace temperature was controlled electronically in the usual manner within *l°C; the temperature was measured using a calibrated Pt/Pt-10 pct Rh thermocouple. For each experiment the iron strip sample was cleaned with fine emery cloth and degreased with tri-chloroethylene prior to the experiment. The ammonia-hydrogen gas mixtures were prepared from anhydrous ammonia and purified hydrogen using constant pressure-head capillary flowmeters. The gas mixture flowed upward in the furnace with flow rate of 400 cc per min at stp. The composition of the gas mixture was checked by chemical analysis at regular intervals. In most cases, the compositions of the exit gas and metered input gas agreed within about 0.3 pct, indicating that cracking of ammonia did not pose a problem at the temperatures employed. Two series of experiments were carried out using two different types of purified iron samples. In the first series of experiments at 550°C, vacuum carbon deoxidized "Plastiron" was used. The main impurities present in this iron were, in ppm: 4043, 50-Cr, 20-Zr, 40-Mn, 20-P, 20-S, 20-C, 50-0, and 10-N. In these experiments the rate data were obtained by measuring the change in weight of the iron specimen suspended in the hot zone of the furnace by a platinum wire from a silica spring balance. The nitride layer formed in these experiments was found to be porous, particularly near the outer surface. In other experiments, high purity zone-refined iron (prepared in this laboratory) was used. The total impurity content of this iron was 30 ppm of which 20 ppm was Co + Ni, 4 ppm 0, other metallic impurities were less than 1 ppm. The zone-refined iron bar, -2.5 cm diam, was cold rolled to a thickness of about 0.03 cm and the specimens were prepared for the experiment as described earlier. After the nitriding experiment, the sample was copper plated electro-lytically and mounted in plastic for metallographic polishing. After polishing, the thickness of the ?' layer was measured using a metallographic microscope. The nitride layer formed on the zone-refined iron was essentially free of pores. RESULTS The different morphology of the nitride layers grown on "Plastiron" and zone-refined iron is shown in Fig. 1. Both samples were nitrided side by side for 55 hr. The holes in the less pure iron, Fig. l(a), are confined to a region about one half thickness from the outer surface. The dense layer grown on zone-refined iron, Fig. l(b), is thinner than the porous layer on the "Plastiron". The impurities in the iron are believed to be responsible for the formation of a porous nitride layer. The pore formation may be due to the high nitrogen pressures existing within the nitride layer, e.g., the equilibrium nitrogen pressure is 1.2 x l05 atm in the 38.6 pct NH3-61.4 pct H2 and 6.6 x l03 atm at the Fe-Fe4N interface at 554°C and 0.96 atm. It is possible that the oxide inclusions present in the electrolytic iron may facilitate the nuclea-tion of nitrogen gas bubbles within the nitride layer. Support for this reasoning is the fact that pores are only encountered in the outer range of the layer where nitrogen pressures are largest. The photomicrographs in Fig. 2 show the effect of reaction time on the thickness of the dense nitride layer formed on zone-refined iron. These sections are from samples nitrided in a stream of 29 pct NH3-71 pct H2 mixture at 554°C for 22, 70, and 255 hr. In all the sections examined the nitride-iron interface was noted to be rugged. These irregularities are be-

Jan 1, 1970

By Frank Firmstone

In April, 1873, No. 2 furnace at the Glendon Iron Works being out of blast, it was decided to alter it from an open to a closed top. The three side flues, through which a part of the gas was formerly taken off, were 15 feet below the top, and as, for various reasons, it was not convenient to cut new flues through the brickwork at the top, as is commonly done with closed-top furnaces, a modification of Coingt's charger was employed. This apparatus, as figured by De Vathaire,* consists of a cup or hopper, like that used with the cup and cone, and a central pipe for taking off the gas, which descends some distance into the furnace, and has a projection around it forming a seat for a ring of a triangular cross-section, which closes the opening between the cup and the central gas-pipe. The charge is put into the cup, and by lowering the ring, is thrown into the furnace, a part going outside of the ring toward the walls, and a part through the inside toward the gas-pipe. In this form the apparatus was not applicable, for: 1st. With a gas-pipe three feet in diameter, in a top eight feet in diameter, the openings left by lowering the ring would not be large enough to let lump coal pass through. 2d. For the charger to shut tight, the ring must bear equally against the projection made for it on the gas-pipe, and against the edge of the cup. This would not be difficult to effect when the apparatus is first put up, but a comparatively small change in the relative position of the parts, such as is almost certain to occur from expansion, would cause the ring to touch the pipe or the cup, whichever happened to be the lower, first, and leave a leak between it (the ring) and the other. In the plan adopted (Figs. 5 and 6, Plate I), the central opening in the ring is closed by the bottom of the gas-pipe, whereby more room is left for the passage of the stock when the charger is open, than if the pipe descended into the furnace; and the pipe, instead of being rigidly supported, rests on the ring, when the charger is closed, and follows it for two or three inches as it opens, until stopped by the counter-balance lever C. When the ring is raised to close the furnace top, it comes in contact first with the bottom edge of the gas-pipe, then both are raised together, until stopped by the ring touching the edge of the cup. In this way a good joint is made at both places.

By B. Blumenthal

THE present investigation was planned as a survey of the lead-rich portion of the ternary lead-antimony-silver system by thermal analysis. Since, however, a rigorous application of the conventional thermal analytical method is time consuming, an attempt was made to speed up the investigation by reducing the time required for a single thermal analysis. This was done by increasing the rate of cooling to 12° to 18°C. per minute. Since such a rate does not permit even an approach to equilibrium conditions, the melt was stirred vigorously by a stirrer operating at the high rate of 665 r.p.m. This proved to be effective in obtaining cooling curves with distinct points of arrest and of excellent reproducibility, which satisfactorily compare with those obtained at a rate of 1° to 2°C. per min. with or without slow stirring (Fig. 1). By this method the lead-rich end of the lead-antimony system and a series of ternary alloys in sections parallel to the lead-antimony side of the ternary system were investigated and it was observed that the two branches of the' liquidus curve of the .binary alloys did not intersect at the eutectic temperature. An equivalent effect was observed in the ternary system. The eutectic temperature of the binary lead-antimony system was found to be 252.0°C., which confirms the recent investigation by Pellini and Rhines,1 who determined the eutectic temperature to be 251.5°C. The observation that the curves of primary crystallization of the lead-antimony system do not intersect at the eutectic temperature was previously made by Dean.2 Dean explains the phenomenon by assuming the existence of a compound Sb4Pb. He felt that super-cooling was not the cause of the phenomena because he was unable to influence them by inoculation. The X-ray investigation by Solomon and Morris-Jones,3. the metallographic investigations by Stead,4 Charpy,5 Gontermann,6 and Dean, Zickrick and Nix,7 and the numerous investigations of physical properties, definitely disprove the occurrence of any compound. The work of Dean was not confirmed by Broniewski and Sliwoski,8 whose experiments did not show any irregularity and who report a eutectic composition of 13 per cent antimony and a eutectic temperature of 250° to 252°C. at a rate of cooling of about 6°C. per min. Abel, Redlich and Adler9 then report a eutectic composition of 12.1 per cent upon reviewing the previous, publications and adding a few of their own cooling curves. In 1934 Quadrat and Jiriste10 found from careful analyses of the bottom portion of slowly cooled hypereutectic melts that the eutectic contains only 11,4 to 11.5 per cent antimony. (Previous analyses by Stead4 in 1881 gave 13 per cent:) Weaver," however, reported in 1935 that cooling curves indi-

Jan 1, 1943

Jan 1, 1967

Jan 1, 1967

By Ralph Arnold

LESS than eight months ago at the annual meeting of the American Institute of Mining and Metallurgical Engineers, attention was called to the demoralizing effect of the abnormal oil production of Mexico on the oil situation in the United States, and it was predicted that this unstabilizing influence would probably become impotent in 18 to 24 months through ' the exhaustion of the principal producing fields of Mexico, unless new fields were found in- the meantime. When this statement was made, the daily production of Mexico was about 600,000 bbl. of crude oil; now it is about 350,000 bbl. No new pools of consequence have been opened, although extensions have been made to two old pools. Over 200,000 bbl., or more than half of the present daily production, comes from Los Naranjos, Amatlan and North Zacamixtle fields, in which practically every well is so affected by salt water that the potential production dropped 50 per cent. in the month of September, clearly indicating that these fields are moving rapidly toward extinction. How much longer the one remaining important pool will last is a matter of conjecture.

Jan 1, 1921

By R. A. Vandermeer

It is usually assumed that the rate-determining step in the migration of a grain boundary involves the thermally activated transfer of single atoms across the interface. Chemical reaction rate theory then gives a migration rate which is proportional to the driving force when this is small compared to kT.1 In their recrystallization studies on aluminum, Gordon and vandermeer2 obtained data which was capable of providing the first experimental test of this proportionality. They correlated stored energy (driving force) release measurements determined calorimetrically with fraction recrystal-lized kinetic (growth rate) data acquired metallo-graphically at a temperature where a significant amount of recovery takes place concurrently with recrystallization. Within experimental error, the results of Gordon and Vandermeer confirmed experimentally, at least over a limited range, the linear dependence of boundary migration (growth) rate on driving force in accordance with theory. In obtaining these results, however, an incorrect, implicit assumption was made in relating the average instantaneous growth rate of the recrystallized grains to the measured fraction recrystallized kinetic data. The purpose of this present note is to point out and correct this assumption. An alternate approach, whereby a more proper average growth rate can be calculated from the recrystallization kinetic data, is presented. The earlier data, reevaluated in terms of this new approach, show the same general trend as before so that the original conclusion of Gordon and vandermeer2 is still valid. As was shown in a detailed study3 of the geometrical features of recrystallization in aluminum, the colonies of recrystallized grains can be regarded as uniform cylinders embedded in a three-dimensional matrix, the number of such colonies being constant. Thus during the early stages of recrystallization the volume fraction recrystallized, Xv, can be written as Xv=ynvlr2 [l] where y is a shape factor and i and r are defined as the average length and radius of a recrystallized colony and are spatial averages over the specimen. -nv, is the number of such colonies in a unit of volume. The erroneous assumption made in the earlier paper2 was that r in Eq. [I] could be replaced by

Jan 1, 1965

By C. D. Stahl, S. M. Farouq Ali

This investigation attempts to describe and simulate the alcohol displacement process by means of a cell model, as employed in chemical engineering practice. The proposed model is more simple than previously proposed models. and utilizes parameters chosen on a theoretical basis. The model successfully reproduced the formation of the stabilized bank and the breakthrough of alcohol, the latter depending on one of the model parameters, which may be correlated with the length of the porous medium. Moreover, the effects of the phase behavior of the liquid system involved, as observed in experimental studies, were reproduced. Several variations of the basic model were devised and tested on a digital computer. These included the cases in which: (1) the actual value of fractional flow was used in cell-to-cell computations; (2) the number of cells was varied within the same run; and (3) incomplete rather than complete phase equilibrium was assumed within each cell. The proposed cell model clarifies the basic mechanism of the process. Detailed concentration profiles obtained for each cell, for instance, showed the mechanism of bank formation in relation to the phase behavior characteristics. The results obtained indicated a varying degree of phase equilibrium concommitant with changes in the velocities of the phases in an actual alcohol displacement. This condition was approximated by changing the number of cells during the simulation. Interesting information was obtained on the influence of path length on the efficiency of alcohol displacement, which has been the subject of some controversy. Certain limitations preclude the use of the proposed model as a substitute for experimental studies. The results obtained were, nevertheless, of value in interpreting the experimental results. INTRODUCTION During recent years considerable effort has been directed toward an understanding of alcohol displacement, the process whereby oil and water are recovered from a porous medium by the continuous injection of a solvent. The complex nature of the physical process involved has so far defied a complete mathematical treatment. Other methods of approach, amounting to an overall material balance, have been proposed, yielding useful information on certain aspects of the process.1-3 Taber et al, in particular, defined the displacement mechanism in terms of the phase behavior of the alcohol-oil-brine system invoIved.2 Wachmann reported a mathematical treatment of alcohol displacement subject to certain simplifying assumptions? Donohue proposed the use of a "cell model" for simulating alcohol disPlacement.5 The nature of the assumptions involved limited the utility of the model. The present work attempts to examine the variables involved in the simulation of alcohol displacement and discusses several possible versions of the basic cell model. Under certain conditions the model results are similar to the experimental results. In particular, the spontaneous formation of of the stabilized bank and the effects of the system phase behavior were successfully reproduced. PREVIOUS WORK ON CELL MODELS Cell models and the theoretical plate concept are often used in solving chemical engineering problems in which an explicit mathematical solution may be difficult or impossible to obtain. Examples of such applications occur in distillation, gas-liquid chroma tography,6 reactor technology, absorption, etc. In petroleum engineering, such a model was used by Attra7 to describe non-equilibrium gas drive, and by Higgins and Leigh ton8 to calculate sweep efficiency in water flooding. Aris and Amundsen pointed out the equivalence between the diffusion model and perfectly mixed cells connected in series.9 Deans proposed a three-parameter cell model to simulate two-component

Jan 1, 1966