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By M. L. Fuller

MOST commercial alloys undergo changes in phase composition after casting. This is a natural result of the fact that the alloys are not in a state of phase equilibrium as cast and phase changes will therefore take place, with more or less rapidity, in an attempt to attain equilibrium. The practical aspect of aging in zinc-alloy die castings concerns the changes in physical properties and in dimensions that may accompany aging phase changes. Harmful alterations have been reduced to a minimum and zinc-alloy die castings are being produced today that are so stable with respect to dimensions and physical properties that they are entirely suitable for most practical purposes1. In the first paper2 of this series, and in this paper, aging phase changes of zinc alloy die castings have been investigated and the possible influence of these changes on dimensional changes of the castings has been evalu-ated and compared with the dimensional changes actually experienced. The change of dimensions has been selected for practical comparison in these papers because the effect of phase changes on the dimensions of a casting is directly calculable; from X-ray crystal-analysis data of the phase structure. The die-casting alloys considered contain, in addition to zinc, 4 per cent of aluminum, about 0:03 per cent magnesium, and from 0 to 3 per cent of copper. It was shown in the former paper that the eutectoidal decomposition of the beta aluminum-zinc phase, while intrinsically capable of causing a considerable shrinkage, can have very little effect on the observed shrinkage of die castings because it takes place within a few days of aging, whereas the observed shrinkage continues for five weeks. It was therefore concluded that the other existing phase change,

Jan 1, 1935

Executive. CHARLES F. RAND, Chairman. JAMES F. KEMP, JOSEPH W. RICHARDS, ALBERT R. LEDOUX, BENJAMIN B. THAYER. Membership. BENJAMIN B. THAYER, Chairman. WALTER R. INGALLS, JOHN H. JANE WAY, JR., JOHN D. IRVING, HERMAN A. PROSSER. Finance. EDWARD L. YOUNG, Chairman. KARL EILERS, JAMES GAYLEY.

Jan 4, 1913

On the following pages are abstracts of papers published by the Institute during the year 1936 as TECHNICAL PUBLICATIONS and CONTRIBUTIONS, papers in bound volumes appearing for the first time, and papers in MINING AND METALLURGY For abstracts of papers that appeared in bound volumes in 1936 but that were published as TECHNICAL PUBLICATIONS in 1935, see the YEAR BOOK dated January 1936.

Jan 1, 1937

By H. H. Kellogg

Available high-fernperatzwe equilibrium measurements and other thermochernical data have been critically reciewed for sulfation reactions of the type: Recommended values for log K and ?Fo as junctions of temperature are given for thirty-six suck reactions involving twenty-six different metals. Methods of calculation and choice between conflict-ing data are discussed. SELECTIVE sulfation now enjoys a considerable renaissance as a metallurgical unit process due, in large part, to the available of the fluid-bed re- actor—a device capable of the close control of temperature and gas composition necessary for a successful sulfation process. An additional need, however, if sulfation chemistry is to be approached in a scientific manner, is a reliable body of data on the equilibrium and kinetics of sulfation reactions in simple and complex systems. This paper offers a critical review and compilation of equilibrium data on pure sulfates (simple systems). The last such review, by K. K. Kelley in 1935:30 has proven itself most useful, but the existence of many new data makes necessary a re-evaluation of the available information. METHODS OF CALCULATION For a simple sulfation reaction such as MS04(c) = MO(c) + SO3 [1] there are two approaches one may take toward establishing the value of ?Fo or K as a function of

Jan 1, 1964

NORTH AMERICA ALASKA Anchorage.-Ames, M. B. Culver, H. W. Fiedler, H. L. Geehan, R. V. Langneas, O. O. Layfield, R. A. Parent, A. Saarela, L. H. Strandberg, H. Candle.-Robbins, J. S. Chichagof.-Russell, J. C. College.-Fox, E. F. Joesting, H. R. Lyman, R. F. Smith, M. C. -Wilcox, H. G. Douglas.-Cahill, W. E. Fairbanks.-Adams, J. M. CANADA Canadian Army Overseas.¬Ball, H. D. Bridges, O. Butterill, H. J. M. Lane, H. C. Millar, W. A.

Jan 1, 1942

By M. C. Flemings, T. Z. Kattamis

Dendrite morphology and grain size were studied in bulk samples of iron and nickel base alloys under-cooled up to 300°C. In the alloys studied, dendrite morphology gradually changes with increasing undercooling from the usual dendritic structure to a structure composed of cylindrical dendrite arms. At a critical undercooling of approximately 170°C in these alloys there is an abrupt transition to a fine-grained structure of spherical morphology. Final dendrite-arnz spacing of melts nucleated at less than the critical undercooling decreases with increasing undercooling and with decreasing distance from a chilled surface. Grain size of melts nucleated at greater than the critical undercooling decreases similarly with these factors. It is concluded that structure coarsening, with reduction of surface area as driving force, is the principal mechanism determining final dendrite-arm spacing in melts nucleated at small undercoolings and grain site in melts nucleated at large undercoolings. IN solidification of highly undercooled melts, nuclea-tion and growth of the solid is accompanied by a rapid release of latent heat of fusion. The heat release is sufficiently rapid in bulk specimens that it takes place essentially adiabatically with respect to the surroundings; hence the specimen heats up ("recalesces") to some maximum recalescence temperature. For bulk liquid metals and alloys, a simple thermal balance shows the undercoolings obtainable in bulk samples are not sufficient to lower the maximum recalescence temperature below the equilibrium solidus temperature. Hence, some liquid always remains at the end of recalescence; this liquid must solidify by rejection of heat to the surroundings. Metals, including iron and nickel base alloys, normally freeze with only a few degrees of undercooling. In general, nucleation begins on impurity particles present in the metal, at a "heterogeneous nucleation temperature" that is quite close to the equilibrium liquidus temperature. Very small droplets of metal can be undercooled considerably before nucleation occurs,1-4 presumably because subdivision of the liquid reduces the probability of solid impurity in a given droplet. Following early work on metal droplets,' a series of studies has shown that it is possible, without great difficulty, to undercool bulk samples of many metals and alloys. Undercoolings obtainable are approximately two tenths of the melting point for nickel, iron, copper, and other metals and alloys.5-9 Specimen sizes have generally been in the range of 50 to 500 g. Studies on undercooling to date have been concerned primarily with techniques of undercooling and with nucleation and growth kinetics. Only limited consideration has been given to dendrite morphology in under- cooled alloys. One such study, in bulk Cu-Ni alloy,8 showed that at small undercoolings a typical dendritic structure was obtained. At undercoolings the order of 175°C the structure of a Cu-40 pct Ni alloy became "ray or starlike", and a dense network of subbound-aries appeared. At still larger degrees of undercooling, of the order of 250°C, the structure became more random and included an ensemble of globular forms. Comparable results were obtained by walker10 on Cu-Ni alloys, and by Kamenetskaya et al.11 in research on Cu-Ni, Sb-Bi, Fe-Ni, and Fe-Cr alloys. In this work, study was made of the processing parameters influencing dendrite morphology and grain size in undercooled alloy melts. Experiments were specifically designed to show the effects of coarsening ("ripening") during solidification on final casting morphology. EXPERIMENTAL PROCEDURE Apparatus used was patterned after that of Walker,10 Fig. l(a). Melting was by induction under reduced pressure of helium. Two different types of crucible materials were used; there was no difficulty in obtaining substantial undercooling in both types of materials. Alumina crucibles were used for the bulk of the runs made, with a glass coating separating the metal from the crucible walls. Other runs were made using fused silica crucibles with or without slag coating. A graphite susceptor was employed around the crucible to aid in melting and to reduce melt stirring. The major portion of the experimental work was on

Jan 1, 1967

By J. L. Kenty, J. P. Hirth

The concept of a critical super saturation, below which the nucleation rate is essentially zero and above which it is essentially infinite, is discussed with reference to vapor-solid nucleation. The necessary and sufficient conditions deduced for observations of this type of behavior are: 1) the nucleation rate must exhibit a sharp dependence on super saturation, 2) the growth rate must be sufficiently large that nuclei become observable in the time period of the experiment, and 3) the number of highly preferred nucleation sites must be small. Experiments reveal that the nucleation of silver on sodium chloride is visually detectable at all experimentally accessible super saturations and does not exhibit critical nucleation behavior. Failure to observe a critical super saturation is attributed to the insensitivity of nucleation rate to supersaturation as a consequence of the particular values of the contact angle and the surface free energy for this system. THE concept of a critical supersaturation, below which the nucleation rate is essentially zero and above which it is essentially infinite, arises naturally in homogeneous nucleation theory. Experimentally this type of behavior has been found by Volmer1 and others for water and other low surface tension liquids, as reviewed by several authors.2'3 The same type of behavior has been predicted and observed for heterogeneous nucleation of solids by Yang et al.4 and others,596 as also recently reviewed.2,7,8 In the work reported here on the heterogeneous nucleation of silver on NaC1, however, no critical super-saturation was found. Similar observations have been made recently for other systems.9-11 These results led to a reexamination of nucleation theory which revealed that there are conditions for which critical behavior is not predicted, either for homogeneous or heterogeneous nucleation. Although heterogeneous nucleation is of primary importance in this paper, some insight into critical behavior for such a case can be gained by considering homogeneous nucleation. Accordingly both types of nucleation theory are reviewed briefly. The requisite conditions for critical supersaturation behavior are then considered. The experimental results for the nucleation of silver on NaCl are presented and interpreted in terms of the theoretical presentation. REVIEW OF NUCLEATION THEORY There are essentially two approaches to nucleation theory, the so-called classical theory involving the concepts of bulk thermodynamics, and the statistical mechanical theory in which nuclei are regarded as macromolecules. The classical theory is based on the work of Volmer and Weber12,13 and Becker and. Doring14 and has been extended by Pound et al.15 The crucial assumption in the classical theory is that the small clusters or nuclei can be characterized by the same thermodynamic properties as those of the stable bulk phase. Thus, the nuclei are assumed to have a surface free energy, y, and a volume free energy of formation (relative to the vapor phase), ,, identical to that of the bulk. For deposition under low super-saturation conditions, the nuclei are large and this assumption is satisfactory. However, in many cases of interest, the nuclei contain only a few atoms and this assumption is highly questionable. The statistical mechanical models originated, for the specific case of a dimer as the critical nucleus, with the work of Frenkel16 and were extended later to larger sizes by Walton,17,18 Hirth19 and, more recently, Ht Zinsmeister. These models describe the nucleus in terms of a partition function, the estimation of which is tractable for clusters of 2 to 10 atoms, but extremely difficult for clusters larger than 10 atoms. Although the classical and statistical mechanical models are expected to apply for the limiting cases of large and small nuclei, both are uncertain for intermediate sizes. In this paper we shall treat only the classical model, recognizing that it is exact only for large nucleus sizes and regarding it as a phenom-enological description for small nucleus sizes. When analyses of experimental data using bulk properties show the nucleus size to be small, the resulting parameters should be regarded as largely empirical parameters describing the relative nucleation potency of the system. Considerable justification for the continued use of classical theory is provided by its general success in predicting nucleation behavior as a function of supersaturation and temperature. We emphasize that the qualitative features of the statistical mechanical models, particularly the critical super-saturation behavior that is central to the present work, are the same as those of the classical model. Of course, potential energy terms and surface partition functions replace the volume and surface energy terms of the latter model. The most recent versions of classical nucleation theory have been extensively reviewed.2,3,7 so that only the results are presented here. For homogeneous nucleation of a condensed phase from the vapor phase, the volume free energy change is ?Gv=vrT = =^ln£ [1] where v is the molecular volume of the condensing species. The supersaturation ratio,

Jan 1, 1970

By Royal Jackman

Two comprehensive papers have appeared regarding the forms of copper that occur in smelter slags, one by Frank E. Lathe1 and the other by C. G. Maier and G. D. Van Arsdale.2 These authors comment on other published results and draw conclusions from their own investiga-tions. The development of X-ray examination of minerals and improve-ment in high-power microscopic methods make it possible today to get additional evidence by means that were not available to earlier investi-gators. The present work was confined to reverberatory slags obtained from five different plants. Some definite conclusions were reached regarding the forms of copper present in these slags. In most cases these agree with some of the findings of Maier and Van Arsdale but new methods of attack were used in the investigation.

Jan 1, 1933

By D. C. Porterfield

ProUuction of crude oil in Venezuela increased from 186,134,000 bbl. in 1940 to 2~8,131,ooo bbl. in 1941, or 22.6 per cent, to establish a new all-time high for the country. While the average production for the year was 625,000 bbl. per day, production during the month of December 1941 averaged 751,000 bbl. per day, and during the last week of the year, 766,000 bbl. per day. Production from the Lake Maracaibo basin averaged 454,000 bbl. per day during the year, or 72 per cent of the total for the country, compared with 73 per cent of the total produced in 1940. Drilling during the year was approximately on the same scale as in 1940, with 438 wells completed in 1941 as compared with 429 the year before. Exploratory completions decreased from 18 in 1940 to 6 in 1941. Of the drilling operations in 1941, 56 per cent was concentrated in the Lake Maracaibo basin and 44 per cent in eastern Venezuela, success being 98 per cent in the Lake basin and 83 per cent in the east. Successful completions for the country as a whole amounted to 92 per cent of the total wells drilled. Exploratory drilling in 1941 resulted in the discovery of three new fields, all in eastern Venezuela; viz., Guara, about II km. to the northeast of the Oficina field but on a separate structure; Santa Rosa, which is east of El Roble field on a structure forming a part of the major Santa -Ana- San Joaquin-El Roble uplift; and Santa Barbara, which is southwest of the Jusepin field on an extension of the main Jusepin anticline. At the close of the year three wildcats were drilling, all of which showed prospects of obtaining production; that is, Mercedes No, 2 in central Guarico, Las Ollas No. I on the Anzoategui-Guarico border near the town of Zaraza, and Quiamare No. I in Anzoategui northeast of the town of San Mateo. In spite of heavy withdrawals and the resultant natural decline in the potentials of older producing areas, new drilling during the year increased the potential production of the country from an estimated 780,000 bbl. per day at the end of 1940 to an estimated 810,000 bbl. per day at the end of 1941, or approximately 4 per cent. Since domestic consumption of petroleum products is insignificant compared with total production, exports of crude and products during the year increased in line with production. Crude exports totaled 196,800,000 bbl., compared with 158,400,-000 bbl. in 1940, and exports of products were 26,100,000 bbl., compared with 21,900,000 bbl. the year before. Exports of crude from Venezuela to the United States amounted to 36,500,000 bbl. In addition, about 2,200,000 bbl. was imported in bond into the United States for transfer to Canada. Total refining capacity of the country in 1941 was approximately 125,000 bbl. per day, including a crude-conversion plant with a capacity of 32,000 bbl. per day, capable of making fuel oil only. Three plants with a capacity of 121,000 bbl. Per

Jan 1, 1945

By E. W. Murbach

The oxidation of uranium carbide by oxygen at various pressures, and by air, has been investigated at temperatures up to 600°C. Arc-melted and cast uranium carbide displays oxidation behavior that appears to be dependent on its treatment after melting. ccReactive" uranium carbide, which results from exposure of freshly melted material to laboratory air, ignites in oxygen at about 275° to 350°C depending on pressure, and in air at about 350°C. The product of the initial oxidation appears to be UO2+.. Continued heating produces U30,. The initial oxidation rate is poportional, roughly, to the square root of the oxygen pressure. The activation energy determined for the initial oxidation reaction is 7.1 kcal, from 400° to 600°C in 10 mm of oxygen. AN investigation of low-decontamination methods for reprocessing uranium carbide reactor fuels is being carried out at Atomics International. One of the reprocessing cycles includes oxidation of the fuel at relatively low temperature (300° to 500°C) and reaction of the product oxide with carbon at elevated temperatures (above 1500°C) to produce uranium carbide. A number of small-scale experiments have been carried out in which uranium carbide was oxidized in air and oxygen at various pressures to measure reaction rates and to obtain other information concerning the oxidation process. In initial experiments with arc-melted UC, ignition was observed at about 275°C in oxygen or 350°C in air. However, similar experiments by Neymark' at 426°C in air showed no ignition. It was soon determined that the difference in oxidation behavior was due to the treatment of the UC following arc-melting. Neymark's experiments were carried out with freshly melted UC while those reported in the

Jan 1, 1963

By M. J. Richards, A. Szirmae, G. R. Speich

The formation of austenite from ferrite, ferrite plus retastable carbide, spheroidite, and pearlite has been studied in a series of irons, Fe-C alloys, and plain-carbon steels using fast heating techniques. In the absence of carbide, austenite nucleates at ferrite/ferrite grain boundaries; nucleation is followed by the rapid growth characteristic of a massive transfornation. The trarnsformation occurs at 950°C at heating rates of 106º C per sec and cannot be suppressed. Metastable carbide dissolves before austenite forms and does not influence the transformation kinetics. For spheroidite structures, austenite nucleates preferentially at the jinction between carbides and ferrite grain boundaries. Growth from these centers proceeds until the carbide is completely enveloped; subsequent growth occurs by carbon diffusion through the austenite envelope. For pearlite structures, austenite nucleates preferentially at pearlite colony intersections. Carbide la)?zellae dissolve at the advancing austenite interface but complete solution of carbide does not occur; the residtial carbide is eventually dissolvled or spheroid-ized depending on the carbon cuntent. The magnitude and temperature dependence of the austenite growth rate into Fe-C pearlite when incomplete carbide dissolution is assumed are satisfactorily explained by an approximate colume diffusion model. The impurities present in plain-carbon steel reduce the growth rate of austenite in comparison to that jound in an Fe-C alloy. The formation of austenite has been studied in much less detail than the decomposition of austenite. This is primarily a result of the importance of harden-ability in determining the mechanical properties of steel. Recently, more interest in the kinetics of austenite formation has resulted from the discovery by Grange1 that rapid heating techniques strengthen steel by refining the austenite grain size. Although the strengthening effect is not large, it is accompanied by no loss in ductility. In addition, interest continues in rapid heat treatment of low-carbon steel sheet for tin plate applications.2,3 Among the few systematic studies of austenite formation are the early work of Roberts and Mehl4 on formation of austenite from pearlite and recent work of Molinder5 and of Judd and paxton6 on formation of austenite from spheroidite. Also, Boedtker and Duwez7 and Haworth and paar8 have recently studied the formation of austenite from ferrite in relatively pure iron, Kidin et al.9,10 have studied the formation of austenite in 8 pct Cr steels, and Paxton has recently discussed various aspects of austenite formation in steels." The present work was undertaken to determine the kinetics of austenite formation for a variety of starting structures including ferrite, ferrite plus metastable carbide, ferrite plus spheroidal cementite, and ferrite plus pearlitic cementite. Emphasis was placed on determining the active sites for austenite nucleation, determining the temperature and time range of austenite formation, and in the case of pearlite a careful study of the growth rate of austenite was made in the absence and presence of impurities. By using a variety of heating techniques including laser-pulse heating, it has been possible to study austenite formation in an isothermal fashion over a wide range of temperatures. EXPERIMENTAL PROCEDURE The alloys studied in the present work are a zone-refined iron with 4 pprn C, an Fe-C alloy with 130 pprn C, 2 Fe-C alloys with 0.77 and 0.96 wt pct C, and a plain carbon steel with 0.96 wt pct C. The zone-refined iron and Fe-C alloys contained 60 pprn and 200 pprn total substitutional impurities, respectively. The plain carbon steel contained 2400 pprn Si, 2000 pprn Mn, and 900 pprn Cr. Various heat treatments were given to these alloys to produce different starting structures of equiaxed ferrite, ferrite plus metastable carbide, fine pearlite, and spheroidite. These heat treatments are given in Table I. A wide range of heating rates were employed in this work because many of the reactions occur so quickly at temperatures in the austenite range that they are completed during the initial heating cycle unless very fast heating rates are used. Essentially the same heating techniques employed by Speich et a1.12 and Speich and Fisher13 were used in this work. For time intervals of 2 sec to 20 hr, simple hand immersion of 0.010-in. thick specimens in a Pb-Bi bath was employed. These specimens were quenched in a 10 pct NaC1, 2 pct NaOH aqueous bath. For time intervals of 100 m-sec to 2 sec, an automatic dunking and quenching device was employed with 0.002-in. thick specimens. Again, liquid Pb-Bi baths were used for a heating medium but now helium gas quenching was employed. For time intervals of 2 to 100 m-sec a laser heating device was employed with 0.002-in. thick specimens; a helium plus fine water-droplet spray was now used for quenching. Additional information on heating times shorter than 2 m-sec was obtained by study of the zones around the centrally heated laser spot. Here diffusion of heat from the centrally heated zone raises the temperature of the specimen locally to all temperatures between ambient and the peak temperature, but for times of the order of microseconds. All the heat-treated specimens were examined by

Jan 1, 1970

Jan 1, 1949

By R. E. Reed-Hill

Recently Levine applied the Conrad-Wiedersich17 equation where H is the activation enthalpy, v the activation volume, T* the effective shear flow stress, T the absolute temperature, and ? the strain rate, to an analysis of titanium single-crystal data. The activation energy as a function of testing temperaturs obtained from specimens oriented for single (1010) prismatic slip is shown in Fig. 12. This diagram indicates a different linear dependence of H on T in the temperature interval from 220° to 300°K than from 0° to 220°K. Levine interpreted the break in this curve as indicating a change in the thermally activated mechanism controlling the flow stress. The purpose of this communication is to point out that the data in Fig. 1 is not consistent with the concept of a flow stress controlled by a simple thermally activated mechanism between 220° and 300°K. The Conrad-Wiedersich relation assumed that the strain rate can be expressed by:

Jan 1, 1968

By W. W. Krysko

In order to calculate the critical particle size of lead oxide entrapped in lead, Stoke's Formula may be applied. All data were available except figures for the density of lead oxide at elevated temperatwes. The density of lead oxide was determined by means of dilatometmetrc and volumetric methods up to 1010°C. Graphs of the density of lead and lead oxide as well as the viscosity of lead are given and discussed, with the conclusion that the most unfavorable region for the separation of lead oxide from molten lead lies just above the melting point of lead. DURING previous investigations, particularly on the dedrossing of lead with aluminum1 and the oxygen solubility in lead,' the critical particle size of lead oxide which could be entrapped in solidifying lead was estimated by calculation, and it was shown that high values found for the oxygen content of lead may be due to the method of sampling and the entrapped particles of dross. Unfortunately, due to lack of data, an exact mathematical solution was not possible. The particle size which will separate under a given condition can be estimated from Stoke's Law, which states that where: d = diameter of the critical particle size ¦q = viscosity of lead in Poise V = constant velocity in cm sec-I g = 981 cm sec-2 61= specific gravity of lead 62= specific gravity of lead oxide The depth of the lead bath and the time before solidifying define the velocity. The viscosity of molten lead is known from earlier work by Krysko and is given in Table I. The specific gravity of lead is also known, see Table II. These values are according to Hofmann. A careful survey of literature revealed no values for the density of lead oxide at elevated temperatures. The present investigation was therefore conducted to provide this information. RESEARCH INVESTIGATIONS The density of lead oxide was determined from the following experiments: 1) Determination of the density of lead oxide at room temperature. 2) Dilatometric investigations on the same samples. 3) Determination of the shrinkage at the liquid-solid trans£ormation. 4) Density determinations on liquid lead oxide. 5) Time temperature curves during cooling. 1) The samples for the determination of the density of lead oxide in the solid state were prepared in the following manner. Molten lead oxide was cast into I hot mold which could be opened along the longitudinal (vertical) axis. The cast samples were cylinders of approximately 10 mm diam and approximately 80 mm length. The cylindrical hot mold was open at both ends and was placed on a large copper chill plate shortly before casting. The solidification of the lead oxides proceeded upwards without any formation of internal cavities. The sample was carefully checked with respect to density and crystalline appearance, and only the lower portions which were crystalline and free from porosity were used. The density was determined in a specially made pyknometer-like container, where the surplus liquid was squeezed out through an orifice approximately 1/10 mm in diameter. Mercury or water was used as the liquid. The densities of the samples were calculated from the weight, volume, and mean specific gravity of eight samples was 9.62 * 0.05 g cm"3 at 22"~. 2) The samples were machined to approximately 1 1/2 in. in length and fitted into a dilatometer. A

Jan 1, 1962

By F. W. SUTTER

IN order to have ore available on the completion of the beneficiation plant at Clifton and to provide for continuous production while underground development was carried out, it was decided to develop an open-pit through the crest of a long hill in which the ore outcropped, using 40-ft. vertical benches.

Jan 1, 1943

By F. H. Deily, Jean M. Quets, Milton E. Wadsworth, John R. 222-000-000-012 Lewis, D. S. Rowley, R. J. Howe

Samples of synthetic magnetite were reduced in hydrogen-water vapor atmospheres in the temperature range 450o to 900oC. The reaction was always surface controlled, indicating the final products of reaction are nonfirotective. Three separate cases have been identified from the kinetic results: Case I, reduction of magnetite to iron below 570°C; Case II, reduction of magnetite to iron above 570°C; and Case 111, reduction of magnetite to wustite above 570 oC. In Cases I and 111 the kinetics have been explained by the formation of oxygen anion vacancies in the magnetite surface followed by associated diffusional processes. In Case 11 the observed kinetics have been related to the concentration of iron cation vacancies in the wustite layer formed, followed by associated steady-state diffusional processes. The concentration of cation vacancies in the wustite is maintained constant by the magnetite-wustite equilibrium. THE reduction of the oxides of iron has been a subject of study and interest for many years. However, few attempts have been made to interpret the results in terms of the mechanism of reduction of an iron oxide by either hydrogen or carbon monoxide. Stalhane and Malmberg' using CO, H2, and CO-Hz mixtures, developed the rate expression: where m = mass of oxide reduced, t = time, k = a constant, s = surface area, P = partial pressure of of CO or H,, and P, = partial pressure of the reducing gas at equilibrium. The rate of reaction per unit area was proportional to the difference between the partial pressure of the reducing gas and its pressure at equilibrium. Hansen, Bitsianes, and Joseph2 studied the reduction of pellets of hematite to magnetite with mixtures of CO-CO,. They concluded that below 450°C the reaction proceeded according to a model in which CO reacts with the hematite surface producing an oxygen ion vacancy. The rate controlling step was then assumed to be oxygen ion diffusion through vacancies resulting in the formation of magnetite. They derived an expression giving the rate of reduction proportional to the cO/CO, ratio. Recently McKewan3 published results for the reduction of magnetite spheres in atmospheres below 570°C. He explained his results by an equation of the form where K, is the equilibrium constant for wustite-iron equilibrium attributed to the formation of wustite as an intermediate in the reduction of magnetite. According to McKewan, Kp is an equilibrium constant for H, -HO adsorption in which oxygen is deposited on the surface from the H,Oand subsequently acts as a poison for reduction by hydrogen. Sample Preparation and Experiments. In this work the authors used the same apparatus and experimental procedure employed in the hydrogen reduction of magnetite. Sintered disk samples weighing approximately 1.5 g and measuring 1.2 cm in diameter and 0.25 cm in thickness were prepared by a method described previously.4 Partial pressures of hydrogen and water vapor were controlled by bubbling hydrogen through a series of flasks containing distilled and deionized water maintained at constant temperature in an oil bath. The total flow rate of the reacting gases—hydrogen and water vapor—was approximately 0.5 liter per min. The entire external system was maintained at a temperature above the oil bath to prevent condensation of water vapor. This was accomplished by wrapping electrical resistance elements over all surfaces. The glass column containing the weighing system-a McBain balance suspended from a gold chain-was enclosed in an aluminum tube heated by nichrome resistance wire enclosed in an insulating material. The temperature of the glass column was held constant by means of a series of thermocouples connected in parallel to a Leeds and Northrup temperature controller. This was necessary since variations in temperature resulted in expansion and contraction of the glass column and could be readily observed with the cathetometer. The spring extensions were measured through a window with a gaertner cathe-

Jan 1, 1962

By W. R. Hibbard

IN ref. 1, on the basis of tension and torsion experiments with single crystals of a brass, the values given in Table I were obtained for elastic coefficients. It was pointed out by Zener that the values for the 71.2 pct Cu were not satisfactory, since they resulted in a negative value for the bulk modulus, namely —4.17X1012 sq cm per dyne. In reevaluating the data of this investigation, it was determined that the reason for this negative bulk modulus lay in the extrapolation of the reciprocal Young's modulus to the zero value of the orientation function shown in Fig. 5 of ref. 1. This extrapolation was reevaluated by the method of least squares (50 pct probability) and a new value of the coefficient S,, was determined as 18.9220.42X 10M sq cm per dyne in lieu of the value originally reported of 18.82x10 sq cm per dyne. This new value of S, leads to a new value of S, of — 9.43 X101" sq cm per dyne. The values of the other coefficients are unchanged. results. This value compares with the value of 12.3X10 sq cm per dyne reported by Schmid and Boas? The new results are summarized in Table 11. These results follow similar qualitative trends, previously published,' relative to the effect of zinc content. However, the derived values of C11, C,, C,, and K are so sensitive to the uncertainty in the first decimal place of the S, values that they are probably not useful. This uncertainty must also apply to the previous results of Masima and Sachs," who obtained S, values from a similar extrapolation drawn wholly above their data points. Acknowledgments Advice and assistance on the statistical methods were obtained from R. W. Guard. The calculations were carried out by Miss E. Saacke.

Jan 1, 1958

By C. E. Kemp, A. B. Dyes

Results of a field research project on the thermal recovery of oil by movement of a combustion front are presented. This field test was conducted in the South Belridge field, This The war paitern was a Southsing1e 2.5-acre five-spot pattern in the 700-ft deep Tulare sand. Results of this project indicate the technical feasibility of producing high viscosity, low-grallity crude oils by thermal means. It was demonstrated that heavy oils could be moved rapidly over considerable distances by thermal drive, and that high percentage recoveries of oil could be effected. The bulk of the oil recovery came after arrival of the burning front at a production well. However, rapid corrosion and high-temperature failure of conventional pipe and equipment both below and above surface occurred. Stainless steels gave more satisfectory performance under these conditions than did conventional steels. Oxygen was seldom observed in gas from wells ahead of the burning front, and it appears that the front was continuous throughout the life of the experiment. INTRODUCTION During late 1953 and early 1954, industry-wide attention was focused on the thermal recovery of oil by movement of a combustion front through an oil zone. Two separate Oklahoma field tests were described in publications by Kuhn and Koch, and Grant and Szasz. To obtain basic information needed for making engineering and economic appraisals of commercial recovery of heavy oil by this thermal recovery method, a new field research projecta3,4 was started May 31, 1955. Twelve oil companies contributed to this project with General Petroleum Corp. as operator. Since combustion recovery experiments* with heavy oils in other areas had been conducted in small patterns,"' an important purpose of this test was to determine whether the process could be operated in a pattern of near-commercial well spacing. The south Belridge field, located 30 miles north of Taft, Calif., was chosen because its oil sands are similar to many heavy oil sands which typically have low primary recovery and leave a large amount of oil in place. such fields are not particularly suited for common secondary recovery methods. DESCRIPTION OF TEST SITE The test interval was a Tulare sand at a depth of about 700 ft. Nine test wells were drilled, cored and completed from Oct., 1955, through Jan., 1956. The initial pattern shown on the map, Fig. 1, consisted of an injection well (II)', four producing wells (1P-4P), and four observation wells (IT-4T). An old well (81) was also recompleted for use as an observation well. The area enclosed by the original four production wells was 2.5 acres; the distance from the injection well to each production well was 233 ft. During the combustion period, Well 5P was drilled to replace Well 2P, and Well 6P was drilled to replace Well 3P. The new wells were 25 ft beyond the old production wells along a diagonal from the injection well, and resulted in an increase in pattern area to 2.75 acres. Isopachs are shown in Fig. 1. The average thickness of the oil sand in the test pattern was 30 ft. Fig. 2 presents two cross sections through the test pattern. Oil sand is represented by white and claystone by gray. The dashed lines indicate layers of conglomerate grading to claystone. The sand thickness was fairly uniform throughout the test pattern except in the 1P area. The sand body dips gently from the northwest to southeast, about 3 degrees from horizontal. The sand is unconsoli-dated, and grades from very fine material to pebbles as large as 2 in. in diameter. Table 1 presents the average initial properties of the formation. The in-place porosity of 37 per cent was estimated from the porosity of coke-consolidated cores taken after combustion. Original core analyses data were adjusted to 37 per cent, giving pore volume saturations of 60 per cent oil, 37 per cent water, and 3 per

By J. L. Lamon, W. Crafts

P. Coheur and L. Habraken—We read this paper with great interest and are glad to congratulate the authors for their valuable work, supplying an important contribution to the mechanism of tempering on the carbides in vanadium steels. We are in a good position to appreciate this work since we have been studying, for more than a year, Cr-Mo steels of a composition similar, but less highly alloyed (namely 0.1 pct C, 3 pct Cr, 1 pct Mo). Our results are quite in concordance with the authors', however, we wish to point out that it is very interesting to use equally the electron microscope in order to observe the variations of microstructure in steels. We have studied simultaneouslv the evolution of the carbides in situ with the electron microscope, and, after extraction, again with the electron microscope, and then with X-rays. The first results which we have obtained have been communicated at the Congress of Delft (July 1949) and at the "Journbes de la Metallurgie" in Paris (October 1949). These may be summarized as follows: After tempering with varying either the tempering temperatures or the tempering times, the carbides show two evolutions. The first one is connected to the carbides existing in the steels, principally in the boundaries of the grains. For some groups of steels these carbides may coalesce and for other groups they may

Jan 1, 1951

THOSE MARKED THUS * ARE MEMBERS, MARKED THUS ?ARE ASSOCIATES. THESE SIGNS DOUBLED INDICATE LIFE MEMBERS AND ASSOCIATES RESPECTIVELY. THE FIGURES AT THE END OF THE ADDRESS INDICATE THE YEAR OF ELECTION. HEAVY-FACED TYPE SIGNIFIES HONORARY MEMBERSHIP. *AARONS, J. BOYD, Vivian Gold Mining Co., Ltd., Harris, West. Australia. '05 *ABADIE, EMILE R., Cons. and Min. Engr., 214 Union Savings Bank Bldg., Oakland, Cal. '76 ?ABBÉ, MAX F., Prest., Abbé Engineering Co, 220 Broadway, New York, N.Y. '07 ? ABBÉ, PAULO., Secy.,Abbé Engineering Co., 220 Broadway, New York, N.Y. '07 *ABBOTT, AI ARTHUR Morococlia, Peru, So. America. '95 *ABBOTT, CLARENCE Chief EDgr., Iron Mines, Dic Tennessee Caol, Iron & R. R. Co., Bessemer, Ala. '04 *ABBOTT, JAMES W., Min. Engr: Ploche, Lincoln Co., Nev. '94 *ABE, MASAYOSHI, Prof. of Mining, Imperial University Kyoto, Japan. '05 ? ACKER, E. O'C., Supt., Treatment Dept., Bethlehem Steel Co., So. Bethlehem, Pa. '86

Jan 1, 1910