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By Archer E. Wheeler, Milo W. Krejci

There are two general methods in use for the production of metallic copper from matte which are worthy of consideration : (1) the Welsh blister process, and (2) the converter process.' As practically all of the copper produced to-day is made in converters, we will give a brief outline of that process before proceeding with the special subject of this paper. Matte may be roughly defined as a mixture of the sulphides of copper, iron, nickel, silver, etc. In the converter process this is blown up to metallic copper in a modified type of Bessemer converter. The conversion of matte consists mainly in, (1) the removal of sulphur in the form of SO2, and (2) the slagging of the iron. With this brief statement we come to the two subdivisions of the process of converting mattes: Converting with acid linings. Converting with basic linings. Converting with Acid Lininys, This is carried out by lining the converter with siliceous rock or ore, which performs two functions: It protects the iron shell of the converter from the molten charge, and it furnishes the silica for combining with the iron as it is oxidized from the matte, to form a ferrous silicate. It follows from the second of these functions that this siliceous lining must be replaced from time to time, and in practice it has been necessary to reline converters every 8 to 40 hr., this time varying in different plants and even with different linings in the same plant, the life of a lining depending upon the grade of the matte treated, and upon the composition, the thickness, the tamping, and the drying of the lining.

Jan 1, 1914

By A. V. Bradshaw, R. I. L. Guthrie

The behavior of large bubbles in the size range 4 to 25 cm3, rising through molten silver, has been studied. It was found that rising velocities were equivalent to those in aqueous systems of low viscosity. Mass transfer coefficients for oxygen bubbles dissolving in silver were found to be 0.036 ± 0.007 cm sec-1, being close to those predicted for transfer through the front surface of the spherical cap bubble only. It is suggested that the surface active nature of oxygen in silver could account for the relatively low coefficients obtained. MANY metallurgical processes involve interactions between gas bubbles and liquids. Examples include the removal of carbon monoxide in Open Hearth Steelmak-ing, the removal of sulfur by blowing air through copper matte during converting, and the removal of hydrogen from steel during vacuum degassing or inert gas flushing. The steps involved in such refining processes include; transport of the dissolved species to the bubble interface, adsorption and chemical reaction of the species at the interface, desorption of product molecules from the interface, and transport of product gas into the bulk gas phase of the bubble. It has been concluded1 that all the interfacial steps involved proceed so rapidly at steelmaking temperatures that transport of the solutes, present in the metal, become the important rate controlling factors provided nucleation phenomena are not restrictive. The O-Ag system was chosen for the investigation into gas bubble-molten metal interactions due to the relatively high solubility of oxygen that enables rates of oxygen transfer to be measured from changes in bubble volume. Other advantages of this system include the absence of a stable oxide phase at an oxygen pressure of 1 atm and the relatively low melting point of the metal which permits the use of a metallic container, providing that it is resistant to oxidation. In those metallurgical processes where bubbles have an important influence, bubble volumes are usually greater than 5 cm3. For this reason the present study relates specifically to single large bubbles of oxygen rising in silver. These bubbles adopt the characteristic spherical cap shape similar to that shown in Fig. 1 for a 30 cc bubble rising in water. After an initial investigation to determine the velocities of inert (nitrogen) bubbles rising in molten silver, experiments were carried out with oxygen and the rates of mass transfer between the oxygen bubbles and the silver were measured. EXPERIMENTAL Apparatus. The apparatus, Fig. 2, for containing molten silver, was constructed from "Nimonic 75" Alloy (75 pet Ni, 20 pet Cr, 5 pet Fe, Mn) and provided for the release of single bubbles from an hemispherical cup, situated at the bottom of the column. The cup was turned by translating the rotation of the drive shaft through 90 deg. This was accomplished by the use of a bevelled gear system, and a smooth drive was provided by the lubricating action of the silver on the gears. Since reliable high temperature seals at 1000°C were found to be impracticable, the filling and drive shaft tubes were extended outside the 3.5 kw resistance wire tube furnace, where connections were made using easily accessible O-ring seals. The apparatus remained gas tight to the atmosphere at pressure differentials far in excess of those used. The filling tube was connected via a small bore tube to the differential pressure transducer. Gas could be bubbled into the inverted cup from two i-in. tubes which passed down the inside of the column to preheat the gas. The temperature of the silver was maintained at 1020°C during all experiments. Measurement of Bubble Volume. In order to calculate mass transfer rates, it was necessary to obtain a continuous record of the bubble's volume during its passage through the column of molten silver. The method adopted for measuring the bubble volume involved closing off the top gas space to the atmosphere prior to each experiment, and recording the variation in gage pressure of this space during the formation and rise of the bubble. Since any change in bubble volume results in an equal change in top space volume, Boyles Gas Law may be applied (for isothermal con-

Jan 1, 1970

By David D. Rabb

Leaching or solution mining, a relatively simple and economical process for beneficiating metallic ores, is likely to find increasing application in the treatment of low-grade ores that are impractical to mine by any other means. This process may be carried out in two different ways: 1) dump leaching, where the ore is moved from its original location to be leached at another site; and 2) In-situ leaching, where the ore is leached in place by introducing the leach solution at the top, letting it flow down through the ore under gravity, and then recovering it plus the dissolved metals it contains. Whichever leaching method is used, it is almost always necessary to break up the ore before leaching. In this paper a study is reported which indicates that rock broken by an explosion-in particular, an underground nuclear explosion-is significantly more amenable to leaching then is rock broken by other methods. These results suggest that the leaching speed and efficiency could be increased by nuclear fracturing of the ore. Not only would the leach time be shortened, but the resulting increase in strength or richness of the solutions would decrease plant installation expense as well as reduce pumping and processing costs. A considerable fund of experience has been accumulated in the course of several hundred experimental underground nuclear explosions, so that the gross results of any given nuclear explosion can now be predicted with a fair degree of confidence.' From this knowledge it seems clear that, under the proper conditions, large ore bodies can be fractured much more economically-macroscopically speaking-by nuclear explosions than by other methods. The present study concentrates on smaller scale effects that is, the cracks in the chunks of rock broken by the explosion-and shows that here too, in the microscopic domain, there are important advantages to nuclear fracturing. The intense shock produced by the very fast acting, high-brisance nuclear explosive fractures the rock in a way that should significantly improve its leachability. Experimental Procedure This study compared rocks broken by nuclear explosives with rocks produced by conventional mining, quarrying, or core drilling. The test samples, granite chunks 6 to 8 in. on a side, plus core sections, came from the area of the Hardhat*2 nuclear explosion and were taken both before and after the explosion. For comparison, several samples of quarried granite were obtained from a local gravestone monument company. The general procedure was to soak the test samples in leaching solution and then determine the extent of penetration. A standard commercial copper leaching solution was used (10 gpl Cu, 10 gpl H2SO4, 5 gpl ferric Fe, 15 gpl total Fe, pH about 1.5), to which a water-soluble penetrant dye, Zyglo 1-c, had been added. Details of the procedure were as follows: 1) Sample leached in solution containing Zyglo penetrant dye. 2) Washed with water. 3) Air-dried. 4) Cut with granite wire saw. 5) One face polished with granite monument polish. 6) Sent directly to be photographed, or heated at 110°C for 2 hr and then sent to be photographed. 7) Photographed under ultraviolet light to show crack patterns. Results After 10 days of leaching at 70-75°F, the samples were removed from the solution, washed, dried, and cut in half with a granite wire saw to study the penetration of the leach solution. Since the Zyglo dye in the leach is visible under ultraviolet light, the degree of penetration of the leach (and hence the cracks in the samples) can be studied on photographs of the crosscut samples made under ultraviolet light. The photos in [Fig. 1] show how the leach solution penetrated various representative samples. Of the 71 rock samples examined, fractures were most frequent and prominent in samples from the rubble produced by the nuclear explosion [(Fig. 1D)]. Fracturing was less apparent in shaft-mined rock [(Fig. 1B)], still less evident in drift-mined rock [(Fig. 1C)], and practically nonexistent in cored or quarried specimens [(Fig. 1A)]. The samples in [Fig. lA-C] were from the same general area as the nuclear explosion, but they were obtained before the explosion. Results of the crack studies are summarized in [Table 1]. The Zyglo-treated leach solution penetrated the test samples at the rate of about 1/2 mm during the first hour, 1 mm by the end of 4 hr, 2 to 3 mm in 12 hr, and 4 to 6 mm in 10 days, showing a progressively slower rate with time.

Jan 1, 1972

By Robert F. Mehl

THE solid solutions which aluminum forms with copper, and with magnesium and silicon, are not extensive, and accordingly could not be expected to form Widmanstätten figures profusely nor with great ease. A study of the Widmanstätten figures in these systems seemed desirable, however, because of the interest which these alloys bear towards age-hardening theories resulting from the necessary relationship between the age-hardening phenomena and the atomic processes leading to the formation of Widmanstätten figures.1 ALLOYS OF ALUMINUM WITH COPPER The most accurate determination f the solid solubility, of copper in aluminum seems to be that by Dix and Richardson,2 whose results are represented in Fig. 1. According to this work, aluminum dissolves 5.6 weight per cent of copper at 548°, and less than one per cent at room temperature. Judging from the constitutional diagram, this solid solution on cooling tends to precipitate the compound CuAl2, and this conclusion has been confirmed experimentally by Schmid and Wassermann .3

Jan 1, 1932

By W. C. Elmore

THE magnetic powder method, long used for roughly mapping mag-netic fields, has recently been refined 1,2 for investigating the microscopic variations in the surface magnetization of ferromagnetic crystals. Bitter2 first discovered regular powder patterns connected with the crystal structure of such specimens. Several other investigators3 have used Bitter's original technique, with slight modifications, to study the varia-tion of the patterns with variations in the magnetizing field applied parallel to the surface, and their dependence upon the state of strain, of polish and of crystal cut. All of the explanations of these patterns on metallic ferromagnetics have been couched in general terms. In a preliminary report we have described an improvement in the powder technique which led us to the discovery of a new effect throwing con-siderable light on the magnetic secondary structure of alpha iron4 and of nickel5 single crystals. We now report additional evidence confirming the existence and stability of a magnetic block secondary structure.

Jan 1, 1936

By G. H. Turner, R. C. Bell, E. Peters

Zinc oxide activities in a typical lead blast furnace slag have been calculated from plant operating data. These activities were used to assess the probable effect of fuel composition, oxygen enrichment, and air preheating on the efficiency and capacity of the slag-fuming operation. THE physical chemistry of zinc fuming has been examined with three objectives in mind: 1—to predict conditions favorable to increasing furnace capacity, 2—to predict the changes required to fume zinc more economically, and 3—to explain reported differences in the efficiencies of various slag-fuming plants. This study, made at ail in the plants and laboratories of The Consolidated Mining and Smelting Co. of Canada Ltd., developed from a program undertaken some three years ago on behalf of the AIME Extractive Metallurgy Div. subcommittee on slag fuming. Lead metallurgists first became interested in the recovery of zinc from lead blast furnace slags in 1905 and 1906. An excellent review of the early experimental work has been made by Courtney,' who described blast furnace, reverberatory furnace, and converter methods of fuming zinc from slag. Some of the investigators did not appreciate the importance of reducing the zinc oxide content of the slag to metal in order to fume it, since they tried compressed air blast without fuel in their earliest attempts. However, by 1908, the importance of reducing the zinc was established.' In 1925, the Waelz process for the recovery of zinc oxide from oxidized zinc ores was developed in Germany.' This process was not readily adaptable to lead blast furnace slags because of the difficulty in handling fusible charges in a kiln. What appears to have been the first slag-fuming operation as it is known was commenced by the Anaconda Copper Mining Co. at East Helena, Mont. in 1927." The first Trail furnace was completed in 1930, and this was followed by the construction of several other slag-fuming plants. During the period in which slag fuming has been extensively employed, little development of the chemistry of this process as a whole has taken place. Several good papers on the petrography of lead blast furnace slags have been published,""= but these studies could do little more than establish the forms in which lead and zinc occur in the initial charge and final products of the slag-fuming operation. In recent years, zinc-smelting problems have been ap- proached from a thermodynamic point of view. Maier has published an excellent thermodynamic treatment of zinc smelting." The important thermodynamic properties of zinc and its compounds have been determined and checked by other investigators.' However, to the best of the authors' knowledge, no thermodynamic treatment of the fuming of zinc from slag has been published. A thermodynamic study of any process requires that the essential chemistry of that process be known. In slag fuming there appear to be some differences of opinion as to whether the active reducing agent is elemental carbon or carbon monoxide. Furthermore, some observers have noted that high volatile coals appear to be more efficient than low volatile coals, indicating that hydrogen is also an important factor in the reducing efficiency of a fuel. That both hydrogen and carbon monoxide are effective reducing agents for the zinc oxide content of lead blast furnace slags can be demonstrated readily by introducing these gases into a slag bath held in a neutral vessel at 2100°F (1150°C). Elemental carbon also will reduce zinc oxide, but it is improbable that much free carbon is available for reduction of zinc, as the reaction between the finely powdered coal and air should be largely completed before the solid coal particles reach the slag. Some large-scale fuming experiments using gaseous hydrocarbons have been carried out by other investigators, but, as far as is known, these have not been developed yet into operating processes. The thermodynamic treatment in this paper is based on the following reactions: 1—to supply the thermal requirements C+V2O2- CO [1] C + 0,-CO, [2] H2+ ~z0,-H,O 131 and 2—to reduce ZnO ZnO + CO + Zn + CO, c41 ZnO + H, e Zn + H,O. [51 The furnace-gas composition also is controlled by the equilibrium constant of the familiar water-gas reaction H,O + CO + CO, + H2. C6l In order for the thermodynamic calculations to be quantitatively applicable, it is necessary that the chemical reactions to which they are being applied

Jan 1, 1956

By L. Stone, H. Margolin

The Ti-C-N and Ti-C-O systems were investigated in the temperature range from 500° to 1400°C and in the composition range up to 2 pct C and 5 pct N or 0. Characteristic isothermal sections at 800°, 900°, 1000°, and 1300°C are presented. The Ti-N-0 system was studied in the temperature range from 900' to 1400°C with alloys containing up to 6 pct total alloying content. Characteristic isothermal sections at 1000° and 140O°C are presented. Melting-point data for all three systems are also included. THIS paper reports on one of a series of investi-gations which have been conducted on the phase diagrams resulting from interstitial alloying with iodide titanium. The other investigations involved delineation of the binary systems with carbon,' nitrogen and boron,h and oxygen. The Ti-0 binary system has also been investigated by Bumps et al.' In varying degrees, each of these interstitial elements has been shown to stabilize the low temperature a modification of titanium1-5 and each forms a face-centered cubic TiX compound (henceforth designated 6). In addition, the Ti-N and Ti-0 systems reveal a low temperature tetragonal phase (6) formed by a peritectoid reaction between a and TiX Experimental Procedure The development of experimental techniques for the study of titanium alloy systems has, to a large extent, become standardized. In this investigation, the equipment and procedures described in detail by Cadoff and Nielsenl have been used. Arc Melting: In general, binary alloys with carbon, nitrogen, and oxygen, prepared in the composition range of interest in this investigation, show negligible composition changes during arc melting. However, the possibility of the formation of some gaseous combination of alloying elements such as CO, CN, or NO during the preparation of these ternary alloys was considered. Calculations showed that the evolution of only 0.05 gram of such a gas would be detectable as a pressure change in the closed system used during preparation of these alloys. Such pressure changes were not observed. Consequently, nominal compositions have been used in plotting the data. The compositions of the materials used in the preparation of the alloys are shown in Table I. After melting for 3 to 5 min at 275 to 350 amp, the alloys were checked for homogeneity by microstruc-tural examination. Alloys containing up to 1 pct C were homogeneous in the presence of less than 3 pct N or 0. At higher alloying contents, some inhomo-geneities in the carbon distribution became evident. Alteration of the melting procedure toward longer times and higher currents did not improve the homogeneity of these alloys. Ti-N-0 alloys were homogeneous in the range to about 3 or 4 pct total alloying addition. Beyond this, almost all of the specimens showed as-cast microstructures consisting only of the phase. Consequently, inhomogene-ities could not be detected by examination of micro-structures. Ten alloys from each of the systems were analyzed for two of the elements present (oxygen being omitted in all cases and titanium being omitted in the Ti-C-N alloys). In all cases the analyses were found not to be sufficiently precise to serve as criteria for the total composition of these alloys. On the basis of phase distribution in heat-treated alloys, however, it appears that carbon is distributed throughout the alloys most uniformly, with oxygen and nitrogen following in that order. Heat Treatment: Specimens for heat treatment were wrapped in titanium sheet before sealing in the argon-filled quartz capsules. Heat-treatment times varied from 100 hr at 800°C to 0.5 hr at 1400 °C. After heat treatment the specimens were quenched by breaking the capsule in water. With the exception of alloys in the low composition region, heat treatment did not have an appreciable effect on the as-cast microstructures. Metallography: Following heat treatment, the specimens were prepared for metallographic examination by grinding on emery paper and electrolytic polishing. For the majority of the specimens a 10-sec etch with Remington "A" agent (25 pct HNO3, 25 pct Hf, and 50 pct glycerin) adequately

Jan 1, 1954

By W. C. Elmore

THE magnetic powder method, long used for roughly mapping mag-netic fields, has recently been refined 1,2 for investigating the microscopic variations in the surface magnetization of ferromagnetic crystals. Bitter2 first discovered regular powder patterns connected with the crystal structure of such specimens. Several other investigators3 have used Bitter's original technique, with slight modifications, to study the varia-tion of the patterns with variations in the magnetizing field applied parallel to the surface, and their dependence upon the state of strain, of polish and of crystal cut. All of the explanations-of these patterns on metallic ferromagnetics have been couched in general terms. In a preliminary report we have described an improvement in the powder technique which led us to the discovery of a new effect throwing con-siderable light on the magnetic secondary structure of alpha iron4 and of nickel5 single crystals. We now report additional evidence confirming the existence and stability of a magnetic block secondary structure.

Jan 1, 1935

By W. C. Elmore

THE magnetic powder method, long used. for roughly mapping mag-netic fields, has recently been refined 1,2 for investigating the microscopic variations in the surface magnetization of ferromagnetic crystals. Bitter2 first discovered regular powder patterns connected with the crystal structure of such specimens. Several other investigators3 have used Bitter's original technique, with slight modifications, to study the varia-tion of the patterns with variations in the magnetizing field applied parallel to the surface, and their dependence upon the state of strain, of polish and of crystal cut. All of the explanations of these patterns on metallic ferromagnetics have been couched in general terms. In a preliminary report we have described an improvement in the powder technique which led us to the discovery of a new effect throwing con-siderable light on the magnetic secondary structure of alpha iron4 and of nickels single crystals. We now report additional evidence confirming the existence and stability of a magnetic block secondary structure.

Jan 1, 1936

By A. Hellawell

Specitlrens of the Al-Ge eutectic alloy have been frozen unidivectionally at rates between 2.5 x 10-6 and 2.5 x 10-4 cm per sec and the structure examined by optical and X-ray methods. There is no epitaxial relationship between phases, the aluminum having random orientation and the germanium a preferred (011) fiber textuve. Lamellar colonies which are BINARY eutectic alloys occur between either silicon or germanium with the metals aluminum or silver. common in this alloy are constructed from axial and nonaxial (111) plates of germanium which are related by a variety of twin configurations. Irregular or globular regions of the microstructure are composed of continuous single crystals of each phase, the germanium being heavily twinned. There is limited solid solubility in these systems, and the eutectic phases all involve diamond cubic with fcc crystal structures. In the microstructures of these eutectic mixtures the silicon and germanium crystals exhibit an almost infinite variety of shapes which are notably sensitive to

Jan 1, 1968

By J. R. Campbell

During the past few years, the writer has had occasion to take several excursions into the realms of the washability of beds 3 and 4 of the Pocahontas coal and the proper handling of these coals in prepared sizes Fig. 1.—Washability curve for 4 by 2½-in. egg, PocahoKtas coal. Note that definite break occurs at about 1.60 sp. gr., and washing at this gravity removes all heavy rock and slate, amounting to about 5 per cent. Curve 2 indicates a bony coal, and washed egg coal might not have a good appcarance, and would be condemned by visual inspection, although it would be well prepared mechanically. to attain the greatest realization for the operator and yet produce a market product acceptable to the consumer. Preparation is not new in the southern field, but some new angles have presented themselves in recent years on account of the progress of mechanical preparation. Mechanical methods are entirely devoid of the five senses given to

Jan 1, 1931

GENTLEMEN : It is my privilege to transmit herewith the reports for the calendar year 1932 of your Treasurer and the Chairmen of the following Standing Committees: Finance, Admissions, Membership, Papers and Publications, Library, and Mining and Metallurgy. To these reports you are referred for additional details of the year's activities. Finances.-Continuation of depressed conditions in the mining industry (in common with other industries) caused the income of the Institute to decline from $168,274 in 1931 to $138,331. However, economies were effected so as to reduce expenditures from $171,198 to $135,977. As a consequence the net result of the operations for the year was a-surplus of income amounting to $2,354 compared with a deficit of $2,924 in 1931. This gratifying result is accounted for in large measure by the foresight of the Finance Committee in anticipating a substantial decline in income and preparing the budget accordingly. Incidentally, the tentative budget for 1933 has been balanced at $125,000.

Jan 1, 1932

A LARGE proportion of the steel that is melted and refined in the United States and poured into ingots is made in basic open- hearth furnaces. The capacity of these furnaces varies over a wide range with a large majority falling within limits of 50 to 200 tons (Fig. 1) The two general types of furnace design used are stationary [ ] and tilting furnaces, the former being much more common. The fuel burned in such furnaces is either one of several types of gas, or a liquid fuel such as oil or tar, or a combination of gas and liquid fuel. GENERAL FEATURES OF FURNACE CONSTRUCTION The design of a modern stationary furnace built to burn liquid fuel and with a capacity of 175 tons is shown in Figs. 2 to 4. The cross- section of the furnace at the tap hole is illustrated in Fig. 2, which shows the bottom construction, sloping back wall, and the rigid steel

Jan 1, 1944

By Anton Sawatzky, Erich Vogt

By means of mathematical solutions to the appropriate diffusion equations, we describe the kinetics of the thermal diffusion of hydrogen in Zircaloy-2 for the various temperatures and concentrations encountered in a heavy water moderated reactor. When the hydrogen concentration is below terminal solid solubility only the a Phase is present. Redistributions are then described in terms of the characteristic functions of the difhsion equation. For higher concentrations both the a and 6 phases are present. We assume the two phases to be always in equilibrium. For moderately small hydrogen concentrations exact solutions of the two-phase equation approach the the approximate solutions derived by Sawatzky and for all concentrations the exact solutions exhibit the qualitative features of his result: the two-phase concentration increases with time, everywhere; in the absence of a hydrogen current at the hot end of the sample an a-phase region always exists there; the interface of the a + 6 , a-phase boundary moves toward the cold md of the sample and the hydrogen concentration is discontinuous at the interface. Simultaneous solulions of the a and a + 6 hydrogen distributims and of the concomitant interface motion are obtained and compared to the observations of Sawatzky and Markowitz. The kinetics of the hydrogen diffusion process are shown to lead to m apparent heat of transport of the a phase which is lower than the actual value (even for samples with long anneals) thus resolving at least partially the disparity between experimental measurements of this quantity. A number of recent papers1"4 have reported measurements on the diffusion and redistribution of hydrogen in Zircaloy-2 under temperature and concentration gradients. These studies were instigated by problems arising from increasing use of Zircaloy-2 as a fuel element cladding material in pressurized-water power-reactors. The Zircaloy-2 picks up hydrogen during the operation of the reactor: the consequent precipitation of zirconium hydride in the Zircaloy-2 has pronounced effects on its mechanical properties. The Purpose of the present Paper is to describe the kinetics of the thermal diffusion of hydrogen in Zircaloy-2 for the various hydrogen concentrations and temperatures likely to be encountered in reactors. When the hydrogen in the Zircaloy-2 is entirely in the solid solution phase (a phase), the differential equation for thermal diffusion is well known and the redistribution can be described by standard mathematical methods some of which are given in Section 11 below. The treatment of the a + 6 (hydride) region differs from the earlier treatment of sawatzky3 by taking into account several modifications of the two-phase diffusion equations as suggested to us by Markowitz4 and Kidson.5 Even with the modifications the results obtained in our more complete treatment are substantially the same as those found by Sawatzky. As we show, the difference between the results of sawatzky3 and kIarkowitz4 is largely due to the difference in the geometry of their experiments. In the next section we derive the modified two-phase equation for arbitrary geometry. The exact solution of this equation is given in Section III for linear and cylindrical geometry. It is shown that Sawatzky's approximate solution is quite accurate for almost all the temperatures and hydrogen concentrations which are actually encountered. In Sawatzky's approximate theory the hydrogen concentration everywhere in the two-phase region increases continuously. As his paper pointed out, this result, together with hydrogen conservation, implies that in a sample with no hydrogen current flowing into the hot end a two-phase region is always accompanied by a single-phase region at the hot end of the sample. The net hydrogen gain in the two-phase region is supplied by the decrease of hydrogen in the single-phase region and by the movement of the (a, a + 6) boundary toward the cold end of the sample. Hydrogen conservation at the (a, a + 6) boundary leads to a discontinuity in the concentration and its derivative there. In Section IV it is shown how these qualitative features of the thermal diffusion kinetics arise from the simultaneous solution of the a-phase differential equation and a + 6 phase equation. Methods derived by us previously for the solution of the redistribution in both phases and the accompanying motion of the boundary are used to obtain approximate solutions valid for large times. The solutions account well for the observed redistributions of Sawatzky and Markowitz. It is shown how the continuing motion of the (a, a + 6) boundary leads to measured values of the heat of transport lower than the actual value, even for specimens with relatively long anneals.

Jan 1, 1963

By G. S. Ansell

RCENTLY, in investigating the high-temperature creep properties of an aluminum, SAP-type alloy, MD 2100, fabricated by Professor F. V. Lenel of Rensselaer Polytechnic Institute, Ansell and Weertman1 found unusually low creep rates. These creep rates are 4 or 5 orders of magnitude lower than is predicted by the slowest creep mechanism based upon dispersion-hardened alloy theory. They ascribed these results to a lack of both normal active dislocation sources and a continuous three-dimensional dislocation network. If one couples these results with the following factors of production and microstructure: 1) The compacted and sintered aluminum powder compact is hot-extruded, with an extrusion ratio of 25:1.2 2) The alyminum oxide particles are approximately 140A units thick, and have a spacing varying from 0.05 to 1.5 1. 3 3) The alloy has plate-shaped grains with minor axes of about 5 X 10 -3 mm and major axes several orders of magnitude greater than this.'

Jan 1, 1960

By L. E. Paulson

INTRODUCTION The Northern Great Plains has 16 billion tons of strippable lignite (1). Presently, 15 million tons per year are mined; essentially all is used for generation of electrical power. In the future, additional large quantities will be consumed in the production of gaseous and liquid fuels. A major consideration in design and operability of power stations and conversion plants is the nature of the ash or inorganic constituents of the lignite used. These inorganic components cause fireside fouling in boilers, exert a catalytic effect in liquefaction and gasification, and contribute to particulate and SO2 emissions. Ash fouling on fireside boiler tubes cause reduced heat transfer and gas flow which limits boiler performance. Severe fouling can result in shutdown of the boiler. A comprehensive test program in both pilot plant and field studies at the Grand Forks Energy Technology Center (GFETC) has shown that ash fouling increases with increased sodium content of low-rank coals (2). The sodium in the coal can be

Jan 1, 1983

By J. S. Aronofsky

The first step in a quantitative analysis ot the mechanism of oil displacement by water in a fractured reservoir is usually conceded to be the solution of the differential equation describing the saturation distribution of two immiscible fluids flowing in a porous medium, where the capillary pressure is taken into account. In such a system the production mechanism may consist of displacement of oil both by the flow of water due to natural or artificially imposed pressure gradients and by imbibition, which implies a flow of water not due to external pressure gradients. Owing to the presence of the two oil displacement mechanisms, the mathematical model given by the differential equation intended to describe the system may not properly represent the behavior of the physical system. In fact, in the reservoir the rate of water advance may be very slow, and in the case of a fractured reservoir with a great number of large fractures, the pressure difference determining the flow of water through the matrix may be much less than 1 lb/'psi over lengths of a few feet. In such a case, imbi-bition (the exchange between oil in the matrix and water in the fractures resulting from capillary forces) may become, with time. a significant element of the production mechanism. It occurred Lo the authors, however, that without going into a physical analysis of the process of production, it might be possible by means of simple abstract reasoning to throw some light on the variation of recovery with time under conditions occurring in a highly fractured oil reservoir with rising water table. The object of this paper is to present both the reasoning and its application to a reservoir of the highly fractured type. Specifically, the analysis given here was undertaken to try to explain the increase of recovery (as defined later) with time as observed in this reservoir, without having to assume unlikely variations in the reservoir parameters with depth. This attempt has been successful as will become clear upon comparison of the computed recoveries with the actual field data. ABSTRACT MODEL Let us consider a small volume. of porous matrix saturated with oil at time, t = 0. Let the process of oil displacement by water start at time, t = t,,. At some time, t, the process will have terminated. Then a volume of oil equal to or smaller than the original oil contained in the matrix will have been produced. The first basic assumption that describes the model and guides the forthcoming reasoning is that the oil production from the small volume. dv, is a continuous monotonic function of time and that it converges to a finite limit. Such an assumption is not inconsistent with the results of laboratory waterflood tests as well as with results of imbibition tests where this is, in fact, observed. The second basic assumption is that none of the properties which determine the rate of convergence change sufficiently during the process to affect this rate or the limit. Let it be assumed that the form of the function of time relative to production from the matrix volume. dv, is given by where V,(t) is the volume of oil produced up to that time t. R is the limit toward which the recovery converges, A is a constant giving the rate of convergence, and V,(t) is the volume of oil originally in place in the volume, dv. It should be noted that recovery at time I will be understood here to he It follows that r. tends to R as t tends to infinity. CONSTRUCTION OF RESERVOIR FROM ABSTRACT MODEL Let the reservoir consist of a series of identical blocks of porous matrix stacked vertically and separated by fractures. Let each of these blocks satisfy the conditions of our abstract model. These conditions are: (1) that recovery is a continuous mono-tonic function of time converging to finite limit, and (2) none of the properties that determine the rate of convergence change sufficiently to affect the rate or the limit. Let water be rising in fractures so that oil production from any part of the block starts when the water comes in conLact with it. TOTAL RECOVERY FROM THE RESERVOIR COMPARED TO RECOVERY FROM A SINGLE MODEL ELEMENT As stipulated in Eq. 1, in the case of the abstract model,

By James E. Lonergan, Young C. Kim

Over the past two and one-half years, various emission control strategies for a coal-fired power plant have been jointly developed by the University of Arizona and the Homer City Owners. The objective of this work was to assist the Homer City management in their efforts to comply with SO2 emission regulations while continuing to use the relatively high sulfur coal from their captive mines as the primary source of plant fuel. One of the operational strategies studied was to have the captive mines minimize the sulfur variability of the run-of-mine coal on a short term basis. A mine production scheduling program called COMPF2 was developed to perform this task. This paper describes the application of this mine planning program at an underground coal mine. A comparison of the planning results with actual production figures showed the ability of this program to schedule production so as to minimize both the sulfur content and the sulfur variability of run-of-mine coal.

Jan 1, 1983

By S. N. Singh, M. C. Flemings

Results are presented of a study on the combined influences of ingot dendrite am spacing and thermo-mechanical treatments on the fracture behavior and mechanical properties of high purity 7075 aluminum alloy. The most important single variable influencing mechanical properties was found to be undissolved alloy second Phase (microsegregation inherited from the original ingot). Ultimate and yield strengths were found to increase linearly with decreasing amount of alloy second phase while ductility increased markedly. At low amounts of second phase, transverse properties were approximately equal to longitudinal properties. In tensile testing, microcracks and holes were invariably found to originate in or around second phase particles. Fracture occurred both by propagation of cracks and coalescence of holes, depending on the distribution and amount of second phase. IN most commercial wrought alloys, second phase particles are present that are inherited from the original cast ingot. These include, for example, non-equilibrium alloy second phases such as CuAl2 and impurity second phases such as FeA13 and Cr2A1, in aluminum alloys. A previous paper1 has dealt with the morphology of these second phases in cast and wrought aluminum 7075 alloy, and with their behavior during various thermomechanical treatments. In this paper we discuss the influence of the particles on mechanical properties and fracture behavior of the alloy. Previous experimental work indicating a direct and major effect of second phase particles on mechanical properties (especially on ductility) includes the work of Edelson and Baldwin on pure copper.' Also relevant are the many studies demonstrating the important effect of nonmetallic inclusions on the fracture of. steel.3'4 Work on aluminum includes that of Antes, Lipson, and Rosenthal5 who showed that a dramatic improvement in ductility of wrought aluminum alloys of the 7000 series is achieved by eliminating second phases. It now seems well established that included second phases play a dominant role in controlling ductility (as measured, for example, by reduction in area in a tensile test) of a variety of materials. There is, therefore, considerable current interest in the mechanisms by which second phase particles affect ductile fracture. Experiments done by various workers have shown that second phase particles or discontinuities in the microstructure are potential sites for nuclea-tion of microcracks and of holes,6-l3 which then grow and cause premature fracture and the loss of ductility. Theoretical attempts have been made to explain the observed phenomena; most are able to explain observations qualitatively, but lack quantitative agreement. Much experimental work needs to be done to aid extension of theoretical models. A recent review article by Rosenfield summarizes work in this general area.14 PROCEDURE Material used in the previously described study on solution kinetics of cast and wrought 7075 alloy1 was also used in this study. Procedures for ingot casting, solution treating, and working were described in detail in that paper. Test bars were obtained for material of 76 initial dendrite arm spacing (11/2 in. from the ingot base) and 95 µ initial dendrite arm spacing (51/2 in. from the ingot base) for the following thermomechanical treatments (solution temperature 860°F; reduction by cold rolling). a) Solution treated 12 hr, reduced 2/1, 4/1, and 16/1. b) Solution treated 12 hr, reduced 16/1, solution treated approximately 5 hr after reduction. c) Same as a) except solution treated 24 hr prior to reduction. d) Same as b) except solution treated 24 hr prior to reduction. e) Same as d) except solution treated 20 hr after reduction. Test bars were taken both longitudinally and transverse to the rolling direction. Transverse properties are in the long transverse direction; since the final product was sheet (0.030 in. thick), properties in the short transverse direction could not be obtained. Test bars were flat specimens, of gage cross section1/-| in. by 0.030 in. and 1/2 in. gage length. After machining the test bars, they were given an additional 1/2 hr solution treatment of 860°F and aged 24 hr at 250°F. Three bars were tested for each location and thermomechanical treatment, after rejection of mechanically flawed bars. The average results of these three bars are reported. Elongation was measured using a $ in. extensometer and reduction in area was determined using a profilometer to measure the area after fracture. INFLUENCE OF THERMOMECHANICAL TREATMENTS AND SECOND PHASE ON MECHANICAL PROPERTIES Results of mechanical testing are presented in Figs. 1 to 4 and in tabular form in the Appendix. A general conclusion from results obtained is that details of the thermomechanical treatments studied were important only insofar as they influenced the amount of residual second phase. Figs. 1 and 4 show the longitudinal properties obtained (regardless of thermomechanical

Jan 1, 1970

By D. Turnbull, J. H. Hollomon

THERE is a large body of evidence'" indicating that solidification during the liquid-solid transition is usually induced by heterogeneities present in the liquid. By dispersing liquid metals into small droplets, the impurities responsible for catalyzing solidification are isolated within a small number of these droplets. The effect of the foreign body therefore is restricted to a single drop by this technique. Thus upon cooling below the melting temperature, solidification is initiated by homogeneous nucleation in the majority of the droplets that do not contain impurities. In the case of solidification of liquid metals, the activation energy for nucleation is so great that its rate changes by orders of magnitude for a change in temperature of only several degrees centigrade.' Effectively homogeneous nucleation occurs at a critical temperature upon continuous cooling. Thus by microscopic observation of single particles during cooling, a temperature at which the rate of homogeneous nucleation becomes sensible can be determined.3 since at the temperatures at which nucleation occurs in the absence of impurities the rate of crystal growth is extremely rapid, the temperature at which the entire particle solidifies is very nearly the temperature at which the nucleation of the solidification occurs. Thus for liquids that freeze at high temperatures the onset of nucleation can be established by simply observing the temperature at which the marked heat evolution and increase in brightness of the particle occur. For liquids that freeze at lower temperatures the onset of nucleation can be determined by a rumpling and change in shape of the particle resulting from its solidification. The microscopic technique for observing the solidification of small particles has already been described." In earlier papers the nucleation of solidification of pure metals 5,6 and of alloy systems7 showing complete liquid and solid solubility have been described. In the present paper, the observations are extended to a simple eutectic system (Pb-Sn) where the possibility of the formation of two solid phases exists. Metals for the investigation were obtained from the American Smelting and Refining Co. in the form of pure lead and pure tin, 99.8 and 99.9 pct purity, respectively. An ingot of each of the pure metals was made into shot by heating the metals at a temperature about 50 °C in excess of the melting point and pouring the liquid slowly into a container of water at 15°C. Samples of the shotted pure metals were weighed out to make alloys containing 5, 10, 15, 20, 25, 30, 40, 50, 60, 70, 80, and 90 atomic pct Pb. Samples of each alloy were then melted in separate beakers. Each melt was poured through a pyrex funnel into a cylindrical mold (% in. ID). The casting solidified in 10 to 20 sec. The inside of the mold as well as the funnel through which the metal was poured were coated with graphite to eliminate adherence of the metal. Analyses were performed on some of the compositions and are given in Table I. The compositions also were checked for these samples and for those that were not analyzed by determining the spread between the liquidus and the solidus upon melting the small metal particles. These measurements agreed as well with the nominal compositions as the analyses listed above. Results The results of the supercooling experiments for the several alloys are summarized in Table II and plotted on the constitution diagram in Fig. 1. Data for the pure lead and pure tin were taken from earlier investigations. The values for the maximum supercooling of the several alloys are the average of several determinations on a number of drops of each alloy. The maximum value in any determination was within about 2 pct of the average. For the alloys containing from 20 to 60 atomic pct Sn, inclusive, two marked changes of the surface structure were observed upon cooling. At the higher temperature, after the first appearance of the solid phase it continued to grow slowly at a constant temperature and then stopped. At the lower temperature the alteration of surface structure was abrupt. For the alloys containing from 70 to 95 atomic pct Sn, inclusive, an abrupt change in surface structure was observed at a single critical temperature.

Jan 1, 1952