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By Henry F. Adams, Guy H. Ruggles

In this paper the authors aim to chronicle the experience and salient points brought out in changing flotation reagents at a concentrator which had probably been using a minimum amount of oil at a minimum cost per ton, to a more complicated system requiring a partial chemical control. The original oils were coal tar and pine oil. The new reagents are lime, xanthate and pine oil. It was found that there were no insurmountable difficulties and eventually the cost of the new reagents per ton of ore proved to be very little more than that of the old. Lime Plant When the question of handling lime came up there were two propositions open: (1) to handle the lime dry; (2) to handle it wet in the form of an emulsion. Granting that a dry lime feeder would function properly, delivering lime uniformly, the chief objection was the dust that would be raised when these feeders were being charged or operated, as the only possible location was on a gallery beneath which men were working. With this objection the handling of lime as an emulsion seemed to be the better scheme. The lime plant which was first installed was for experimental work on one section. This was gradually changed and developed until it was of sufficient size to accommodate 20 sections. The various changes will not be discussed and the following description deals only with the fully developed plant. Crude as it is, and perhaps somewhat expensive to operate, the lime-handling plant has been quite successful. Much has been learned which will pave the way for a better installation in the future. Burnt lime is received loose in standard gage box cars. This is the product of the kilns and has had no screening or sorting. A grab sample is taken from each car as it is unloaded. An average of the analyses of samples from 44 cars gave the following: Available CaO Total CaO, Oxide and Hy- MgO, Fe²O³ + Al²O³, Insoluble, Per Cent. drate, Per Cent. Per Cent. Per Cent. Pek Cent. 88.3 79.2 1.6 ' 1.3 2.2

Jan 1, 1928

By E. N. Silverman

Mixtures of' MnS, ZFeO-SiO,, ZMnO.SiO, FeO, and MnO were prepared synthetically and used to study the planes ZFeO. Si0,-ZMnO.SiO,-MnS, FeO-MnO-MnS, and Fe0-MnO.Si0,-MnS in the quaternary system. Because the oxides and silicates studied flux MnS, inclusions in this system are partly liquid during rolling. Also, oxygen can modify subsurface inclusions through the reaction MnS + FeO—FeS + MnO during the soaking of ingots and the reheating of blooms and billets. NONMETALLIC inclusions in steel have long been a subject of study and conjecture because the properties of many steels are known to be affected by the the kind and amount of inclusions present. In free-machining steels, the type of inclusion present has a direct bearing on their machinability; in other steels, cleanliness is important and metallurgists direct their efforts at reducing the amount of non-metallic inclusions. Thus, the accumulation of knowledge about the formation and behavior of inclusions during all stages of steelmaking and processing should aid in improving the quality of steels and decreasing the production costs resulting from rejections. Previous studies of inclusions have contributed greatly to our understanding. The investigators have generally examined inclusions in finished steel. Boulger, Moorehead, and Garvey1 found that in Bessemer steels, low silicon contents results in globular sulfide inclusions with attendant high machin- ability ratings. Van vlack2 also found that low silicon contents favor inclusion morphology that contributes to high machinability ratings. Boquist and Stoll* found that silicon content affected sulfide inclusions and machinability of blooms, billets and bars more than did the finishing temperature in the range between 1775° and 2075°F. Carney and Rudolphy3 studied the distribution of sulfur, manganese, silicon, and carbon in a commercial ingot of resulfur-ized steel and found that silicon was concentrated near the bottom. This helped to explain why bottom cuts had poorer machinability. Klinger and Koch4 developed techniques for extracting inclusions from steel, and the technique devised by Gurry, Chris-takos, and stricker5 for extracting carbides can also be adapted to the study of inclusions. A different approach to the study of inclusions in steel consists of synthesizing the constituents that form inclusions and determining the phase eauilibria in the system that contains the constituents. The resulting phase diagrams can then be used to determine the effect of the various constituents upon each other. In this way, it becomes possible to under-

Jan 1, 1962

By G. C. Kuczynski

Two particles in mutual contact form a system which is not in thermo-dynamical equilibrium, because its total surface free energy is not a minimum. If such a system is left for a certain period of time, the bonding of the two particles will take place in order to decrease the total surface area, even though the temperature is lower than the melting point. This phenomenon of bonding of two or more particles with the application of heat only and at temperatures below melting point of any component of the system will be called sintering, although the powder metallurgists use this term in a broader sense, including the presence of molten phase and pressure. It is the objective of this paper to study this process and the mechanisms involved in it. This problem is of utmost importance to powder metallurgy and powder ceramics, and its technological aspects have been studied for a good many years. However, the powder metallurgical operations are too complex and include too many superimposing mechanisms, and too many variables for a direct study. It was therefore advisable for the purposes of this study to reduce the variables to a minimum. In this work the radius of the interface formed during bonding in a simple system composed of a spherical particle and a large block of the same metal was studied as a function of time and temperature. It is believed that the mechanism involved in this simple process is fundamental to any sintering operations. Previous Work J. Frenkell was the first to make a serious attempt to develop a theory of sintering. He assumed that the process consists of a slow deformation of crystalline particles under the influence of surface tension which reduces to a viscous flow where the coefficient of viscosity n is related to the self-diffusion coefficient D by the following equation 1 _ D D6kT [1] where 6 is interatomic distance, k the Boltzman constant, and T the absolute temperature. This type of viscous flow of a crystalline substance is essentially different from the ordinary plastic flow. The latter is a specific propcrty of crystals and cannot take place in amorphous bodies. According to Frenkel this viscous type of flow is due to the diffusion of the holes or vacancies arising in the lattice. He was able to derive an equation relating the growth of the interface between two spherical crystalline particles or between a particle and a semi-infinite crystal (Fig 1) to time t at constant temperature. This relationship can be written as follows: x²— 3/2 a/nt [2] where x is the radius of the interface assumed to be circular, a the original radius of the sphere and a surface tension of the material. The other assump- x tions are that x is less than 0.3 and that during the period 1 the original radius, a, of the metallic particle did not change appreciably. A. J. Shaler and J. Wulff2 followed closely the ideas of Frenkel in their theory of sintering of a mass of metallic powder. Neither Frenkel nor Shaler has validated his theoretical speculations with conclusive experimental data. Two measurements reported by

Jan 1, 1950

By Earl Greiner

THE constitution of the iron-silicon alloys containing from 14 to 33.4 weight per cent silicon has been studied by a number of investigators, whose results have been reviewed in a monograph published by the Engineering Foundation1. In these previous researches, the solubility of silicon in iron was determined by thermal, microscopic or magnetic methods and the compound Fe3Si2 was reported to be stable at tempera-tures from 0 to approximately 1030° C. This paper describes the results of an X-ray investigation of the solubility of silicon in iron and gives data which prove that the Fe3Si2 phase is unstable below 825° C. In order to obtain the present results on the solubility of silicon in iron, the authors have utilized the lattice constants of the alpha-phase iron-silicon alloys given in a previous publication2, and also some addi-tional data which will subsequently be described.

Jan 1, 1936

By A. E. Himebaugh

A SEMI-AUTOMATIC hoist has been installed at the 2966 station of the Copper Queen mine, since neither the bulk of supplies handled nor the number of men engaged in developing the 3100 level justifies the constant attendance of two cagers and two hoist operators. The connecting service shaft between the 2966 and 3100 levels is actually a two-compartment raise. Below the 2966 level the shaft is 7x13 ft-slightly oversize to permit downcast ventilation and provide space for the 16-conductor flexible control cable. The raise extends 52 ft above the 2966 level for a 3-ft diam head sheave. Another 3-ft sheave is mounted as an idler between the hoist and head sheave, eliminating the need for an inclined cableway. The main compartment serves as a cageway; the other compartment provides a manway and space for service lines. Since vertical travel is limited, rope speed is of minor importance.

Jan 5, 1958

By William E. Ford, Edward Salisbury Dana

WheweUite. Calcium oxalste CaCz04.Hz0. In small colorless monoclinic crystals. Optically +. j3 = 1.555. From haxony, with coal; also from Bohemia, and Akace. Oxammite. Ammonium oxelate, (N&)rC20r.2HzO. From the guano of the Gudape Isbnds, Peru.

Jan 1, 1922

By T. R. Ingraham

When aluminum sulfate was decomposed in an evacuated apparatus and the sample cooled, Q alumina was found. The thermodynamics of the decomposition reaction were resolved by measurements of the total pressure of SO3, SO2, and O2 generated over the sample at various temperatures. The results were correlated with other published data to calculate the rmges of thermodynamic stability of the various compounds involved. The thermal decomposition of aluminum sulfate was studied by Wijhler, Pluddeman, and Wöhler1 and by Warner and Ingraham.2 The results of both studies were critically reviewed by Kellogg,3 who observed that "each set of data shows considerable scatter and strong curvature on a plot of log pso3 vs 1/T".3 He agreed with Warner and Ingraham2 that both the discrepancy in the two sets of results and their curvature may arise from the indefinite properties of the particular form of A12O3 which is formed during the decomposition. While studying the thermal stability of other sulfate systems, we had noted the presence of nonequilibrium oxide properties in both the cobalt4 and manganese5 systems, but neither had shown any appreciable curvature on a logPSO, vs 1/T relationship, and the data from both systems agreed reasonably well with prior work. It therefore seemed reasonable to reexamine the technique which had been used in our earlier work on aluminum sulfate.2 The principal difference was that a tightly compacted pellet had been used for the earlier aluminum sulfate work, whereas a loose powder, contained in a platinum boat, was used for our work on other sulfate systems. In addition, a better technique had been developed for dehydrating the samples. From work done on the nickel system,6 we had become aware of the highly protective nature of some sulfate layers on their oxjdes, and hence of the necessity of providing a large surface area of P3e sample when equilibrium was to be attained in a reasonable time. That observation suggested that perhaps a steady state, rather than equilibrium, had been reached in the earlier work on aluminum sulfate. This paper reports a repetition of the experimental work with large, finely divided samples of anhydrous aluminum sulfate. APPARATUS AND PROCEDURE The apparatus used in the experimental work was described in earlier papers.2,7 The source material was Anachemia reagent-grade Al2(sO4)3 - 18H2O which was first partly dehydrated by heating at 400°C for 48 hr and then completely dehydrated by repeated baking of an aluminum sulfate-oleum slush to dryness at 450°C. ? Alas was prepared by decomposing some of the sulfate in a muffle furnace at 800° C overnight. Approximately equal amounts of the 7) alumina and aluminum sulfate were used in the experiments. The finely divided samples were handled under dry box conditions, and in addition some of the aluminum sulfate was decomposed in the apparatus while it was under vacuum, to ensure its complete dehydration prior to sealing the apparatus. The samples were heated to a series of constant temperatures on both increasing- and decreasing-tem-perature programs. Two to three days were required to obtain steady readings of the total decomposition pressure on an increasing-temperature program, and 5 to 6 days on a decreasing-temperature program. Three samples were examined on both programs. Within experimental error, the results for each sample and each program could not be distinguished.

Jan 1, 1969

"Located in Madison River Canyon, about 14 miles by road from Norris, Mont. Built in 1907 by Madison River Power Co.DAM: Rock filled wooden crib structure, 183 ft. long, 34 ft. high or 44 ft. to top of flashboards.SPILLWAY: 140 ft. long, equipped with flashboards 10 ft. high.PIPE: One 10-foot and one 12-foot wood-stave pipe, 7,515 feet long.PRESSURE: One pressure chamber, 32 ft. high, 30 ft. wide and 81 ft.CHAMBER: long, built of concrete.PENSTOCKS: 4 9-foot steel penstocks about 200 ft. long, one for each wheel.WATER WHEELS: 4 double horizontal, center discharge, Sampson special 44-inch turbines, 3,600 h-p., at 100 ft. head. Speed 300 r. p. m„ direct connected to generators.GENERATORS: 4 G. E., W. C., 2,250 k-w., 4,000 volts, 300 r. p. m., 3 phase, 60 cycles, alternators, with exciters mounted on same shaft.TRANSFORMERS: 12 G. E., W. C., 900 k-w., 60 cycles. High tension voltage 23,100, 34,650, 46,200; low tension voltage 4,000, 3,800, 3,600. Now operating at 46,200, delta connected. They can be connected Y for 40,000, 60,000 or 80,000.OPERATION: This is the principal plant of the whole system and carries most of the load."

Jan 1, 1913

By D. W. Levinson, L. F. Mondolfo, N. A. Gjostein

MANY investigations are reported in the literature on the age hardening of Al-Mg-Zn alloys but most of them are concerned mainly with mechanical property changes. The present investigation was started to determine the structural changes in an AlMgZn alloy. The alloy composition was chosen in the existing phase diagram" so as to lie on the quasi-binary section Al-(AlZn)Mg Actually, it was found that the diagram as published was inexact at the lower temperatures and that the phase in equilibrium with aluminum at the lower temperatures is not the ternary compound. Technique The alloy used for the investigation was prepared from high purity materials and the resulting composition as determined by chemical and spectro-graphic analysis was: Zn, 6.17 pct; Mg, 2.13 pct; CU, 0.03 pct; Si, 0.009 pct; Fe, 0.005 pct; and the remainder, aluminum. An ingot -in. thick was cast, homogenized, hot and cold-rolled to strip 0.064-in. thick for dilato-metric and powder work, and to foil 0.005-in. thick for single crystal work. Solution treatment temperature for all specimens was 475°±5°C for periods of at least 1 hr, either in air furnaces or lead baths. Aging was done in oil or Pb-Bi baths controlled to within ±3°C. The aging was investigated at the following temperatures: room (30°), 130°, ZOO0, 260°, and 300°C. For the dilatometric study, the length changes were measured continuously, at temperature, using strips of alloy 10 in. long, shaped as channels to eliminate undesirable deflection due to bending. To compensate for thermal expansion and contraction due to the variations in the temperature of the aging baths, the dilatometers were built of the same alloy as the one being tested, with the same shape and size, but with material fully annealed. Gages on which 0.0005 in. could be read and 0.0001 in. estimated were used to measure the dilation. Length changes were also measured at room temperature. Strips approximately 10 in. long were solution-treated, quenched, and measured in a supermicrome-ter in which 0.0001 in. could be read and 0.00001 in. estimated. The specimens were immediately aged for a given time, remeasured, and then the cycle was repeated, including the solution treatment. The error of measurement with this technique was somewhat larger, but the results confirmed those obtained by continuous measurements. The sheet used for the dilatometric work was checked to determine grain orientation. Both X-rays and etching methods revealed a rather coarse grain size but only a negligible amount of preferred orientation. Thus, volume changes calculated from length changes are not invalidated by preferential orientation effects. Pieces of the sheet used for the dilatometric work were also used for the metal -lographic work. Filings for the powder X-ray study were produced from a homogenized piece of sheet. These filings were magnetically purged of iron, screened to 200 mesh, sealed in a Pyrex tube containing an argon atmosphere, and solution-treated. When quenching, the glass tube was broken, so that the powder dropped directly into cold water. After drying with alcohol, the powder was sealed into capillary tubes containing an argon atmosphere and then aged for the required times. In spite of all these precautions the three strongest lines of a( Al2o) appeared in all patterns, and were used as internal standards. By the use of these standards, accurate corrections for film shrinkage were obtained. For the back reflection patterns, annealed nickel powder was mixed with the specimen to act as internal standard. A preliminary investigation was made in small (57.3 mm diam) powder cameras. From these patterns the changes which took place in the solid-

Jan 1, 1957

By P. H. G., Durville

ANY metal which contains even a small percentage of aluminum possesses certain peculiarities of appearance and properties which are exhibited both when the metal is melted and after it solidifies. Pure aluminum, or an alloy containing a small proportion of aluminum, can be melted without flux-except for a layer of charcoal-because a film of aluminum oxide and metal forms at the surface of melted aluminum. Although very thin, this film is air-proof, and it prevents the metal underneath from oxidizing. This oxidized film does not move easily on account of its toughness and high surface tension. One very important point in connection with this process of still casting has not been strongly enough stressed, namely, that the same kind of surface film with the same peculiarities forms over the surface of all melted alloys that contain even a small proportion of aluminum. Experienced foundrymen know how desirable it is to cast aluminum under its "skin" or under the surface of the film which tends to remain still. In the case of red copper, when in fusion, the surface shows pure copper only. This' is due to the fact that liquid copper constantly absorbs the copper oxide which forms on the surface. By closely examining melting copper the oxide can be seen dissolving in the bath, and going into solution just as pulverized sugar dissolves in water. When copper is cast in the open, either in wire bars or cakes, the surface of metal exposed to the air is covered by a film of black oxide that cannot be absorbed by the metal.

Jan 1, 1927

By W. M. Robertson

The rate of crack Propagation thvough a solid meta1 in the presence of a liquid metal has been calculated. The crack is assumed to propagate by solution of the solid in the liquid under the influence of an applied stress, with volume diffusion of the dissolved solute through the liquid controlling the propagation. The calculated velocities can be tens of centimeters per second or higher. THE embrittlement of normally ductile solid metals by liquid metals has been the subject of extensive study, as summarized in the book by Rostoker, McCaughey, and arkuus.' In experimental studies of liquid-metal embrittlement it is usually concluded that the observed crack-propagation rates are too high to be accounted for by diffusion processes. Diffusion is considered to be an unimportant factor and various other mechanisms are invoked to account for the experimental observations. The similarities of liquid-metal embrittlement to stress-corrosion cracking, to hydrogen embrittlement of steel, and to low-temperature embrittlement of bcc metals are frequently used as analogies for these mechanisms.1"3 The present paper assesses how rapidly a crack could propagate by a mechanism of volume diffusion through the liquid metal. We assume that the crack propagates by solution of the solid in the liquid at the crack tip under the influence of the applied stress and diffusion of the dissolved solute away from the crack tip. The model uses only macroscopic thermodynamic, kinetic, and elastic concepts. The calculations indicate that this dissolution-diffusion mechanism can give high crack velocities. In some previous treatments4'' of crack propagation in a liquid-metal environment the fundamental step has been the breaking of atomic bonds at the crack tip. The liquid greatly decreases the energy necessary to break these bonds. The present model assumes the crack is filled with liquid metal; the presence of the liquid is essential because diffusion through the liquid is assumed to control the rate of propagation. With proper modification this model could also apply to stress corrosion in a liquid environment. THEORY Consider a crack in a homogeneous elastic continuum, ignoring all the structural details of the solid. This neglects a host of metallurgical details which can be significant in the problem of liquid-metal embrittlement;' but this simple assumption is a useful approach in evaluating the role of diffusion through the liquid. The stress distribution around the crack tip establishes a gradient in the chemical potential at the tip, which causes a diffusion flux through the liquid away from the tip. The solid-liquid interfacial tension works against crack propagation, since propagation requires creation of interfacial area. From these two considerations we derive the diffusion flux, which then yields an expression for the velocity of the crack tip. The concentration of the solute in the liquid, C, is equal to the equilibrium concentration in the presence of an unstressed, flat surface, Co, plus the excess concentration due to the stress, AC(a), plus the excess concentration due to capillarity, AC(y): We calculate AC(o) and AC(y) and then obtain the diffusion flux. Consider (Fig. 1) a long flat crack of length 2L, thickness 2r, and tip radius r, where r remains constant as the crack propagates in the positive x direction. There is no stress ay in the y direction across the flat surfaces of the crack. The magnitude of the stress at the crack tip due to the applied stress, a,, is given by the relation6 ^=^[l-2^] 12] which, for long narrow cracks, becomes The stress increases the chemical potential in proportion to the strain energy.? The excess chemical potential due to the stress, Ap(a), is given by where 52 is the atomic volume of the solid and E the Young's modulus. Inserting Eq. [3] gives Now consider the crack to be filled with a liquid metal. The excess solubility due to stress, hC(a), is given by the excess chemical potential due to capillarity, Ap(y), is given by8 where y is the solid-liquid interfacial energy, and v1 and YZ are the two principal radii of curvature of any surface point. At the crack tip, r1 = -r and vz = m, so TRANSACTIONS OF THE METALLURGICAL SOCIETY OF AIME

Jan 1, 1967

By Garland R. Dever, Preston McGrain, George W. Ellsworth

Limestone resources for industrial, constructional, and agricultural uses occur on the surface and at minable depths in several areas along the Ohio River and its navigable tributaries in Kentucky. High calcium and high carbonate limestones suitable for use in cement and lime production, steel manufacture, environmental control measures, and other special uses are present in the High Bridge Group (Ordovician) and Warsaw and Ste. Genevieve Limestones (Mississippian). Deposits with thicknesses of 7.3 to 20.7 m,(24 to 68 feet) have been documented by the analysis of samples taken at 0.3-m (1ft) intervals. Active and potential mine and quarry sites afford access to water transporation and proximity to a number of industrial and metropolitan centers. Geologic factors affecting the distribution of deposits include the Cincinnati arch, regional dip into the Appalachian and Eastern Interior basins, complex faulting in and near the western Kentucky fluorspar mining district, and late Paleozoic erosional unconformities in northeastern Kentucky.

Jan 1, 1979

By Garland R. Dever, Preston McGrain, George W. Ellsworth

Abstract-Limestone resources for industrial, constructional, and agricultural uses occur on the surface and at minable depths in several areas along the Ohio River and its navigable tributaries in Kentucky. High calcium and high carbonate limestones suitable for use in cement and lime production, steel manufacture, environment control measures, and other special uses are present in the High Bridge Group (Ordovician) and Warsaw and Ste. Genevieve Limestones (Mississippian). Deposits with thicknesses of 7.3 to 20.7 m, (24 to 68 feet) have been documented by the analysis of samples taken at 0.3-m (1- ft) intervals. Active and potential mine and quarry sites afford access to water transporation and proximity to a number of industrial and metropolitan centers. Geologic factors affecting the distribution of deposits include the Cincinnati arch, regional dip into the Appalachian and Eastern Interior basins, complex faulting in and near the western Kentucky Fluorspar mining district, and late Paleozoic, erosional unconformities in northeastern Kentucky.

Jan 4, 1978

By R. S. Shoemaker, D. L. Harris

PST investigations into the possibility of concentrating the low-grade iron ores of the Gogebic Range in Wisconsin have been hampered by the complex association of the constituent minerals. In part the problem arises from the fact that the iron occurs essentially as two minerals, hematite and goethite, having nearly the same chemical composition but exhibiting different physical properties. Individual grains of these minerals are usually so small that the ore must be ground to a size finer than 325 mesh if substantial liberation of the minerals is to be secured. Appraisal of beneficiation tests on this iron ore requires, therefore, some method of determining quantitatively the contents of constituent minerals in the various products of the beneficiation. Because of the chemical similarity of the two iron minerals, chemical analyses do not provide a means of differentiation. Although the minerals are different physically, they are both opaque and friable, and as the ore must be ground to a very fine size for liberation to be secured, quantitative microscopic methods of analysis are extremely difficult at best. In an effort to overcome these analytical problems, a quantitative X-ray diffraction analysis method has been developed at the University of Wisconsin for the research program on iron ore beneficiation. The X-ray diffraction analysis of chemical compounds of crystalline form has proved of inestimable value for structure studies and rapid qualitative analytical purposes in a number of fields.' In some cases X-ray diffraction analysis has been found suitable for quantitative determinations. H. P. Klug2 found that quantitative procedures for quartz powders when mixed with calcium fluoride were reproducible within ±1.0 pct. Talvenheimo and White3 reported quantitative analyses of clay minerals to be accurate within 10 pct and also detected 1 pct of bentonite in 99 pct illite. In other investigations,'" powders of quartz and mica have been analyzed quantitatively with accuracies from 1 to 5 pct. A powder of tungsten carbide was analyzed similarly by Redmond7 and Rooksby8 reported the determination of small amounts (0.11 pct) of calcium oxide in magnesium oxide. In the most generally practiced use of X-ray diffraction, traces of the diffracted beam are recorded as lines on a film much as lines of elements are recorded on an optical spectrograph film. As with the spectrograph, the darkness of the lines denotes the amount of the constituent in the sample. If the film is replaced by a Geiger tube assembly and a graphic recorder or a scaling unit, the intensity of the diffracted beam can be registered as a peak on a chart or energy impulses per unit of time on the scaler. Several methods of quantitative measurement have been investigated and reported in literature. Klug2 used manual operation of the goniometer and a counting technique to determine the difference in counting rates at the diffracted angle and for the background. In another case3 the area under the recorded diffracted peak was the basis for the determination. In other instances the height of the recorded diffraction peak above background, measured while the goniometer was moving, has been the basis for the measurement. The sizes of particles most suitable for diffraction techniques are reported in the literature as follows: for tungsten carbide a maximum of 40 microns7 and for quartz a maximum of 5 microns.' Very fine sizes of crystals are known to cause a broadening of the diffused beams; hence some workers have set a lower limit of 0.1 micron for quantitative results. Guinier10 has indicated that broadening of the diffracted X-ray beam is not appreciable for crystallites larger than 0.02 to 0.03

Jan 1, 1956

By E. Miller, K. L. Komarek, M. Ettenberg

The activity of aluminum in solid Co-A1 alloys has been measured by an isopiestic technique between 850° and 1200°C from 45 to 80 at. pct Al. The activity shows a Precipitous decrease around the stoichzornetric composition of CoAl. Free energies of mixing have been calculated over a limited composition range. Considering an antistructure-vacancy defect mechanism, the degree of intrinsic disorder, a , in CoAl was related to the alunminum activity. Excellent agreement between the calculated and experimental activity curves was obtained for a = 1.25 x 10-4. ThERMODYNAMIC properties of solid aluminum-transition metal alloy are being studied in an investigation of disordering in ordered compounds. In a continuing series of investigations, activities of solid Fe-1,' Ni-A1, kd r-A13 alloys have been measured. From the results for Fe-A1 and Ni-A1, the degree of intrinsic disorder for the equiatomic compounds was calculated2 using equations derived by Wagner and chottk. From the results for Cr-A1 the degree of intrinsic disorder was calculated from equations derived by Orr.' In this paper, the results of the study of Co-A1 alloys are described. Published activity data in the Co-A1 system has been limited to liquid alloys at 1600°C.° A heat capacity study7 of stoichiometric CoAl indicated that a second-order phase transformation occurs at 790° C, attributed to an order-disorder reaction. Oelsen and Middel,' employing the calorimetric mixing of pure liquid metals, obtained heats of formation for compositions from 6 to 90 at. pct Co. Heats of formation for 50 and 78 at. pct Co alloys have also been measured by acid solution calrimetr. The Co-A1 phase diagram, as compiled by Hansen and Anderko,lo is in good agreement with more recent X-ray evidence. The method for measuring activities of aluminum in this study is essentially that employed in the studies of the Fe-1,' i-Al, and r-A13 systems. This isopiestic method entails placing cobalt specimens, in a temperature gradient, in a sealed alumina system containing a pure liquid aluminum source of fixed vapor pressure. The specimens are equilibrated, cooled to room temperature, and their final compositions determined. From the measured temperature of the specimens and the known vapor pressure of pure aluminum the activities of aluminum in the alloy can be calculated. EXPERIMENTAL PROCEDURE The cobalt was 3-mil-thick sheet of 99.9 pct purity (herritt Gordon Mines Ltd., anada). The major impurities were 0.1 pct Ni, 0.014 pct C, 0.018 pct Fe, 0.004 pct S, and 0.005 pct Cu. The aluminum metal had a purity of 99.99 pct (Aluminum Corp. of America) and all alumina parts were 99.7 pct A1,O3 (Triangle RR Grade, Morganite Refractories, Inc.) with major impurities 0.05 pct SiOz, 0.1 pct Fe203, 0.2 pct NazO, and 0.05 pCt K20. Runs 1 to 3 were made with annular cobalt specimens (12 mm ID by 21 mm OD) punched from the sheet. The specimens were deburred and degreased in carbon tetrachloride and in acetone. The samples, each weighing about 150 mg, were then positioned along an alumina rod, a in. OD by 14 in. long, separated by alumina spacers, i in. ID by | in. OD by & in. long. The lower end of the rod was placed in a hole drilled in the center of an 80-g aluminum cylinder. This assembly was put into an alumina crucible, 1+ in. ID by 13 in. OD by 3+ in. high, and the position of each sample was measured to within 50.5 mm relative to the bottom of the crucible. An alumina tube, 28.5 mm ID by 35.5 mm OD by 14 in. long, closed at the top, was slipped over the whole assembly, so that it fitted snugly into the bottom crucible. The entire reaction assembly was tied with molybdenum wire and lowered into a mullite tube, closed at the bottom. A quartz thermocouple tube, closed at one end, containing a t/Pt-10 pct Rh thermocouple, calibrated according to the specifications of the National Bureau of standards,'' was placed along the reaction assembly inside the mullite tube. The temperature of each specimen could be determined by gradually raising the thermocouple and measuring the temperature gradient along the reaction assembly. The combined error in temperature measurement and sample position resulted in a total error of Q°C in the recorded temperature of each sample. The mullite tube was sealed at the top by a water-cooled brass head, connected to a conventional glass vacuum system. The aluminum reservoir is heated to its melting point sealing the alumina system containing the samples. During this process the pressure is maintained below 0.01 li Hg. During subsequent heating to establish the proper temperature gradient and throughout the entire run the pressure is maintained below 2 1 Hg by means of a two-stage mechanical pump. Equilibration runs lasted from 4 to 6 weeks and were terminated by air cooling. The temperature of the liquid aluminum reservoir was brought below its melting point in less than 20 min. For runs 4 and 5, alloy buttons with 49 and 69 at. pct A1 were prepared from the initial high-purity metals by arc melting under purified argon. The alloy buttons were comminuted to powder with an alumina mortar and pestle until the powder passed through a 400-mesh screen, particle size 0.0014 in. Portions of this powder weighing between 50 and 200 mg were placed in small alumina trays, 25 by 15 by 5 mm, which were then

Jan 1, 1969

By J. A. Lund, A. M. Lawson

THE structures of quenched eutectoid and hypereu-tectoid Fe-Cu alloys have been examined by X-ray diffraction and by optical and electron microscopy. The relevant portion of the Fe-Cu phase diagram is given in Fig. 1. Several values have been reported for the solubility of copper in a Fe at the eutectoid temperature, including 1.4 wt pct by orton' and 2.13 wt pct by Wreidt and Darken.2 Alloys containing 4.8 and 7.5 wt pct Cu have been prepared from two batches of Ferrovac E iron (0.005C and 0.013C) and electrolytic tough pitch copper (99.90 Cu). Specimens of dimensions 0.8 by 0.8 by 0.1 in. were cut from hot-rolled material, austenitized, and quenched into brine at 25°C. Similar specimens were also cooled in the furnace, after a short soaking treatment at 1100°C, at a rate estimated to be 10°C per min in the temperature range of 900" to 500°C. X-ray diffractometry was performed on quenched and on furnace-cooled bulk specimens using iron radiation. Only a bcc phase could be detected in all samples. Lattice parameters were calculated from measurements on four lines, made up of two resolved high-angle doublets. Comparisons were made against a silicon standard. Results are shown in Table I. Based on X-ray diffraction studies of a series of alloys of lower copper concentrations, orton' estimated that the tattice constant of a Fe at 25°C increases 0.0014A per wt pct Cu in solution. Extrapolating Norton's data, it may be concluded that all copper was retained in solution in the brine-quenched 4.8 pct Cu alloy, and that approximately 5 pct Cu was also held in solution on quenching the 7.5 pct Cu alloy. Typical microstructures of brine-quenched specimens, as observed by optical microscopy, are shown in Figs. 2 and 3. Precipitation of the E phase (copper-rich) occurred along the y grain boundaries on quenching the 7.5 pct Cu alloy, rendering them readily detectable in the microstructure, Fig. 3. The original boundaries in the 4.8 pct Cu specimens were gener- ally not discernible, however. This indicates that the z phase which was seen in the higher-copper alloy was probably of proeutectoid origin. Thin foils for transmission electron microscopy were obtained from bulk specimens by spark machining to 0.006 in. thickness, followed by electrolytic polishing. Typical transmission electron micrographs

Jan 1, 1967

By R. L. Dietrich

Magnesium alloy sheet has less ability to accept bending at room temperature than most of the heavier metals. In work designed to improve the bend properties, the preferred orientation of the sheet is of major importance as it is in all studies of the properties of wrought magnesium products. When rolled into sheet, all of the common magnesium alloys form an orientation texture having the basal (002) planes approaching parallel to the surface of the sheet. This texture is only slightly affected by annealing. Magnesium single crystals are highly anisotropic, and, as might be expected, so are magnesium alloy wrought products in which a strong preferred orientation is developed. It is therefore not surprising that bend properties are affected by orientation. Ansel and Betterton1 reported that the orientation of AZ3lXt sheet varies from surface to center and that bend properties are improved by etching away the sharply oriented material at the surface of the sheet to reach the more broadly oriented structure below. This paper covers a study of that orientation, either during the rolling process or by treatment of the finished sheet, in an effort to improve the bend properties and toughness of sheet. Literature The orientation texture of magnesium and magnesium alloy sheet has been studied extensively. Early determinations2 showed that pure magnesium sheet has a preferred orientation in which the basal planes are parallel to the sheet surface within very narrow limits. J. C. hIcDonald3 and J. D. Hanawalt4 reported that sheet containing a small amount of calcium develops a "double" texture, that is, the majority of the basal planes are a few degrees from parallel to the surface and there is a noticeable vacancy at the parallel position. Bakarian5 made careful quantitative pole figures of both pure magnesium sheet and MI alloy SEPTEMBER 1949 sheet which show these features. In all of these studies, however, the orientation was determined by transmission methods in which the resulting pattern is an average through the thickness of the sheet. The tendency of wrought metal to exhibit a different orientation at the surface from that in the center has been reported by many investigators. G. von Vargha and G. Wasserman6 found that with copper, aluminum, iron, and brass the textures of rolled compared to drawn wires were the same at the center but differed markedly at the surface. It was also reported by investigators7 that the orientation of rolled aluminum varies from surface to center. Har-greaves8 found that the surface texture of AM503 (magnesium alloy similar to MI) sheet was different from the center texture. It is reported by Edmunds and Fuller9 that zinc alloy sheet sometimes had a thin layer at the surface with a strong orientation of the basal planes parallel to the surface, which, if present, impaired the bend properties of the sheet. Part1 Surface Orientation ofMag- nesium Alloy Sheet and the Effect on Properties Attempts to correlate the bend properties of magnesium alloy sheet with tension ductility over short gauge lengths proved unsuccessful and the subsequent investigation showed that nonuniformity in orientation is a con- tributing factor as the properties of the surface material have a much more important effect in bending than in tension. A program to study the relationship between surface orientation at the surface and bend properties was then undertaken. First, the effect of etching away the surface of sheet on the bend properties and the orientations at the various depths were studied. Sheet samples of M1, AZ31X, and AZ61X were etched in dilute nitric acid to remove the surface material for various depths to 0.015 in. As may be seen in Table 1, the minimum bend radius improved considerably as the surface layers were etched away but it was necessary to etch the sheet quite deeply, much more so than was found necessary by Edmunds and Fuller9 on zinc sheet. It is also apparent that the amount of etching required is a function of the sheet thickness. In all of this work, radii were measured as R/t, the radius divided by the sheet thickness, in order to eliminate the effect of the reduction in sheet thickness produced by the etching. To determine the orientation texture of the sheet, X ray reflection patterns were taken using copper radiation with the bearn striking the specimen at an angle of 17' to the surface, which is the Bragg angle for the (002) planes of magnesium. Two exposures were made of each specimen, one with the beam perpendicular to the rolling direction and the other with the beam parallel to the rolling direction. The symmetry of the preferred orientation in magnesium sheet is such that these two photographs gave an approximation of the pole figure sufficiently accurate for qualitative work and it was not thought worthwhile to make complete pole figures. These X ray patterns show that the orientation has a much narrower spread at the original surface of the sheet than below the surface. The narrow spread is found in sheet having the majority of the basal planes (002) parallel to the surface, and since this is an unfavorable position for slip, it is

Jan 1, 1950

By S. G. Proctor, D. L. Baaso, W. V. Conner

A double crucible system was developed for I-g scale plutonium reductions. The equipment consists of an inner MgO crucible, an outer MgO crucible, and a stainless steel pressure vessel. The reduction charge is PIaced in the inner crucible and the annulus between the inner and outer crucibles is filled with a mixture of calcium and iodine. The exothermic reaction between the calcium and iodine in the annulus supplies the heat required for complete reaction of the reduction charge ana' good metal coalescence. Metal yields of 80 to 85 ,pct were obtained from I-g scale reductions and yields as high as 97.5 pct were obtained from 0.5-g scale reductions. The system was used to reduce charges containing as little as 0.1 g of Pu resulting in metal yields up to 90 Pct. THIN metal foils of highly enriched plutonium isotopes are used as targets for cross section and other measurements. The isotopes are separated in the calutrons at Oak Ridge and are very expensive to prepare. Often, only 1 or 2 g of material are available thereby emphasizing the need for a method of preparing these small quantities of metal. Procedures for 1-g scale plutonium reductions have been described, but these procedures require elaborate or expensive equipment. For example, the procedure described by Anselin et al.1 requires an inert atmosphere glovebox and induction heating equipment. The procedure described by Baker2 also uses induction heating equipment to obtain the recommended heating rates and liner temperatures. Baker's procedure also requires high purity PuF4 with very little PuO2 present. The procedure described in this paper resulted from a search for a simple and inexpensive method for making 1-g scale plutonium reductions. EXPERIMENTAL Equipment. The equipment required for the double crucible system consists of a pressure vessel, two MgO crucibles, a MgO crucible lid, and a resistance-heated, vertical crucible furnace. The crucibles were slip cast from high purity MgO and were supplied by the Coors Porcelain Co. and the Norton Co. The pressure vessel and lid were fabricated from 316 stainless steel. Materials. The PuF4 used for this study was obtained from the P1utoniu:m Metal Production Department at Rocky Flats. The PuF4 was prepared in a con- tinuous hydrofluorinator by reacting Pu02 with HF at 650°C. The isotopic composition of the plutonium was approximately 93 pct 239PU, 6 pct 240PU, and 0.5 pct 241PU. Some of this PuF, contained less than 1 pct Pu02 (Batch No. 6 and 7), while other batches contained up to 15 pct Pu02 (Batch No. 3). The chemical analyses of all the PuF4 used for this study is given in Table I. The calcium was 99 pct pure, AEC grade, and only that fraction which would pass through a 20 mesh screen was used. The I2 was USP grade re-sublimed I2 which was ground before being used. Procedure. Various charge compositions and methods for loading the double crucible system were tested. The optimum conditions for 1-g scale reductions are described below. The double crucible system was loaded as shown in Fig. 1. The outer crucible was placed in the pressure vessel and the annulus between them was filled with MgO sand. The inner crucible was placed in the outer crucible, supported by a layer of MgO sand in the bottom of the outer crucible. A mixture of 5.2 g of Ca and 25 g of I2 was placed in the annulas between the two crucibles. The upper portion of the annulas was filled with MgO sand. Next, a layer of a mixture of calcium and I, equal to 20 wt pct of the calcium and I2 used in the main charge was placed in the bottom of the inner crucible. The PuF, to be reduced was mixed with a 30 pct excess of calcium and 1 mole of I2 per mole of Pu and this mixture was placed in the inner crucible. The charge was topped with a layer of a mixture of calcium and I2 equal to 20 wt pct of the calcium and I2 used in the main charge. The pressure vessel was sealed with a flat copper gasket and was purged by alternately evacuating and filling with argon. The purge valve was closed and the vessel was placed in a vertical crucible furnace which was preheated to 950°C. The furnace was turned off after 20 min of heating and the vessel allowed to cool. Experience has shown that. this amount of heating is sufficient to assure complete reaction of the charge. RESULTS AND DISCUSSION The double crucible system has been used to produce plutonium metal on a 0.1- to 1-g scale. Reduction

Jan 1, 1970

By Albert D. Brokaw

The accompanying charts are presented to extend and improve a chart published under the title "A Chart to Provide Approximate Correction for Temperature and Deviation from Boyle's Law."' The applicability of this earlier chart was limited by the fact that it was based on the work of Burke and Keyes² and Kvalnes and Gaddy3 whose experiments were conducted with pure methane, the adjustments suggested for natural gases of higher specific gravity were unsatisfactory except within limited ranges of temperatures and pressures, and precise interpolation was difficult. The extensive work of G. G. Brown, D. L. Katz and their associates on the heavier natural gases has provided better bases for the needed corrections, and the present charts. which are based largely on their work, are intended to simplify the computations involved. The design of the charts has been changed by plotting temperatures as a function of pressure and correction factor, on a semilogarithmic or "ratio" grid, which gives fairly even spacing of the graphs and simplifies interpolation. Charts have been prepared for natural gas with specific gravities of .60, .65, .70, .75 and .80. The standard computation for use in estimating the quantity of gas in a reservoir may be expressed as follows: _ PA X 520 X VR ZT where: Q is the volume of gas at 60°F and one atmosphere pressure PA is the absolute formation pressure in atmospheres

Jan 1, 1949

By Albert D. Brokaw

The accompanying charts are presented to extend and improve a chart published under the title "A Chart to Provide Approximate Correction for Temperature and Deviation from Boyle's Law."' The applicability of this earlier chart was limited by the fact that it was based on the work of Burke and Keyes² and Kvalnes and Gaddy3 whose experiments were conducted with pure methane, the adjustments suggested for natural gases of higher specific gravity were unsatisfactory except within limited ranges of temperatures and pressures, and precise interpolation was difficult. The extensive work of G. G. Brown, D. L. Katz and their associates on the heavier natural gases has provided better bases for the needed corrections, and the present charts. which are based largely on their work, are intended to simplify the computations involved. The design of the charts has been changed by plotting temperatures as a function of pressure and correction factor, on a semilogarithmic or "ratio" grid, which gives fairly even spacing of the graphs and simplifies interpolation. Charts have been prepared for natural gas with specific gravities of .60, .65, .70, .75 and .80. The standard computation for use in estimating the quantity of gas in a reservoir may be expressed as follows: _ PA X 520 X VR ZT where: Q is the volume of gas at 60°F and one atmosphere pressure PA is the absolute formation pressure in atmospheres

Jan 1, 1949