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By Woolf, W. G.

Filtration of hot (60°C) supersaturated zinc sulphate solution (sp gr 1.540) from slimy leach residues at the electrolytic zinc plant of Sullivan Mining Co., Kellogg, Idaho, is de- scribed. Separation of liquids and solids in the finished leach is by Burt filters modified to meet conditions of high-acid, high-density process for electrolytic zinc. Operating characteristics of the Burt filter on this pulp are presented.

Jan 1, 1950

By Arthur R. Kommel, Robert F. Mehl, Gerhard Derge

The orientation relationships resulting from allotropic transformations and the formation of segregate structures in metals and alloys have been the subject of the eight earlier papers in this series'. A brief summary of orientation studies has also been given by Sachs2. A survey of these papers discloses that the factors that determine the orientation relationship of a precipitated phase to its parent solid solution, as well as the outward form and appearance of the new phase, are not completely understood. It is now evident that crystallographically analogous systems, as a rule, exhibit the same type of Widmanstatten figure and orientation relations, so that useful information is not to be expected from examination of a new alloy involving lattice combinations of which the orientation relationships are already known. Therefore, the determination of the relations existing between lattice types that have not already been studied seems to be the most promising mode of attack upon the problem; both of the systems reported in this paper represent new combinations of lattice types. A. The Mg-Mg2Sn System The magnesium-tin equilibrium diagram given by Hansen3 shows the phase Mg2Sn to be the only intermediate phase. The solid solubility of Sn in Mg decreases from 14.8 weight per cent at the eutectic temperature, 561' C., to 2.3 per cent at 450°, while no solid solubility of Mg in Mg2Sn has been observed. The crystal structur: of Mg is close-packed hexagonal with a0 = 3.202 A. and co = 5.199 A.4, while Mg2Sn is of the CaF2 type with a. = 6.78 A., with four molecules in a unit ce115,6. Alloys from two different sources have been used: (1) those supplied by the Dow Chemical Co., which contain 6 and 8 weight per cent Sn, and (2) those prepared in this laboratory, containing 8 and 13.5 per cent Sn. The latter were made from Dow high-purity Mg and Baker chemically

Jan 1, 1937

By T. J. Smolik, Harman, D. W. Fuerstenau

By means of electrokinetic measurements, the surface properties of the aluminosilicate polymorphs (sillimanite, andalusite, and kyanite) and also mullite have been found to depend on the ratio of A10 bonds to SiO bonds in the surface. The Al-toSi ratio in the surface is dependent upon the crystal lographic properties of the mineral, which in turn determine coordination numbers of A1 and of Si, cleavage characteristics, and density of the various solids. Mullite with a greater bulk Al-toSi ratio has the highest zpc of the aluminosilicates. By treatment in dilute acids or by cycling between acidic and basic solutions, alumina is selectively dissolved from the surface of these orthosilicates. This shifts the apparent zpc to lower pH values as the fraction of SiO groups in the surface increases. Thus, surface properties can be altered by procedures that alter the A l-to-Si ratio in the surface. Flotation of these aluminosilicates results from electrostatic interaction of the collector ions with the mineral surfaces. As a result, flotation response shifts in accord with any shift in apparent zpc by pretreatment. Separation of minerals by flotation is based on differences in the physicochemical properties of their surfaces.'-3 For many minerals, adsorption of flotation collectors results from their functioning as counter ions in the electrical double layer at solid-water interface. In such systems, separation depends on differences in the zero point of charge (zpc) of the various minerals. The zpc is defined as the concentration of potential determining ions in solution at which the surface is uncharged. The potential determining ions for inorganic oxide-water interfaces are hydrogen and hydroxyl.4,5 This work is concerned with the effects of crystal structure, composition, and surface preparation on the surface properties and flotation behavior of aluminosilicates. Differences resulting from crystal structure were studied by measuring electrokinetic potentials and determining the flotation behavior of three different aluminosilicate materials having the same chemical composition (Al2O3 SiO2), namely andalusite, kyanite, and sillimanite. Furthermore, the effect of the Al2O3-to-SiO2 ratio on flotation behavior and surface properties was investigated by including synthetic mullite, 3A12O3 .2SiO2. Gaudin and co-workers 6,7 have clearly shown how crystal structure determines the native floatability of certain minerals. Those solids in which the surface is comprised mainly of broken residual bonds possess naturally hydrophobic surfaces. It was found by Bakakin8 that for a number of oxidized lead minerals, differences in floatability were due to the distance of Pb atom from the surface. Only limited work has been done on relating electrical properties of surfaces to crystal structure and composition. Healy et. a1.9 found that the zero points of charge of various manganese dioxides ranged from about pH 1.5 to pH 7.5, and these differences in the zpc's were interpreted in terms of the atomic packing in the various crystals. The research presented here clearly shows that crystal structure and chemical composition do affect the surface properties of aluminosilicates and, in addition, that these effects can be altered by changing conditions under which the surfaces are prepared. CRYSTAL STRUCTURE OF THE ALUMINOSILICATES Sillimanite, andalusite, and kyanite are composed of regionally metamorphosed rocks differing mainly in degree of metamorphism. All three minerals have the same chemical composition, Al2O3 - SiO2, of which sillimanite is the high temperature polymorph and kyanite and andalusite the lower temperature polymorphs. Andalusite and sillimanite crystallize in the orthorhombic system while kyanite crystallizes in the triclinic system. The structure of these three minerals is essentially chains of aluminum-oxygen octahedra linked laterally by silicon and aluminum. The arrangement of these chains in the three minerals is shown in Fig. 1.l4

Jan 1, 1967

By R. V. Higgins

This paper presents a computer method to obtain the shape factors and equal cell volumes of the channels for any well spacing pattern from a potentiometric model. By using this program the authors have processed the data for the seven-spot, direct line-drive and the staggered line-drive patterns. The data for the five-spot pattern had been previously processed by a noncomputer method and are included for completeness. The shape factors and volumes for the channels are presented in tables for those who want to use them to process data using their own permeability relationships and viscosities of their reservoir oils. The authors have used the data and sets of representative permeability curves to process sample calculationr of waterflood performances. The comparison of the calculated results shows that the influence of well spacing is small. The permeabilities of the reservoir rock to oil and water had a greater influence on oil recovery for a given pore-volume throughput of water than the well spacing pattern. The more water-wet the reservoir rock, the better the possibility of permeabilities which are conducive to good recovery. The viscosity of the reservoir oil also influences the recovery more than the well spacing pattern. The reduction in the percentage recovery of oil with increase in viscosity of the reservoir oils is small when oil viscosities are in the range of 0.1 to 3. Above this range the reductions in recoveries are extensive. Sample comparisons of the time required for different patterns to recover the oil are presented. Results of an example calculation are given to show the effect of the permeability profile on recovery. INTRODUCTION The effect of well spacing pattern on the recovery of oil when flooding with either gas or water has been studied by many investigators. Muskat et al.1 presented an analysis using conductivity, sweep efficiency and unit mobility to the time of breakthrough. Dyes et al.2 used experimental techniques (X-ray shadowgraphs) and different mobility ratios. They presented quantitatively the relationship between mobility and sweep efficiency at and after breakthrough. Hauber3 presented a method to predict waterflood performance for arbitrary well spacing patterns and mobility ratios. Craig et al.,4 using techniques similar to Dyes et al. to determine sweep efficiency for a five-spot pattern, added the use of relative permeability curves at breakthrough and thereafter. Douglas et al.5 sed rela- tive permeabilities and continuously changing saturations throughout the entire five-spot flood pattern. In obtaining their solutions they used finite-difierence equations. Hig-gins and Leighton6,7 also used relative permeabilities and continuously changing saturations throughout the pattern before and after breakthrough. They employed techniques that process a flood-pattern calculation on the computer in about one minute. The methods of Douglas et al. and Higgins and Leighton both checked closely the laboratory results for a wide range of mobility ratios. This paper presents some sample performances calculated by the Higgins and Leighton method that show the effect on recovery of different permeabilities and viscosities using the seven-spot, the line-drive and the staggered line-drive, as well as the fivespot flood pattern. No previous paper has presented these data using different permeability curves and continuously changing saturations throughout the flood patterns. The paper also presents (1) the results and analyses of the flood-pattern prediction, (2) the computer techniques for determining the shape factors and volumes from the potentiometric models for the foregoing flood patterns, and (3) the shape factors and volumes of the channels of the flood pattern in the event reservoir engineers may like to process waterflood calculations using their own permeability curves and reservoir oils. DESCRIPTION OF METHOD VOLUMES AND SHAPE FACTORS The use of channels taken from a potentiometric model (see Fig. 1) to aid in calculating the performances of water floods of nonlinear patterns has been thoroughly explained in the literature.0,7 Therefore, very little theory, discussion, or proof regarding this phase will be repeated in this paper. The computer method presented in this paper to calculate the volumes and the shape factors of the channels of potentiometric models employs the trapezoidal rule for the volumes and the Pythagorean theorem (the hypotenuse equals the square root of the sum of the squares of the two sides of a right triangle) for the shape factors. In calculating the volume of a channel, the area of each cell in the channel is determined and then multiplied by the thickness to obtain the volume. In determining the areas of the cells, trapezoids are constructed whose vertical sides are spaced Ax apart, as shown in Fig. 2. The length of the sides is the difference between an ordinate cut off by the top and bottom of the cell — usually equipo-tentials. The coordinates of the points along an equipo-tential or streamline are obtained by Lagrange's8 equation of interpolation for which the constants are coordinate points at the intersections. Three intersections for con-

Jan 1, 1965

By Ellsworth Daggett

THE system of pitwork used with the Cornish pumping engine, and which, for want of a better name, we may call the Cornish system of pitwork, consists essentially of a series of plunger-pumps, situated one below the other, in a shaft or incline, the plungers being operated by a rod called the pitman or pump-rod, which must, therefore, extend from the motor at the surface to the lowest pump. The subject will be best understood by reference to Fig. 1, in which k may be taken as typical of the ordinary plunger-pump, in which S is the suction pipe, u, the lower valve situated in the H piece T; v, the upper valve situated in the valve-box O; I, the mounting-pipe or column through which the water is carried to the surface; L, the plunger-barrel, and P, the plunger working through the stuffing-box, and actuated by the branch rod r, which is attached to the main pump-rod, R. The action of the pump is as follows : On the ascent of the plunger, acting now by suction, the water flows from the reservoir through the valve u, into the barrel, L. On the descent of the plunger, the water is forced up through the valve, v, which acts merely as a check valve, into the pipe, I, through which it is, at each successive down-stroke of the plunger, forced upward until it reaches the next reservoir, from which it is taken by another similar pump, and so on until it reaches the surface or drain-tunnel. The pump is obviously only single-acting, i. e., it acts only during one-half of its entire stroke. The weight of water raised during the up-stroke of the plunger is equal to the weight of a column of water whose base is the area of the plunger and whose height is the mean distance between the plunger-face and the surface of water in the lower reservoir, a distance not usually exceeding 12 or 15 feet, and which obviously cannot under the most favorable circumstances, exceed 25 or 30 feet. The water forced up during the down-stroke is equal to the weight of a column of water whose base equals the area of the plunger and whose height equals the length of the mounting column above the mean position of the plunger-face, say from 150 to 300 feet. Almost all of the useful work, therefore, is done on the de-

Jan 1, 1879

By Charles H. Fulton

THE Engineering Education group began its sessions Tuesday morning, Feb. 16, as a Committee and wound up the day as the Institute's fifth " Division." C.II. Fulton presided. The first paper for discussion was entitled "Teaching Management in Engineering Schools,"' by Eugene McAuliffe, president of the Union Pacific Coal Co., space for which may be found later in these pages. In it, Mr. McAuliffe argued that an engineering student should be taught the knowledge of men, much as a medical school teaches surgery. He then went on to indicate, out of the wealth of his administrative experience, the problems an executive needs to be equipped to handle, and said that every student engineer should look on himself as a potential manager.

Jan 1, 1932

By R. Woods

INTRODUCTION Gaudin (1), considered that "the mechanism of mineral collection is the central problem of flotation theory". From their work on adsorption phenomena in flotation for more than fifty years (2), Gaudin and his co-workers have made major contributions to the elucidation of this mechanism, a fact acknowledged by their contemporaries in the field (e.g. (3)). Their investigations in a number of areas, e. g. demonstrating that submonolayer quantities of adsorbed collector species can induce flotation, or identifying the influence of substances which can activate or depress (1), have helped to provide the basis for and the development of a theory to account for the interaction between mineral and collector. It was established in the late fifties (4) that the presence of oxygen is a prerequisite for the flotation of metal sulfides with thiol collectors. This fact rendered inadequate the concept of simple ion adsorption being responsible for rendering these minerals hydrophobic. The requirement for oxygen has been explained (1) in terms of this species being a component in chemical reactions between the sulfide surface and the collector. Gaudin has been instrumental in identifying the products of chemical reactions at sulfide minerals (1, 5), a line of work which has been continued particularly by Finkelstein and co-workers in South Africa (6). In presenting a detailed mechanism of the mineral-collector- oxygen interaction, it has often been considered that the mineral surface [must] first be oxidized to a metal oxy-sulfur species which

Jan 1, 1976

By Joseph E Pogue

Over a period of years the writer has presented a number of studies1 on various aspects of proration, in a progressive attempt to analyze critically and constructively the economic complexities of this interesting institution, which in a decade has revolutionized the economics of oil production in the United States. In the course of the investigations leading to these papers, the changing nature of proration and the principles underlying its evolution have gradually become clear, so that it is now possible to depart from the analytical method and to construct a synthesis of the steps that, if furthered by the industry, should carry proration past the economic hazards that still surround it to the goal of maximizing the value of the petroleum resource to the industry and the public alike. Nature of Proration Proration literally means the allocation of demand among competing producers on a pro rata basis, but the term now carries a much broader significance for it is employed to describe the entire process by which the production of crude oil in the United States is regulated. There is naturally much confusion of thought on the subject, for proration is an evolving system of control based upon principles of conservation and equity and embracing a body of practices that are tending to adjust themselves to the needs of the situation but are subjected to varying and divergent influences in the process. As it is now constituted, proration is a planned production measure designed to prevent waste, insure ratable takings, and balance supply and demand. The procedure is administered by State regulatory bodies through use of the police power of the States under authority of State conservation laws; the practice is supported by a considerable degree of voluntary conformance on the part of operators; and the Federal Government has accorded its cooperation by providing advisory quotas, circumscribing imports, checking movements of hot

Jan 1, 1939

By Joseph E. Pogue

Over a period of years the writer has presented a number of studies1 on various aspects of proration, in a progressive attempt to analyze critically and constructively the economic complexities of this interesting institution, which in a decade has revolutionized the economics of oil production in the United States. In the course of the investigations leading to these papers, the changing nature of proration and the principles underlying its evolution have gradually become clear, so that it is now possible to depart from the analytical method and to construct a synthesis of the steps that, if furthered by the industry, should carry proration past the economic hazards that still surround it to the goal of maximizing the value of the petroleum resource to the industry and the public alike. Nature of Proration Proration literally means the allocation of demand among competing producers on a pro rata basis, but the term now carries a much broader significance for it is employed to describe the entire process by which the production of crude oil in the United States is regulated. There is naturally much confusion of thought on the subject, for proration is an evolving system of control based upon principles of conservation and equity and embracing a body of practices that are tending to adjust themselves to the needs of the situation but are subjected to varying and divergent influences in the process. As it is now constituted, proration is a planned production measure designed to prevent waste, insure ratable takings, and balance supply and demand. The procedure is administered by State regulatory bodies through use of the police power of the States under authority of State conservation laws; the practice is supported by a considerable degree of voluntary conformance on the part of operators; and the Federal Government has accorded its cooperation by providing advisory quotas, circumscribing imports, checking movements of hot

Jan 1, 1939

By A. L. Mincher, W. F. Sheely

Mechanical properties of columbium have been studied over the temperature range of -196 to 1093oC. The decreased strengthening influence of cold-work at temperatures below ambient has been interpreted in terms of the Peierls-Nabarro effect. Maxima in the rate of strain hardening observed during tensile testing in the range 250-600°C. have been correlated with interstitial impurities to indicate the temperature ranges at which carbon, oxygen, and nitrogen, respectively, are responsible for strain aging. THE growing need for structural materials for use above the useful service temperatures of the iron-, nickel-, or cobalt-base alloys has caused the refractory metals to be considered as potential engineering materials. These metals, which include columbium, tantalum, molybdenum, and tungsten, are called refractory because the lowest melting point among them,that of columbium, is about 1000°C higher than the average melting temperatures of conventional high-temperature alloys. They are all body-centered cubic transition metals and, as such, their mechanical properties have basic characteristics which distinguish them from the face-centered cubic metals. For example, all show a much steeper rise in strength with decreasing temperature below room temperature than do the face-centered cubic metals, and their mechanical properties are strongly influenced by interstitially dissolved impurities. In order that these new metals may be used efficiently, it is necessary that their characteristics of behavior be fully known. In this paper, the mechanical properties of columbium will be examined over a wide range of temperatures. In particular, the influences of cold-work and individual species of interstitial impurity atoms on mechanical properties will be described, and basic mechanisms which may control the observed characteristics will be explored. EXPERIMENTAL The material used in this investigation was Union Carbide Metals Co. columbium roundels consolidated to four 4-in. diam ingots, three by consumable-electrode arc melting and one ingot by electron beam melting. Impurity contents of the ingots and methods of ingot conversion and treatment are summarized in Table I. The only metallic impurity occurring in any significant quantity was tantalum at about 0.1 pct. Iron, silicon, titanium, and zirconium were each less than 0.015 pct; boron was 1 ppm or less. This should have no appreciable influence on properties. The electron beam melted material, being the purest, will be used as the basis for comparison in the discussions to follow. Tensile tests were conducted from-196 to 1093oC, on both cold-worked and fully recrystallized arc-melted and electron-beam melted columbium using standard 1/4-in. diam, 1-in. long gage length test specimens. A strain-rate of 0.005 in. per in. per min was employed until the 0.2 pct yield strength was achieved and then the strain-rate was increased to 0.05 in. per in. per min for the balance of the test. Samples were protected in an inert atmosphere at tests above 300°C. The tensile properties obtained on the electron-beam melted columbium, E, in both the cold-swaged and recrystallized conditions are given in Fig. 1. The yield strength data of Dyson, et al.,' obtained on recrystallized electron beam melted columbium and the tensile strength data reported by Tottle2 on powder metallurgy columbium are included in Fig. 1. The material used by Tottle had been purified by vacuum sintering. There is excellent agreement between Dyson's data and those obtained in the present investigation. The tensile strengths obtained by Tottle were slightly greater than those obtained in this investigation on electron-beam melted columbium but varied with temperature in a similar manner. Tottle's data showed a maximum in tensile strength near 500°C, as did our data on electron-beam melted material, and also showed a small maximum at 300°C. The significance of these maxima will become evident later in the discussion. The tensile properties of cold-swaged and recrys-tallized arc melted columbium are plotted in Fig. 2. It was found that the properties of the recrystallized arc-melted columbium from all three heats showed very close agreement except at temperatures between about 500" and 800°C. A reason for this range of disagreement will be suggested in the discussion. The generally good agreement, however, attests to the ability of cold-working and subsequent recrystal-lization to erase the effects of the three different primary breakdown procedures and to produce nearly equivalent structures in the samples derived from the three different heats. wesse13 reported tensile data on columbium having interstitial impurity contents between those of the

Jan 1, 1962

By John H. Hollomon

A REVIEW of the steps which have been made to increase knowledge in the field of ferrous physical metallurgy during the closing period of World War II brings both pleasure and disappointment. Contributions of great value have been made, to be sure. However, due partly to the stress of the times, researchers in this field have been in the main directing their attention toward the short-range problems involved in the development and production of materiel for war. Furthermore, publication of the results of a great number of studies has had to be delayed. Much of the German work may, indeed, be lost entirely, owing to the efficiency of our bombers, which managed to account for most of the famous Kaiser Wilhelm Institut of Dusseldorf, not to mention the other large laboratories and manufacturing plants throughout that country. It would seem safe to assume, however, that fundamental research in Germany had been forced to give way to the shallow, but more pressing, engineering problems of a country trying to avoid defeat. In Russia the picture has been clouded by the limitations imposed upon comunication; but this much does seem clear: Russia alone among the great nations of the world has maintained her long-range view and has continued to foster research of the most fundamental type. English workers; on the other hand, appear to have been able only to meet the demands of the pressing problems of war, and their studies have been of the short-range variety. That metallurgical research of any sort should have continued in France during this chaotic period in her history would seem impossible, but, amazingly, a small handful of scientists did manage to carry on their work, and it is to be hoped that more will be heard from them in the future.

Jan 1, 1946

By B. S. Hickman

Using primarily quantitative single crystal X-ray techniques studies have been made of the precipitation of the metastable w phase in alloys of titanium with Mo, Mn, Fe, Cr, and Nb. It is shown that, in agreement with earlier work on the Ti-V system, the composition of the w phase during aging approaches a constant; the value varies from one system to another in a systematic manner with the electron concentmtion. Results relevant to the mechanism of w precipitation during quenching and during aging are presented and discussed. Results are presented to confirm that the w phase is coherent and the nzorphology of the Necipitates is described and discussed. PRECIPITATION of the metastable w phase in alloys of titanium is of interest because of its severe embrittling effect and also because of the enhancement of the superconducting properties which accompanies precipitation.1 The general features of w phase precipitation have been discussed by cuillan and by Bagaratskii et d3 The work described in this paper forms part of a general study of w phase precipitation which was undertaken to elucidate various unknown or controversial features of the process, namely: i) What is the mechanism of formation of the phase ii) How does its composition, morphology, volume fraction, and particle size vary with the type and content of the alloying element and with the heat treatment conditions? iii) What is the relation between the w phase and the equilibrium a phase? In a previous paper4 the results of a detailed study of w phase in Ti-V alloys were presented. It was shown that: U During aging the composition of the w phase approached a saturation value of 13.5 to 14.0 at. pct V. ii) w precipitated as cube shaped particles and once precipitation was complete, particle coarsening did not occur. iii) a phase formed initially by direct conversion of w-phase precipitates. In this paper similar measurements are reported on Ti-Mo alloys and some more limited data given on the Ti-Cr, Ti-Fe, Ti-Mn, and Ti-Nb systems. The results i.1 the six systems are then compared. It has been shown previously by electron microscopy that the w precipitates as ellipsoids in both the Ti-Nb system,&apos; and in i-o.&apos; Blackburn and williamsz3 have reported the precipitates in Ti-Fe, Ti-Cr, and Ti-Mn are cubic, i.e., similar to the Ti-V system.476 EXPERIMENTAL METHODS 1) Specimen Preparation. Samples of the compositions shown in Table I were prepared by arc melting. High purity electron beam zone refined titanium (Materials Research Corporation Grade I—total impurity content =250 ppm) was used; the other source materials are given in the table. A commercial Ti-8 wt pct Mn alloy was used for studies of this system. After homogenization the materials were rolled or cut into strip approximately 1/4 in. by 2 in.; the strip was then heated at temperatures of 1200" to 1300°C for several hours by passage of a direct current through the strip in an ultra high vacuum system (<10-torr) and then quenched by admitting high purity helium and switching off the current. This treatment resulted in crystals up to 2 in. by 2 in. by A in., almost all of which had a [100] direction nearly perpendicular to the plane of the strip. The crystals were cut from the strip by spark machining and their composition checked by lattice parameter measurements supported by chemical analysis. 2) X-Ray Diffraction Methods. Lattice parameter measurements were made using a modification of the single crystal spectrometer described by ond. In this technique the crystal angles for reflection on either side of a highly collimated primary beam are measured. Generally the 400 CuK, or the 400 CuKp reflections of the bcc lattice were used. In the as-quenched crystals a precision of 1 in 105 was obtained, but due to line broadening the parameters in aged materials could only be measured to 1 in lo4. This accuracy was, however, quite adequate for the purposes of these experiments and enabled the composition of the p phase to be obtained to 10.1 pct in all systems except Ti-Nb where the lattice parameter change with composition is very small. The precipitation and growth of the w phase was examined using a single crystal goniometer attached to a Phillips diffractometer. The relative intensities and line shapes of b-phase and w-phase reflections

Jan 1, 1970

By John Wulff, J. H. Hollomon

THE opinion has been widely held that the corrosion of alpha brass occurs by the selective solution of zinc. As late as 1939, Fink1 and Evans2 suggested that in the initial stage of the corrosion the selective solution of zinc produces copper-rich areas, which subsequently act as cathodes that facilitate the deposition of copper. Previously Abrams3 had shown that most of the copper found on corroded brass was redeposited and not residual, although he did not consider the nature of the initiation of the corrosion process. Enough data exist to indicate that any metal surface is sufficiently heterogeneous to provide the anodes and cathodes necessary for the initiation of corrosion.4,5 Thus, for alpha brass we need postulate not an initial selective solution of zinc, but only the existence of local differences in electrochemical potential. The heterogeneity responsible for potential differences may arise from oxide and other films as well as from alloy concentration gradients. Even though selective corrosion may be possible in some alloy systems, previous data on alpha brass as well as the experimental work reported in this paper do not require this supposition. Bengough and May,6 in a discussion of Abrams&apos; paper, first suggested the addition of small amounts of arsenic (0.03 per cent) to alpha brass to prevent the redeposition of copper (dezincification). This suggestion was later substantiated by Nixon.7 In their studies of the inhibiting influence of arsenic, Evans and Fink were led to the selective-solution hypothesis in order to explain the initial corrosion of such alloys. They believed that an arsenic film covered anode areas and prevented the formation of copper-rich spots capable of acting as cathodes for the deposition of copper. They did not consider, however, the mechanism by which the arsenical film was formed. Bengough and May,8 in another publication, suggested that the commonly found gray or black arsenical film may act to: (I) carry oxygen to the brass surface, (2) increase the discharge potential of copper on brass, (3) precipitate cuprous chloride from colloidal suspension in chloride solutions. Masing9 assumed that the film found upon arsenical brass was metallic arsenic. His measurements of hydrogen overvoltage of bulk arsenic led him to believe that the inhibition of dezincification occurs because the overvoltage of a brass surface is lowered by the arsenic film. He reasoned that this film would permit the more rapid reduction of hydrogen at the cathode, which would prevent the redeposition of copper. In a recent paper,10 we have pointed out that the film formed during the corrosion of arsenical brass and copper in stagnant solutions is essentially arsenious oxide (As203),

Jan 1, 1942

By William P. Blake

Postscript to the paper read by Prof. William P. Blake at the Lake Superior meeting, September, 1904. POSTSCRIPT.*-Since the publication of my paper upon the blackening of the surface of rocks in desert regions, I have noted that similar views of the origin of superficial discoloration in the case of certain rocks from the Salt Lake basin of Utah have been expressed by Prof. George P. Merrill. In the pamphlet, he described the brown-coated weathered boulders from Tooele county, reaching the conclusion that the discoloration was due to the solution of the manganese and iron compounds &apos;in the interior of the boulder, while they were in the water, and the gradual bringing of this material to the surface through capillarity and its oxidation when exposed.

Mar 1, 1905

By K. Mukherjee

A quasi-thermodynamic calculation is presented for estirt~ating vacancy Parameters in fcc metals. For fcc metals the equilibrium vacancy concentration at the melting point can be approximated by a constant mole fraction. The Gibbs free energy of formation of the vacancies can then be expressed as a simple function of the absolute melting temperature alone. From this description the formation energy Ef, the vibrational entropy Sv, and the formation volume of a vacancy can be calculated in terms of known thermodynamic parameters. The calculated values are in good agree-rnent with available experimental results. IT appears that many of the physical parameters associated with lattice defects can be empirically related to thermodynamic melting parameters.&apos;-7 Besides the implicit correlations between melting phenomenon and point defects, the melting temperature itself at atmospheric pressure can be used as a reference temperature for the purpose of comparison of vacancy concentrations in a given crystal class. The concentration at the melting point then corresponds to the maximum vacancy super saturation in the crystalline state at a fixed pressure. For pure fcc metals such as Au, Cu, Al, Ag, Pb, and Pt the mole fraction of vacancies at the melting point8 is of the order of 10*"3 to 10"1. The equation expressing the equilibrium vacancy concentration at the melting point contains three parameters: the formation energy, the vibrational entropy, and the absolute melting temperature, see Eq. [2]. Since these three parameters cover a wide range of values8 in the above-mentioned metals, it can be assumed that in other fcc metals, for which no reliable data are available, the mole fraction of vacancies at the melting point most likely lies in the range 10~3 to lO"4. This is then the basis of the calculations described in this article. Within this range the mixing entropy can be linearized and the vibrational entropy, the formation energy, and the vacancy formation volume can be calculated in terms of known thermodynamic constants. 1} LINEARIZATION OF MIXING ENTROPY The Helmholtz free energy of a crystal containing n vacancies at the melting point can be writteng as where Ef, T,, k, and S, are the formation energy of a vacancy, the absolute melting temperature, Boltz-mann&apos;s constant, and the vacancy formation entropy, respectively. After applying Stirling&apos;s approximation in Eq. [l] and minimizing with respect to n where (n/N), is the equilibrium vacancy concentration in mole fraction at the melting temperature at 1 atm pressure. If instead of setting (6~/6n) = 0 immediately after Stirling&apos;s approximation in Eq. [I], the configurational partition function is simplified, then some useful and significant results can be obtained by utilizing the experimental inforrnation After applying Stirling&apos;s approximation and rearranging is plotted as a function of (n/N) in Fig. 1. The points, not all of which are shown, are fitted by a straight line substituting from Eq. [5] into Eq. [I] and minimizing with respect to n combining Eqs. [6] and [2] It must be emphasized that Eq. [7] is only a crude approximation based on an oversimplified model of

Jan 1, 1967

By William Romanoff

IN AN ARTICLE on "Recovering Smelter Dust and Oxide," published in the Engineering and Mining Journal (Vol. 131, No. 2), the authors briefly described some dust-recovery equipment and its operation at a secondary-metals brass-smelting and refining plant. A description of our experience in overcoming certain operating difficulties may prove of interest or value to those who are confronted with some of the same problems or who should equip their furnaces with dust-collecting equipment. The dust loss from reverberatory smelting and refining of brass con¬sists largely of zinc, with smaller percentages of lead, tin, and copper in the order named. At the Kramer plant, the fume discharge from the two stacks amounted to 3 to 4 tons of solids per day, making a dense smoke. With dust equipment in operation, the discharge from the stacks is invisible and approximately 2500 lb. of zinc and other metals is recovered daily thereby from each furnace operating.

Jan 1, 1933

By W. L. Phillips

Single crystals of aluminum, brass, and copper oriented for (100) and (110) slip were extended at 25°, 400°, and 600°C in simple shear. Aluminum specimens oriented for nonoctahedral slip began to shear at a higher critical resolved shear stress than specimens oriented for octahedral slip. Parabolic stress-strain curves were obtained from zero strain. The initial rate of parabolic hardening was lower for specimens sheared on the (100) plane in a close-packed direction <110>, than for specimens sheared in a nonclose-packed direction <100>. metallographic evidence, however, showed that all slip traces could be explained in terms of (111) <100> slip. All attempts to cause nonoctahedral slip in copper and 70-30 a-brass single crystals were unsuccessful. Instead of shearing, the crystals bent, allowing {111} type planes to come into action. NONOCTAHEDRAL slip in aluminum has been reported under three different conditions: first, as the main mode of slip in tension experiments at elevated temperatures;&apos;-&apos; second, as the main mode of slip in direct shear experiments at room temperat~re; and third, as a minor mode of deformation, i.e., as cross-slip, in tension, shear, and bicrystal experiments at room and elevated temperatures."-l2 However, as far as the author knows, nonoctahedral slip has not been reported in either copper or 70-30 a-brass. The present study was undertaken to determine whether nonoctahedral slip could be obtained in aluminum, brass, or copper at room or elevated temperatures when the shear stress was approximately constant over the cross-section, a maximum at the center, or a maximum at the surface. EXPERIMENTAL PROCEDURE A detailed description of the crystal preparation and shearing apparatus has been given previo~sly. Cylindrical crystals 1/2 in. in diam and 8 in. long were grown from the melt in a temperature-gradient furnace. The aluminum contained 0.001 pct Zn, 0.001 pct S, and 0.001 pct Fe; the 70-30 brass contained 0.015 pct Pb, 0.001 pct Fe, 0.01 pct Ni, 0.02 pct Sn, and 0.005 pct Se; the copper was certified OFHC of 99.98 pct purity. All samples were electropolished prior to testing. The shear apparatus was a modified Bausch type. The strain sensitivity was 4 x lob4 Load was applied by clamping the rods attached to the shear plates in an Instron tensile machine. The rate of loading was 0.02 in. per min. In all cases a 1/8-in. gage length was used. For the tests performed at 400° and 600°C the shear plates, collars, and rods were made of stainless steel. These elevated-temperature tests were performed in an argon atmosphere. A) Aluminum at Room Temperature. Values of a and ß for the various slip planes and slip directions investigated are shown in Table I where a is the complement of the angle between the specimen axis and the slip direction, and ß is the angle between the specimen axis and the normal to the shear plane. The shear stress is a function of a (assuming ß - 0);10 when a is less than 27 deg, the shear stress on the slip plane for which the specimen is oriented has a maximum at the center of the crystal; at a = 27 deg the shear stress is constant across the slip plane; for a greater than 27 deg the shear stress is a minimum at the center. Fig. 1 shows the stress-strain curves for specimens cut from crystals 1, 2, and 5, which were sheared on the (010) plane in the [loll direction at room temperature. These three crystals have shear-stress distributions corresponding to the three dif-

Jan 1, 1962

By P. G. Shewman, T. L. Wilson

Using published surface-diffusion (D,) data and published sintering equations, it is shouln that surface difusion should dominate the neck-growth stage of intering for all materials in which D, has been measured (six metals and A1as). Also, grain boundary diffusion can be expected to contribute appreciably to shrinkage and possibly to neck growth below some critical temperature of the order of 70 pct 01- the absolute melting temperatuve. In view of the widespread conclusion in previous sintering work that volume diffusion dowzinates neck gvowth, experiments were conducted using spherical copper powders to test this conclusion. Scaling studies on neck growth at 950°and 1020°C clearly demonstrated that suyface diffusion dorninates. Kinetic studies on shrinkage gave more equivocal results that indicated an increasing role of&apos; grain boundary transport at lower temperatures. Five diarszeters from 100 to 300 u were used in the scaling sludy and a temperature range of -650&apos; 10 950 C was covered in the shrinkage studies. All experiments were conducted in dvy hydrogen. In 1949, Kuczynski published his now classic paper on the determination of the transport mechanism in sintering from the time laws of neck growth. In the interim, these laws have been applied to many systems and slightly modified by several authors. Essentially all these authors concluded that, for crystal- line materials, the dominant transport mechanism in neck growth is volume diffusion. This stems from the observation that the neck radius increases about as t"5 and that the activation energy approximates that for lattice diffusion. A related but independent series of studies stems from Mullins&apos; rigorous analysis of the growth of the groove formed where a grain boundary meets a free surface." xperimental work stemming from this analysis has shown that for each crystalline material studied (Au, Ag, Cu, Ni, Fe, Pt, Al2O3) surface diffusion was clearly the dominant transport mechanism for groove widths up to the order 10 to 20 p. The ratio of the quantity of material being carried by lattice diffusion to that carried by surface diffusion increases linearly with the groove width, so surface diffusion is dominant for all widths under 10 to 20 u. The analysis of the relative contributions of surface and volume diffusion to grain boundary grooving, and to neck growth in sintering, shows that they are quite similar. Thus, using the available surface-diffusion data and the approximate equations of Kuczynski, or the more rigorous recent equations of Nichols and Mullins, 3 it can be shown that the small necks between particles must grow almost entirely by surface diffusion. The purpose of this study was to re-examine the basis for the conclusion that the neck-growth stage of sintering proceeds by volume diffusion. Using spherical copper powders, of several different diameters, precise experimental measurements were made of both neck growth and shrinkage. Application of Herring&apos;s scaling laws to the neck-growth data clearly indicated that neck growth occurred by surface transport, even though the neck radius increased as or Using the recent analysis of Mullins and Nichols as well as published data on surface diffusion, it is shown that the observed time law, as well as actual rate of neck growth, can be satisfactorily explained by a surface-diffusion mechanism.

Jan 1, 1967

THE metal iron has physical and chemical properties which are somewhat different from those of steels, but a knowledge of the pure metal is a useful starting point in studying the behavior of steels. Solid iron exists in two different crystalline forms, called alpha (a) and gamma (?) iron, the former being the ordinary form at room temperature. When heated above the "A2 point," 1400°F. (760°C.), the metal becomes non-magnetic, and at the "As point," 1670°F. (910°C.), it undergoes a change in crystalline form to become gamma iron. In the range 1400 to 1670°F., it is sometimes called beta (0) iron to distinguish it from the magnetic alpha, but the two are identical in crystal structure. When gamma iron is further heated to 2550°F. (1400°C.), it changes into delta (d) iron, which is identical with beta or non-magnetic alpha iron. Pure iron melts (in a hydrogen atmosphere) at 2795°F. (1535°C.); the melting point is generally lowered by alloys or impurities. PROPERTIES OF IRON AT HIGH TEMPERATURES Many of the properties of iron undergo abrupt changes at the transition temperatures. (1) For example, in heating through the As point a sudden shrinkage in volume occurs. Similarly, melting is attended by sharp physical changes such as an increase in volume. Table 27 contains a summary of the measured physical properties of pure iron at several temperatures. Usually the properties change smoothly within the range of stability of a given form, but this is not always the case. For example, the specific heat reaches a sharp maximum at the A2 point although no transformation occurs. Solvent Powers of Liquid Iron. Liquid iron is capable of dissolving most of the other metals and many nonmetallic elements as well. Of the metals which are liquid at the melting point of iron only lead, silver, and bismuth refuse to dissolve to an appreciable extent. The non-metals presumably dissolve by virtue of the formation of an iron compound; for example, sulphur is thought to dissolve as the compound FeS. However, there is no satisfactory method of proving that this

Jan 1, 1944

By E. C. W. Perryman

IN spite of the large amount of work which has been carried out on the recrystallization of aluminum and its alloys, there has been no complete investigation of the recrystallization characteristics of A1-Mg alloys. The most complete investigation is that reported by Bungardt and Osswald&apos; who, working with commercial-purity materials, found that the temperature both of beginning and of complete recrystallization increased with magnesium content up to about 2 pct Mg, then decreased with a further increase in magnesium up to 5.0 pct, and thereafter increased again. Michaud and Segolz working with 99.93 pct A1 also found the temperature of beginning of recrystallization to decrease as the magnesium content increased from 2.13 pct to about 4.5 pct. Chossat3 using aluminum of 99.99 pct purity found that 0.12 pct Mg had no effect but that 0.4 pct Mg increased the recrystallization temperature by about 30°C. That no effect was found for 0.12 pct Mg does not agree with the later results reported by Demer and Beck4 who found that 0.025 pct Mg in 99.99 pct A1 increased the time for complete recrystallization and furthermore increased the activation energy for the recrystallization process. Kratz" using 99.997 pct A1 found that 0.5 pct Mg increased both the temperature of beginning and of complete recrystallization by 100°C. Chadwick and Hooper" working with commercial-purity material found that 1 pct Mg increased the temperature of complete recrystallization by about 40 °C for cold reductions in the range 17 to 72 pct. With smaller amounts of cold work produced by stretching (10 pct strain), they found no significant effect of magnesium. The latter result agrees with that obtained by Williams and Eborall&apos; who found no effect of 2 pct Mg on the recrystallization temperature of commercial-purity aluminum strained 10 pct or less by stretching. Experimental Procedure Material Used: The chemical analyses of the materials used throughout this investigation are given in Table I. Fabrication: The alloys were cast in iron molds which had been washed thoroughly with alumina. After scalping, the ingots were annealed for 16 hr at 450°C, pressed, annealed at 450°C for 16 hr and hot rolled to 0.25 in. After hot rolling, the slabs were alternately annealed and cold rolled to 0.036 in. Cold-rolling reductions between intermediate anneals were kept at about 30 pct and a high intermediate annealing temperature of 450°C was used so as to obtain, as nearly as possible, similar starting grain sizes for the different materials. All intermediate anneals were done in a salt bath and were followed by cold-water quenching so as to retain all the magnesium in solid solution. The final cold reductions investigated were 20, 30, 40, 50, 60, and 80 pct. The initial grain sizes, that is, the grain size before the final cold reduction, were all very similar. Annealing Procedure: Specimens, 1 in. sq, were cut from the 0.036 in. sheet and annealed in a salt bath, the temperature of which was controlled to k2"C. Separate specimens were annealed for different times at 350°, 375", 400°, and in one or two cases at 415°C and after annealing were quenched in cold water. The time taken for a specimen to reach temperature was approximately 5 sec. Metal-lographic examination after annealing showed that no precipitation of Mg+413 occurred during cooling. Procedures Used for Determining Recrystallization Characteristics: All specimens were electrolyti-cally polished and etched by the method described previously1° and polishing was continued until about 0.002 in. had been removed from each side of the specimen. Using this technique, the smallest recrys-tallized grain which could be observed with cer-

Jan 1, 1956