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By S. W. Poole, J. A. Rosa

The object of this investigation was to determine the distribution of chemical elements within a large, killed alloy-steel ingot, by sulphur printing and quantitative chemical analysis. With regard to segregation in steel ingots, the factors of melting practice, pouring temperatures, mold design, etc., and the mechanics of solidification and its attendant functions, have been the subject of intensive study over a period of years by many investigators. Notable among these is the Sub-committee of the No. 5 Committee of the British Iron and Steel Institute. For an exposition of the many problems awaiting the researcher on the heterogeneity of steel ingots, the methods of attacking these problems, together with some of the answers, the reader is referred to the nine reports and numerous papers of that committee and its membership. Steelmaking Data Melt.—The heat was made in a 70-ton direct arc-type basic electric furnace. Furnace charge consisted of nickel-chromium-molybdenum steel, most of it in the form of heavy mill scrap. All of the scrap was charged cold. The standard double-slag method was employed, the heat being finished under a strong carbide slag. Aluminum was used as the deoxidizing agent. Tapping tempera- ture, as observed with an optical pyrometer, was 3000°F. Detail of Mold and Ingot Size.—Details of the ingot mold and the ingot itself are given in Fig. I. Teeming.—Teeming temperature of the subject ingot as observed with an optical pyrometer was 2830°F. The ingot was top-poured directly through a 1 1/2-in. nozzle and required 7 min., 44 sec. to fill up to the hot top. An additional 2 min., 30 sec. were required to fill the hot top. The ingot was stripped hot and charged with the remainder of the heat into an annealing furnace. There it was given the standard annealing cycle used for these ingots. Subsequent heat-treatments are described elsewhere in this paper. Sectioning and Preparation for Sulphur Printing Because of previous favorable experience in sectioning ingots up to 21 1/2 in. square with an oxyacetylene torch, it was decided to use this method to section the subject ingot. The ingot was preheated to 900°F. for 12 hr. It was then placed on a steel bed in a horizontal position so that the longitudinal axis was level and parallel to the track of the motor-driven torch carrier. Two cuts were made, one 2 in. above the longitudinal axis and the other 2 in. below. The time required to make each cut was approximately 75 min. The cutting operation is shown in Figs. 2 and 3. The 4-in. thick slab was mmediately charged into a furnace standing at 1200F.

Jan 1, 1945

By T. E. Eagan, W. R. McCrackin

IN dealing with segregation in babbitt, and its effect on the final cast structure, which is a bearing, it is obviously impossible to cover all of the compositions manufactured. Each composition, of course, will exhibit certain specific types of segregation. However, as examples,, two compositions of babbitt are presented: one a tin-base of well-known analysis and the other a lead-base, which in the past few years has found wide usage. Bearings usually are cast either statically or centrifugally; therefore the effect of these two methods on segregation is presented. EXPERIMENTAL PROCEDURE A slab of babbitt 1/2 in. thick by 5 in. wide and 17 in. long was cast, using a book mold with the long edge vertical. An A.S.T.M. grade 2 babbitt was used (3.5 per cent copper, 7.5 per cent antimony, remainder tin), to which 0.10 per cent tellurium had been added. Unfortunately, no metal without tellurium was available. The mold to hold the babbitt was heated to approximately 300°F., the temperature being judged by the babbitter. The pouring temperature of the babbitt was 875°F. (470°C.). One slab was made by allowing the babbitt to cool without stirring. The other slab was stirred during the entire cooling cycle. This stirring consisted of a vigorous churning or puddling into the mold until complete solidification had taken place. Three samples were removed from these slabs. One was taken at the extreme bottom, another half way to the top, and another at the extreme top, all at the center of the width. Chemical, macroscopic and microscopic examination was made of all samples. Table I shows the chemical analyses obtained at the described positions [ ] in the slab. The analyses show no serious amount of gravity segregation. Microscopic examination from edge to edge of the slab showed little change in structure. From top to bottom there was a progressive coarsening of the grain size in the stirred slab but little change in the slab that was not stirred (Fig. I). No definite exhibit of segregation could be detected. In line with our experimental study on the tin-base babbitts, we cast an almost duplicate slab using A.S.T.M. Alloy No. 15, containing 0.9 to 1.25 per cent tin, 14.75 to 15.5. per cent antimony, 0.80 to 1.25 per cent arsenic and 0.4 per cent copper. The slab was 16 in. long and 3/8 in. thick, cast with the long side vertical. One slab was allowed to cool normally and the other was stirred continually during cooling. The pouring temperature of the babbitt was

Jan 1, 1944

By C. G. Dunn

MANY investigations have been made concerning the nature of plastic deformation and recrystallization of metals either in the form of polycrystalline materials or in the form of single crystals. However, similar work on strip materials composed of large grains as thick as the strip and having a high degree of preferred crystal orientation has not been carried out extensively. Such materials are ideal not only for studying changes in single crystals under conditions where neighboring grains exert their influences but also for obtaining the, complete change in orientation of a grain or group of grains during the course of plastic deformation and subsequent recrystallization. It is well known that first-order twins in the form of Neumann bands may be produced during the plastic deformation of ferrite crystals, particularly silicon ferrite crystals.1-3 Furthermore, it is believe that high-stress regions exist in the vicinity of these bands4a and it has been said that these banded regions would be active in recrystallization processes.5 Evidence to that effect in silicon ferrite had already been presented with photomicrographs showing recrystallization among Neumann bands during the early stages of recrystallization.5,6 Similar evidence has been published for nonferrous metals.5 Merging of fine parallel deformation bands during annealing to form twin bands of ordinary appearance in alpha brass has been offered not only as evidence of an active role being played by mechanical twins but also as evidence that such twins existed prior to recrystallization.5 Proof that such new structures are actually first-order twins, or even twins at all, must be considered inadequate except for those cases where X-ray or optical data have been obtained to confirm the necessary orientation relationship.7,8 A. B. Greninger has obtained excellent iliustrations of annealing twins in alpha irons Since his material was previously deformed by sharp hammering, a process that generally induces Neumann bands, the existence of twins following annealing might suggest that they grew from mechanical twins. In connection with transformation twins in alpha iron, Greninger reported that grains containing. three twin orientations occurred rarely and none occurred with three sets of well-developed bands.9 The work at the Pittsfield Works Laboratory on silicon ferrite in the form of large-grained strip steel deformed a small amount and annealed to partially recrystallize the grains indicates that the deformation and recrystallization processes that lead to annealing twins involve more complex processes than the formation of Neumann bands and the growth of such bands. Some groups of annealing twins are obtained which contain not only three well-developed twin structures, but also contain more than one order of twins. It is also shown, in one case, that an interrelated group of twins did not arise within one single parent grain and, furthermore, orientations of grains in the group

Jan 1, 1944

By Henry Eyring, Jay W. Fredrickson

MANY theories have been advanced to explain the phenomena of elastic and plastic deformation. The object of this report is to present a mechanism for deformation, not radically differing from existing theories, but embodying certain principles and concepts of these theories. This proposed theory cannot be the complete answer to the age-old problem of deformation but it is believed that it will be a step further in the proper direction. The plastic properties of solids have recently been reviewed by Seitz and Read.1 Zener2 has reviewed and correlated the existing work on the anelasticity of metals. With these and othersa3,4,5 present theories of deformation are well-known. Of the many theories now extant, those receiving most attention have been proffered by Griffith,6 Becker,7 Smekal,8 Polanyi,9 Orowan10 and Taylor.11Although differing quite widely in details, these theories are based more or less on a common principle of flaws or dislocations that exist in the crystal lattice. The effect of stress concentrations surrounding a flaw or crack has been treated most recently by Fisher and Hollomon.12 The various authors differ as to the exact nature of the flaws or dislocations, the causes of their appearance, or the manner in which they initiate slip. All of the theories agree that the number of dislocations increases with progressing deformation. It is universally agreed that the shearing process is not a simple gliding of ideally perfect atomic lattice planes. It is also agreed that the "macroscopic process of gliding, or slip, is brought about by the spreading of a large number of locally initiated "glide steps" through the whole crystal. The occurrence of these "glide steps" is closely related to the presence of some kind of deviations from the "ideal" lattice structure, even in the undeformed crystal. These deviations are overcome "one at a time," in a manner of speaking, due to some stress-concentrating effect." PROPOSED THEORY Many solids show a continuously increasing deformation if subjected to a constant load of suitable magnitude in an extended range of temperature for a sufficient time. This deformation, or flow, may be said to be due, in general, to the tendency of the atoms or molecules in an elastically stressed body to readjust themselves in such a way that if the deformation were kept constant, a release of stress would take place. If rupture does not occur, this process of relaxation causes the rate of flow to obtain a final constant value, as shown in the curve (Fig I) obtained by Taylor and Quinney.14 In. this state the release of stress by relaxation exactly counterbalances the increase due to the elastic strain on the test pieces. .

Jan 1, 1948

By John J. Schanz

INTRODUCTION The two prior Seeley W. Mudd books on mineral economics devoted their final chapters to themes having to do with the future. In 1932, the last chapter in Mineral Economics8 was "The Future Value of Mineral Property" by J. R. Finlay. Both the first edition (1959) of Economics of the Mineral Industries7 and the slightly revised second edition (1964) closed with "Minerals and Man's Future" by Zay Jeffries. We are not inclined in this third AIME volume on mineral economics to ignore the tradition of the prior volumes. Moreover, it always is fitting and proper to close a book about the mineral industries by examining in a rather general way the challenges and uncertainties that are perpetually strewn in our path as we pick our way into the future. Unlike its predecessor volumes, which were written to acquaint the nonspecialist with the economic characteristics of mineral resources and to provide data about the mineral industries, this edition was also designed with the mineral economics student and practicing specialist in mind. Thus it is anticipated that it will be both a reference as well as suitable for use as a textbook. Consequently, this closing examination of our changing perspectives about mineral resources devotes some space to the past events and current status of mineral economics as a field of study. The fears and forecasts of the past can be a perceptive and usually deflating way to begin an examination of the future. As we look up and down the track of time from the 1975 platform, we find that many of the past views of the future were transient in character, others were imperfect in their prognosis, while others were based on fears that now seemed unfounded. But down through the years some of the observations or expressions of concern have a persistency which perhaps reflects some elemental characteristics of mineral resources. On these "truths" rest our contemporary understanding of the economics of the mineral industries. The uncertainties and priorities for the next 25 or more years, not surprisingly, have a somewhat different mix than those that seemed most compelling to our predecessors in 1932 or 1959. So it is appropriate that we review how the perspective of the mineral economist has changed over the span of a half century. In light of the particular interest of AIME on the role technology must play, it is fitting that we close with some observations on that topic. THE EMERGENCE OF MINERAL ECONOMICS AS A FIELD OF STUDY The publication of Mineral Economics by the AIME in 1932 as a Seeley W. Mudd volume marked the end of emerging interest in

Jan 1, 1976

By B. N. Bose, M. F. Hawk

SINCE Davenport and Bain' introduced the isothermal transformation technique for the study of austenite decomposition in steels, a new field of investigation has opened up. Extensive research has been carried out on many different steels, but relatively little work has been done on eutectoid transformations in analogous alloy systems. The researches of Smith and Lindlief,² Mack,³ and Klier and Grymko²0 on the beta-phase transformation in copper-aluminum alloys, of Hibbard, Eichelrnan, and Saunders4 and Smith5 on the kappa-phase transformation in copper-silicon alloys, of Chaudron and Forester6 on the decomposition of "FeO," and of Wasserman7 on similarities between the iron-carbon, copper-aluminum, copper-tin, and copper-beryllium systems essentially comprise the field. The iron-nitrogen system, in view of its remarkable similarity to the iron-carbon system, is particularly attractive for the study of eutectoid decomposition. The present investigation is concerned with the study of isothermal transformation, proceeding by the familiar nucleation and growth processes, and of martensitic transformation characteristics of pure iron-nitrogen alloys. The kinetics of transformation and the morphology of the transformation products have been investigated, for these must be the factors determining the properties and behavior of the final product. The Iron-Nitrogen System he binary iron-nitrogen phase diagram has been a matter of considerable disagreement among vari01.1s investigators. However, the phase diagram according to Eisenhut and Kaupp8 and Lehrer10 is now considered essentially correct as reproduced in fig. 1. The important values, 2.35 pct nitrogen and 591°C, for the co-ordinates of the eutectoid point (obtained from this diagram and used in the re- search to be described) were confirmed in a concurrent study of Paranjpe, Cohen, Bever and Floe." The eutectoid decomposition involves the transformation of the ? face-centered cubic interstitial solid solution of nitrogen in iron to the a body-centered cubic interstitial solid solution of nitrogen in iron and the ?' nitride of iron. This nitride is essentially the compound Fe,N; it also possesses a face-centered cubic lattice but a considerably larger one than the ?; the nitrogen atoms in ?' are arranged in an ordered way in the centers of the unit cubes.8,10,11 A martensitic structure has also been reported8,12 in iron-nitrogen alloys and was studied in the research to be described here. Materials and Methods The specimens used in this investigation were prepared by nitriding "pure" iron. This iron was supplied by the Westinghouse Research Laboratories and is the product bearing their trade name "Puron"; it contains about 0.04 wt pct total impurities, the major portion of which is oxygen. Specimens were ribbons several inches long, a tenth of an inch wide, and 0.125 mm thick; this was the

Jan 1, 1951

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 re-deposited 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 May16 in a discussion of Abrams' paper, first suggested the addition of small amounts of arsenic (0.03 per cent) to a1pha 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,a 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 (As2O3),

Jan 1, 1942

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 re-deposited 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 May16 in a discussion of Abrams' paper, first suggested the addition of small amounts of arsenic (0.03 per cent) to a1pha 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,a 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 (As2O3),

Jan 1, 1942

By A. W. Jenike

A theory of gravity flow of bulk solids like ores, concentrates, coal is outlined and an example of design for unobstructed flow is given. Mass-flow and plug-flow patterns are defined and related to the geometry of the bin. The effect of these patterns on segregation, first in-first out flow, and caking is described. This paper is a report on the results from the AIME sponsored project "Flow of Bulk Solids" which was carried out under the author's direction at the Utah Engineering Experiment Station, University of Utah, during the period 1956-1962. The theory has been applied to the design of numerous industrial storage plants. A QUANTITATIVE METHOD OF DESIGN FOR FLOW There is hardly an industry which does not store and handle solid materials in bulk form. When the volume of the solids is large, gravity is invariably relied upon to cause the solids to flow out of storage, through channels and chemical reactors. Such materials as ore, coal, cement, flour, plastics, clay, soil, to which a general term of bulk solids is applied, flow by gravity or are expected to flow by gravity in thousands of installations and by billions of tons annually. The chemical and process industry depends on gravity flow of solids in process and out of storage. Mining relies on gravity flow in block-caving, in ore passes, as well as in storage and loading bins. Agriculture uses gravity flow in elevators, in feed plants, and in farm silos. In practice, satisfactory gravity flow is seldom attained. Such problems as doming, piping (rat-holing), lack of live capacity, segregation, deterioration in storage, harass industry. In spite of the universality of these problems, until recently, there has been no theory of solids flow, no method of predicting how a solid would behave, and how the channel, bin, or hopper should be designed. In the late nineteen forties and early fifties, the theory of plasticity came of age and simultaneously the computer became widely available. These two factors permitted the development of a theory of flow of bulk solids. The work was conducted during the years 1953-1961. In conjunction with the development of the theory a method to measure the flowability of solids was also developed1-7 and the theory was ap-plied to the design of ore pockets, storage plants,16 chemical reactors and adsorption columns. A comprehensive report of this work is given in a previous work." THEORY OF FLOW The most important question which a theory of flow has to answer is: what conditions need to be satisfied for a given solid to flow uniformly and without obstructions through a channel? First of all, the following observations are made:

Jan 1, 1967

By John Chipman, Raymond L. Orr

Recently reported high -temperatlnre thermal data have been incorporated in a reuieu' of the therinody-r~ar,zic propesties of iron. The recent data permit mot corlsisterlt and reliuble choices to be made for many of the pvoperties, resnlling in bettev eslablished tabrtlations of the thermodynamic functions. Values of Cp, h°t- - H°298. s°t - S2sa, and (G°T -H298/T are tabulated for -the solid and liquid phases of iron in both stable and melastable regions. Consistency of the tabulations has been maintained to the precision necessr~vg to yield the Gibbs energy change belween the bcc (a, 8) and fcc (y) phases of iron at temperatures pertinenl to alloy studies. THE importance of the metal iron has stimulated many investigations of its thermodynamic properties at elevated temperatures. Reviews and summaries of the data have appeared from time to time. Among these the 1951 paper of Darken and smith' deserves highest recognition for the quality of its criticism and for the precision and thermodynamic consistency of its tabulations. These and the more recent table of Kaufman, Clougherty, and weiss2 reproduce the Gibbs energy of the (a, 6)--Y transformation with sufficient sensitivity for alloy studies. Other recent compilations of equal validity3-' make no attempt to do this. Since this Gibbs energy change is not greater than 22 cal per g-atom over the temperature range 1100° to 1800°K, it is obviously desirable to tabulate values of (G°t - H298)/T to four places of decimals even though the absolute accuracy would not warrant such precision. The necessity for reconsideration of the problem is emphasized by the recent publication of several important researches on the enthalpy and heat capacity of iron. The older work is well-covered in the reviews cited and will be mentioned here only when actually employed in the tabulations. GAMMA IRON Transition temperatures are taken from the selec -tions of Elliott and Gleiser,5 based on the work of Boulanger7 and earlier workers. For the a-y (A3) transition at 1184°K we retain the value 215 cal per g-atom adopted by Darken and smith.' It has received confirmation in the recent work of Dench and Kubaschewski,' and of Braun8 using adiabatic calori-metry, and of Wallace, Sidles, and Danielson10 using a pulse heating technique. The enthalpy data of Olette and ferrier" and of Anderson and Hultgren12 at higher and lower temperatures may be extended to 1184°K to give the following values which are adjusted to the required value of ? 1184 Ha,1184 Ha 298 = 8030 cal per g-atom [11 hr,1184-ha298 = 8245 cal per g-atom [2]

Jan 1, 1968

By H. L. Gilbert, C. Travis Anderson, W. J. Kroll

IN a previous paper,1 the use of a split graphite tube resistor as a heater element for high-temperature furnaces has been described. The principal advantages of this type of construction are: I. The quadruple resistance or voltage compared with the top-bottom clamp resistor furnace. 2. Free expansion of the resistor. 3. The ease of protection from oxidation by air. 4. The firmness by which it may be held in the compact split clamp. This construction appeared to be well adapted for the fusion of high melting metals which require fusion in a vacuum. Zirconium metal had previously been melted at the Albany Laboratory of the Bureau of Mines in a vacuum arc furnace on a water-cooled plate, using a movable tungsten top electrode.2 When larger furnace capacities were desired, this type of construction proved to have its limitations as the largest tungsten rods available were about 7/8in. in diameter. The supply of direct current of high amperage for producing the . desired arc characteristics was also not available. Considerable difficulty was also found in compensating the atmospheric pressure on the flexible tubing of the movable electrode, at the same time keeping its movement sufficiently free to enable the striking of an arc on any part of the metal briquet. Among the various materials used for the electrodes in conducting experiments in the vacuum arc furnace was graphite. It was found that zirconium fused in a graphite cup with a carbon arc was contaminated to only 0.2 pct carbon. It was therefore decided to melt zirconium directly in graphite crucibles. A high-frequency furnace was first used in the attempt to melt the zirconium in graphite crucibles. The high-frequency heating coil was placed outside a silica tube which was evacuated by means of an oil diffusion pump backed up by a mechanical pump. The graphite crucible was thoroughly degassed at 1900°C before use. Considerable difficulty was experienced in operating at such temperatures in vacuo because, as shown by Zintl,3 carbon vapor formed and reacted with silica according to the reaction: Si02 + C = SiO + CO. The silicon monoxide which is volatile at these high temperatures reacted with the zirconium, thereby contaminating it with silicon and oxygen. The presence of carbon monoxide was detected by means of a gas discharge tube placed in the vacuum system as indicated by the pale blue glow of the tube as soon as carbon vapor started to react with the hot silica. The reaction between the carbon vapor and hot silica was avoided by the use of split cylindrical molybdenum shields which were inserted between the graphite crucible

Jan 1, 1948

By G. P. Gladis, R. H. Atkinson

PALLADIUM has been used for jewelry for many years, particularly in conjunction with gold. This use increased in amount during the war, as palladium and gold were only moderately used for war purposes while demands for platinum and some of the other members of the platinum group were so great that their use in jewelry was prohibited. Palladium hardened with a small percentage of ruthenium has the necessary technical properties and appearance for good jewelry, and it is sufficiently rare to be desirable for luxury items-at least 100 times as rare as gold. Although both visual and spectrophotometric examination demonstrated that the color of palladium was almost the same as that of platinum, a few jewelers found the surface of palladium, even after some polishing, rather dark in areas that had been repeatedly heated during the soldering necessary to assemble certain types of handmade ornaments. This phenomenon is not to be confused with the thin, bluish oxide film that can be produced by heating in air over the range 400° to 800°C., as that film is easily reduced by dipping in warm 5 per cent formic acid or in warm methanol. It was suspected that the difficulty arose from heating in atmospheres that were alternately oxidizing and reducing, as Wise and Vines1 had found that this opened the grain boundaries of palladium and palladium-silver alloys in the same manner as in pure silver, as reported by Martin and Parker.2 This damage is caused by the reaction between oxygen in solid solution in the metal, acquired when heated under oxidizing conditions, and hydrogen diffusing in from subsequent heating under reducing conditions; the steam cannot diffuse out and therefore builds up sufficient pressure to disrupt the metal near the surface. Copper and various other metals can be damaged similarly, but platinum is nearly immune; therefore the problem was new to the platinum jeweler. Sulphur in the fuel gas also can cause trouble but did not appear to be dominant in the present instance. Metallographic examination of both pure palladium and ruthenium-palladium showed that the usual torch using oxygen and city gas as normally operated did in fact cause the surface and subsurface damage that had been observed, and also disclosed that a reducing flame caused more damage than an oxidizing flame and was very damaging even in the absence of any intentional swing in atmosphere from oxidizing to reducing (Fig. 7); besides the surface damage, there was serious loss of ductility. A full explanation of the mechanism of attack is not evident at the moment, but may be allied to the attack that occurs on heating catalytically active metals in nonequilibrium atmospheres.

Jan 1, 1946

By J. W. Hickman, E. A. Gulbransen

In a previous paper' the authors have investigated the structure of the oxide films formed on most of the metals that make up the alloys of this study. The metals were studied in order to provide basic information on the structures, both physical and chemical, of the oxide films and to determine how these structures are effected by the temperature, time of oxidation, and surface preparation. It was felt that an understanding of the physical and chemical structure as well as the stability of the oxide film might furnish clues as to the nature of the reaction process and the protective quality of the film. The oxidation of the metals was studied over the temperature range 300' to 7o0°C. except for copper, wherc the range selected was 100' to 500°C. The results of these studies were presented in graphical form as existence diagrams of the oxides on a time-temperature scale. For some of the metals the existence diagrams were simple and showed few chemical transitions, but there were numerous cases where the physical state of the oxide surface was a function of time and temperature. In general the physical state of the oxide surface changed with increasing temperature so as to increase the sharpness of the diffraction patterns and to cause orientation effects to be more pronounced. Deviatiois in lattice Darameters from X-ray values were noted. In general these deviations were of positive nature and may be due to solid solution of the metal in the oxide lattice. This effect might be expected in thin oxide films. In a study of the oxidation of alloys containing two or more metals, there may arise the complicating factor of identification of the oxides formed. A thorough understanding of the oxides formed on the pure metals, therefore, was, essential before investigation of the oxidation of alloys. In this paper it is our purpose to present a study of the following problems: 1. The existence diagrams of various alloys. 2. The effect of the structure of the alloying metal on the existence diagram of iron. 3. The effect of the percentage of chromium on the oxides formed on Fe-Cr alloys. 4. The relationships, if any, between the oxides formed and the protective quality of the oxides. The following alloys are included in this study: alloys of iron with body-centered cubic, face-centered cubic and other metals, 13 Cr-Fe, 18-8 stainless steel, K4²B, Nichrome V, Hipernik, Inconel, Stellite "²I," Refractaloy, Kovar, mild steel, a series of Cr-Fe alloys and a series of Co-Fe alloys. Since many of the commercial alloys in this list contain more than two metals, various complicating factors in the identification of the oxides formed may arise.

Jan 1, 1947

By E. A. Gulbransen, J. W. Hickman

In a previous paper' the authors have investigated the structure of the oxide films formed on most of the metals that make up the alloys of this study. The metals were studied in order to provide basic information on the structures, both physical and chemical, of the oxide films and to determine how these structures are effected by the temperature, time of oxidation, and surface preparation. It was felt that an understanding of the physical and chemical structure as well as the stability of the oxide film might furnish clues as to the nature of the reaction process and the protective quality of the film. The oxidation of the metals was studied over the temperature range 300' to 7o0°C. except for copper, wherc the range selected was 100' to 500°C. The results of these studies were presented in graphical form as existence diagrams of the oxides on a time-temperature scale. For some of the metals the existence diagrams were simple and showed few chemical transitions, but there were numerous cases where the physical state of the oxide surface was a function of time and temperature. In general the physical state of the oxide surface changed with increasing temperature so as to increase the sharpness of the diffraction patterns and to cause orientation effects to be more pronounced. Deviatiois in lattice Darameters from X-ray values were noted. In general these deviations were of positive nature and may be due to solid solution of the metal in the oxide lattice. This effect might be expected in thin oxide films. In a study of the oxidation of alloys containing two or more metals, there may arise the complicating factor of identification of the oxides formed. A thorough understanding of the oxides formed on the pure metals, therefore, was, essential before investigation of the oxidation of alloys. In this paper it is our purpose to present a study of the following problems: 1. The existence diagrams of various alloys. 2. The effect of the structure of the alloying metal on the existence diagram of iron. 3. The effect of the percentage of chromium on the oxides formed on Fe-Cr alloys. 4. The relationships, if any, between the oxides formed and the protective quality of the oxides. The following alloys are included in this study: alloys of iron with body-centered cubic, face-centered cubic and other metals, 13 Cr-Fe, 18-8 stainless steel, K4²B, Nichrome V, Hipernik, Inconel, Stellite "²I," Refractaloy, Kovar, mild steel, a series of Cr-Fe alloys and a series of Co-Fe alloys. Since many of the commercial alloys in this list contain more than two metals, various complicating factors in the identification of the oxides formed may arise.

Jan 1, 1947

By B. M. Larsen, L. S. Darken

SOME years ago we collated all laboratory data then available to us on the distribution at equilibrium of manganese and of sulphur between metal and simple slags, and used the results in setting up an equation, which proved to be in accord with determinations of the distribution ratio of manganese and of sulphur between liquid steel and open-hearth slag, over a wide range of operating conditions. We now present an outline of our calculations and inferences on these two closely related questions, which are of especial importance because of the advisability of conserving manganese wherever possible. In general. our results show that in the open-hearth furnace equilibrium between metal and slag, with respect to both manganese and sulphur, is substantially attained during the finishing period of the heat, or in about a half hour to an hour after any additions were made. This implies that the end result will be identical whether manganese is added as alloy or metal to the liquid steel or as oxide to the slag. The proportion of total manganese retained by the steel is favored: (I) by use of the minimum amount of lime, consistent with other operating limitations, required to give a lime-silica ratio of about 2.4, which usually corresponds to a minimum practical slag volume; (2) by a high concentration in the slag of MnO relative to FeO; (3) by high operating temperature. Absorption of sulphur by the slag from the liquid metal is favored: (I) by large slag volume; (2-by a high concentration of active (or "free") lime and of manganese oxide dis) solved in the slag; (3) by low concentration of silica, iron oxide, and phosphate dissolved in the slag. DISTRIBUTION OF MANGANESE BETWEEN SLAG AND METAL AT EQUILIBRIUM On the basis that the distribution of manganese between liquid steel and slag is controlled by the reaction [FeO + Mn ;7± MnO + Fe [A] slag metal slag metal] the distribution at equilibrium, at a given temperature, is expressed by the equilibrium constant for this reaction, which is defined as [K" aFPI OFeO ? aMn] where a is the activity of the molecular species denoted by the subscript. The activity of each of the several components, although it is not known precisely, is approximately equal to the concentration of each component expressed as its mol fraction; that is, as the ratio of the number of mols of the given component to the total number of mols of all the molecular species present in the metal or slag, as the case may be. Moreover, since the activity, or concentration, of iron in the liquid metal is in fact substantially constant, the term aFe may he combined with K" to give a new constant K'. Making these changes.

Jan 1, 1942

By S. Vela, R. M. McKinley, L. A. Carlton

Johnson et al. have described a new well-testing technique that measures formation flow properties between wells.' The technique, called pulse-testing, requires a sequence of rate changes in the flow at one well and measzcrement of the re.rulting pressure changes at an adjacent well with a very sensitive differential pressure gauge. This paper describes an extensive application of the technique in a producing oil field. Pulse-tests on 28 of 45 possible well pairs in the field provided a picture of the areal distribution of reservoir hydraulic diffusivity, trans-missibility and storage. The primary objective in presenting these data is to demonstrate the potential of the methcid for reservoir description. A second objective is to show in three ways the qualitative and quantitative accuracy of reservoir parameters determined from pulse-tests: (I) pulse-test data show a nonuniformity in the field, closely correlating with the oil-water distribution as given by production data: (2) pulse-test values for permeability are comparable with core va1ue.s; and (3) perhaps most important, the field responds to a conventional interference test in the manner in which pulse-test data predict it should. The pulse-testing technique by Johnson et al.' is an ideal source of data for purposes of reservoir description, for it provides a measurement of formation storage S = +ch, hydraulic diffusivity 91 = k/+cp and transmissibility T — This paper describes an application of this method in a producing oil field. Results were analyzed to give numerical values for the parameters 7, T and S. These values were compared with oil-water production data (for the effect of fluid saturation), with core data and with data from an interference test. The reservoir in which the pulse-test survey was run is the result of a structural trap formed by a fault along the east side of a north-south trending anticline. A down-structure aquifer providcs a natural flank water drive for the pool. The producing formation is a dolomitic lime- stone having mainly vugular permeability; the formation oil has a gravity of 29" API with negligible dissolved gas. The field contains 19 wells, all on pump, arranged on 40-acre spacing along the top of the anticline. Fig. 1 shows the location of all these wells except two at the south end of the field. The dashed line on the right-hand side of the figure represents the approximate location of the fault with respect to well positions. Pulse-Test Survey and Analysis of Data A pulse-test requires a pulsing well and a responding well. In the field, changes were made in the rate of flow at the pulsing well by stopping and starting the pump periodically and measuring the corresponding pressure

Jan 1, 1969

By W. L. Fink, L. A. Willey

DURING the war there was introduced a new higher strength aircraft alloy designated 75S.1,2.3 The properties of this alloy assure extensive applications in both military and commercial aircraft. It is therefore important to understand its limitations as well as advantages. The properties of 75S alloy in the heat-treated tempers, like those of many other aluminum alloys, are affected by the rate of quenching. In general, low quenching rates tend to cause low strengths and to adversely affect the resistance to corrosion. Commercial quenching procedures are usually sufficiently rapid to permit the development of maximum properties. However, in the center of heavy sections, such as large rolled and extruded shapes, the quenching rates may not be rapid enough to develop maximum strength or resistance to corrosion. The investigations of 75S alloy described herein reveal the most critical range of temperature and the effects of quenching sheet and extrusions at different rates through that temperature range, on the tensile properties and resistance to corrosion. PROCEDURE Preparation of Specimens Sheet specimens (3 in. by 9 in.) were prepared from a commercial lot of 75S "as rolled" sheet (0.064 in. thick). The composition° was as follows: Weight Percentage Cu Mn Mg Zn Cr Al with Normal Impurities 1.64 0.16 2.58 5.66 0.27 Remainder The specimens employed for the determination of the time-temperature relations during quenching of sheet were prepared by the following procedure: the hot junction of a 28-ga. iron-constantan thermoelement (asbestos insulated) was brazed to a thin strip of aluminum which was in turn brazed into the end of a 3/16 in. i.d. by ¼ -in. o.d. by 30 in. long aluminum protection tube. Before brazing, the tube was flattened to 0.064 in. thickness over the junction and adjacent lead wires for a distance of 1 ½ in. The flattened end of the tube was fitted into a slot cut from one edge to the center of the 3 in. by 9 in. by 0.064 in. sheet and brazed into place. The brazed joint was dressed to the thickness of the sheet and the entire specimen buffed to approximately the brightness of "as rolled" material. Because of the brazing operations required, these specimens were prepared using 3S alloy. For the investigation of quenching rates in heavy sections, there were used 75S extrusions which had compositions similar to that of the sheet. The specimens consisted of 14 in. lengths of ¾ in., 2 in., 3 in. and 4 in. diam cylindrical rods and a roughly rectangular extruded section which was approximately 4 in. by 7 ½ in. Thermocouples were peened into the bottoms of 1/8 in. diam wells drilled into one end and parallel to the axis to a depth of

Jan 1, 1947

By Daniel R. Hull

IN 1026 Genders' reviewed the existing theories of this subject and stated his views in support of the gas-pressure theory. Again, in 1937, the subject was thoroughly reviewed by N. B. Vaughan,3 and by Phillips and Brick,2 so that no resume is called for here. The purpose of this paper is to describe certain observations made in the course of mill work, and to point out that they mostly tend to confirm the gas theory of Genders. VAPOR SEGREGATION There is, however, one type of inverse segregation that can be accounted for by considering the volatility of one of the constituents of an alloy. The most familiar case is ordinary brass, which is subject to a zinc enrichment of a few tenths of a per cent at the surface of a chill casting. This has been noted in 70-30 brass by Genders, and a typical example of it is given in Table I, which represents a [ ] cylindrical billet 7 in. in diameter by 5; in. long. After lathe-turning 1/32 in. from the surface, the remaining distance to the center was sampled at six equally spaced intervals. The lead, which is essentially the same throughout, will be mentioned later. Consider a brass-mill mold, either round or rectangular in cross section, standing several feet high. It may require a minute or two for pouring. Before it is full, the metal in the lower end has partly solidified and contracted somewhat away from the mold. The initial shell of solidification follows not far behind the top of the column, even if the central portion is liquid for a long way down. There is, then, a space between metal and mold that is filled with zinc vapor. The vapor has no exit, because the liquid at the top of the rising column is not only in contact with the mold but keeps up a fresh supply of zinc vapor, which has, perhaps, already begun to condense in the lower portion. The cycle is short. Within a minute or two after the mold is full the bar has cooled enough to condense all the zinc. Some of it may condense on the mold; it might be expected that most of it would condense there, but the mold at that time is well coated with a velvety carbon residue from the oil dressing, overlain by fluffy zinc oxide that commenced covering the inside of the mold as soon as pouring began. The clean skin of the freshly cast brass offers a preferred surface for condensation. Reabsorption is quick and inevitable. A simple experiment indicates that a surprisingly large quantity of zinc vapor is trapped in the space between mold and

Jan 1, 1941

By H. J. Snyder

Both the room-temperature and 600°F (315°C) primary solid-solution phase boundaries for the silver comer of the Ag-Cd-In temary system have been determined using X-ray diffraction and metallo-graphic techniques. Solid solubility of indium in silver at room temperature and 600°F (315°C) is shown to be between 20.3 and 21.7 wt pct, and corrects the previously extrapolated value of 18 wt pct appearing in the literature. The solid solubility of cadmium in silver at room temperature, not previously established, is shown to be between 34.9 and 41.3 wt pct. The solid solubility of cadmium in silver at 600°F (315°C) is confirmed as 43.2 wt pct. The shape of the primary phase boundary line for the subject temary system appears straight at room temperature and curves con-vexly towards the solvent (silver) comer at 600°F (315°C). THIS investigation was undertaken to initiate development of the Ag-Cd-In ternary diagram by establishing the primary solid-solution phase boundary in the silver corner of the diagram. At the present time, a diagram for this ternary system is not available, while this system appears to offer potential for a variety of uses. One alloy in the system has already proven to be useful as a control rod material in nuclear reactors.1"3 To encourage additional exploration of the potential of the system an understanding of its ternary diagram would be beneficial. It is towards this end that the present study is directed. LITERATURE SURVEY In undertaking this study, a comprehensive literature survey was first conducted to find information that would be useful for guidance. Useful knowledge did result from investigating the respective solubilities of indium and cadmium in silver as indicated in the binary constitutional diagrams of the systems Ag-In and Ag-Cd and also reviewing possible shapes of ternary primary phase boundaries. Weibke and Eggers~ used metallographic techniques to establish the system In-Ag as illustrated in Fig. Is This diagram shows that silver in the solid state is capable of dissolving approximately 18 wt pct In. This solid solubility of indium in silver holds true from room temperature up to 1276°F (691°C), then decreases continuously up to 1'761°F (960.5"C), the melting point of the silver. The solid-solubility limit of indium in silver established by Weibke and Eggers has been confirmed by Hume-Rothery and Reyno1ds. G Durrant' used a method which consisted of microscopic examination of quenched specimens to establish the Cd-Ag system as displayed in Fig. 2.' The primary phase boundary of Fig. 2 proved to be in good agreement (ie., within 1 wt pct) with other studies*'1' of the Ag-Cd system made using X-rays and metallog-

Jan 1, 1968

By A. G. Preban, R. J. De Angelis, J. B. Cohen, P. Gordon, D. C. Brillhart

Changes in stored energy, resistivity, density, X-ray line broadening, and dislocation arrangements (from transmission electron microscopy) have been mensured on copper specimens shock-loaded at 75 to 435 kbars. The stored energy in shock-loaded copper and changes in density and resistivity are larger than those after conventional deformation. A high density of twins makes an appreciable contribution to all the measured quantities. Dislocation densities rise to values of 1011 lines per sq cm at the highest pressure. The resistivity, density, and X-ray In a study of the effects of shock loading on copper, changes in stored energy, resistivity, density, hardness, lattice parameter, line broadening, and dislocation structure have been examined after subsequent annealing of specimens shocked to various pressures. This paper presents certain aspects of the data, taken by two groups, one at the Illinois Institute of Technology, and the other at Northwestern University, and compares the changes in these properties, and what they indicate about the effects of shock deformation. measurements yield dislocation densities in substantial agreement at all pressures, after correcting for the effects due to the twins. At the higher pressures, electron microscopy yields dislocation densities that are lower by a factor of about 5 to 10. Dislocation densities from stored -energy measurements are high; this finding can be rationalized by the consideration that the deformation twin boundaries present are largely incoherent. There is no evidence for homogeneous dislocation nucleation during shock loading. Shock loading any metal or alloy, such as copper, causes a large increase in yield strength, with dimensional changes of the order of only a few percent."' Other properties have not been extensively studied, but this result clearly indicates the importance of examining the substructure. Previous studies of the substructure of conventionally deformed specimens have been made using electron microscopy,3-6 X-ray diffraction,7,8 and etch pitting.9,10 The dislocation density can reach values of about 10" per sq cm; and the dislocations are arranged in cells approximately 0.15 in size. The substructure varies widely, however, from point to point in the specimen. The substructure of explosively loaded copper consists of cells of about the same dimensions6,11 but their size is more uniform.6 Profuse twinning occurs12,13 and the twins are often too small to be detected optically.6,13 The boundaries outlining these twins appear to be incoherent.14 There is now ample evidence 13-15 that twinning is a strengthening mechanism in fcc metals but this is only part of the strengthening effect in shock-loaded copper.* From the twinning systems which operate in shock-loaded single crystals,13 and from changes in texture on shock loading,17 it has been shown that both the

Jan 1, 1968