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By C. E. Cottrell, G. W. Preckshot, N. D. Delisle, D. L. Katz

Most crude oils contain asphaltic substances that may be naturally or artificially precipitated. In the Greeley field, California, this asphaltic bitumen is precipitated during the flow of the oil from the reservoir to the stock tank The mechanism of such precipitation is not well understood. This paper presents the progress that has been made by using the electron microscope as a new tool and by observing the effects of the streaming potential on the formation of bitumen particles. Crude oils at atmospheric pressure viewed in the electron microscope in very thin films under a vacuum showed no asphaltic particles. A technique of preparing slides of thin films by dilution of the oil with benzene and washing in petroleum ether was used at first, and these observations showed that the solvents caused the formation of the particles, varying from 0.01 to 0.2 micron in diameter. The electrical effects of fluids flowing through porous solid were studied, with emphasis on the formation of colloidal particles by the streaming potential. The streaming potential of crude oil flowing through sand was measured and was shown to be responsible for the formation of bitumen particles. These results bring out a new phenomenon, which may occur when crude oil flows through the porous oil reservoir. mechanisms. Asphalt has been the subject of widespread investigation but, owing to the complexity of the substances being considered, progress has been slow. Investigators working primarily with the asphaltic substances have treated the subject from the colloidal standpoint and have developed theories that picture the asphaltic particles as surrounded by adsorbed materia1s.14,15,17,24 The deasphaltization of lubricating oil by the use of solvents treats the subject primarily from the standpoint of liquid-liquid equilibria.'' A complete understanding of asphaltic substances would make possible the following of the material from its initial state in the crude oil through precipitation processes to the final plastic stage, the most common form of which is used in asphaltic pavements. Since these asphaltic particles are very small, it appears 'hat the electron microscope4 might be a useful tool in studying the precipitation processes. Specimens are examined by the electron microscope in a vacuum and as very thin films, requiring special techniques in preparation of samples. A brief description of the electron microscope and its operation will bring out the difficulties and advantages of its use for this problem. The first work was done with crude oils that had been diluted with solvents for the preparation of the film to be examined. Later a technique was developed by which the undiluted oil film could be made thin enough for direct examination. These two techniques show vastly different results Asphaltic particles have been precipitated from crude oils by a variety of

Jan 1, 1943

By V.K. Zworykin

Throughout its development the science of electronics, like so many other branches of science and industry, has been indebted to the metallurgist. Metallurgy has provided the electronic engineer with conductors to furnish passage for electrons outside of his evacuated tubes: it has developed tungsten and tantalum wires for emitting electrons and various refractory metals and alloys suitable for electrodes, which receive them and guide them within the tube; finally it has supplied ferromagnetic materials both for shielding electronic apparatus from magnetic fields and for forming highly concentrated fields for deflecting electron . Today I hope to show you that electronics has not been altogether ungrateful for this assistance. More specifically, I wish to indicate the role that the electron microscope, a relatively recent product of electronic engineering, is playing even now in the study of metals. Every metallographer is aware that his standard metallographic microscope will not reveal structural detail involving separations smaller than a certain fraction —at the very best a tenth—of a micron. This limitation, he knows, is a consequence of the fact that the wave length of the light employed for forming the image has this order of magnitude. It is, thus, a property of all light microscopes. TO overcome it, a different imaging medium must be employed, The existence of such a medium became evident when it was demonstrated1 that electrons were affected by magnetic and electric fields with axial symmetry just as light is affected by glass lenses; these fields, or "electron lenses," curve the paths of electrons reaching them from an object located on the axis of symmetry in such a manner that, at some distance from the lens, a true image of the object is formed. Furthermore, although a wave length may . be ascribed to electron beams just as to light, this wave length is much shorter; for electrons accelerated through a difference of potential of 50 kilovolts, the wave length is only about one hundred-thousandth of that of visible light. Actually, the elcctron microscopes of today resolve detail one hundred times as fine as light microscopes; if the maximum useful magnification of the latter is taken to be a thousand, that of electron microscopes is one hundred thousand. The Electron Microscope Since electrons are readily scattered and absorbed by matter, specimens to be observed in the electron microscope must be prepared to be less than one micron in thickness; furthermore, the interior of the microscope must be carefully evacuated to prevent collisions between the clectrons and the molecules of the air. Finally, as already mentioned, the lenses are formed by axially symmetric magnetic or electric fields, and not by any material medium such as glass. Apart from these basic differences, the electron microscope closely

Jan 1, 1943

By A. G. H. Anderson, A. W. Kingsbury

Silicon bronzes containing ken are used to a considerable extent in industry, under the trade name of P.M.G. alloys. Various classes of wrought alloys fall in the composition range 1.5 to 3.5 per cent silicon, and 0.5 to 2.5 per cent iron. Castings may contain as much as 6 per cent silicon and 3 per cent iron at present. The constitutional diagrams of these alloys are thus of considerable practical importance. Copper-silicon-binary alloys have been thoroughly investigated by a number of workers, the latest reports being those of C. S. Smith1 and of A. G. H. Andersen.2 Although much work has been done on iron-copper alloys,3 recorded investigations on the copper-rich copper-iron binary constitutional diagram are not numerous. Tammann and Oelsen4 etermined the solubility limits of iron in copper by means of magnetic measurements, and found that the solubility of iron in copper amounts to a fraction of one per cent at 400°C., increasing slowly to one per cent at 800°C. From 800°C., the solubility increases rapidly and attains 4 per cent at iioo°C. Hanson and Ford,5 using electrical resistivity measurements and the microscope, determined a somewhat different solubility limit. of earlier X-ray works on the copper-iron system, very little has been published. The work by Bradley and Goldschmidt6 on copper-iron-aluminum alloys includes some information on the copper-iron binary. These investigators conclude that substitution of iron in the copper lattice decreases the spacings, which is contrary to the evidence of the present work. Hanson and West? have investigated the ternary alloys of copper with iron and silicon. Although their diagrams are valuable contributions to the understanding of these alloys, they did not recognize the kappa phase,l,2,7,8 and their diagrams do not everywhere conform to the phase rule. The present work contains a check by means of X-rays of the solid solubility limit of iron in copper, and an X-ray investigation of the ternary-phase diagram, which, owing to present conditions, it became necessary to curtail considerably. Preparation of Samples Castings weighing about 75 grams were melted under vacuum. The charges were made up of ingot iron, copper cathodes from Laurel Hill, and refined silicon supplied by the Electrometallurgical Co. Alundum crucibles were generally used. The exceptions were alloys 77 and 78, which were melted in graphite crucibles. The ingots were annealed at 800°C. for one week, then samples were cut for chemical analysis. Longitudinal sections of the binary alloy ingots were hammered into plates 1/8 in. thick. Wherever possible, these plates were homogenized at temperatures ensuring

Jan 1, 1943

By Eric R. Jette, Earl S. Greiner

Although the mechanical and chemical characteristics of certain iron-nickel-silicon alloys have been investigated,1 the available literature shows no results of a systematic investigation of the constitution of this system. 'This paper describes the results of an X-ray investigation of the constitution of the iron-rich iron-nickel-silicon alloys at 600°C. Data 011 the constitution of the included binary systems obtained in other investigations have been correlated with the structure of the ternary alloys. Jette and Foote2 have presented a tentative constitutional diagram of the iron-nickel system. following X-ray studies on quenched specimens. This diagram shows that the alloys at 600°C. containing from zero to approximately 4 atomic per cent nickel consist of a body-centered cubic (alpha) phase, the alloys containing 4 to 24 atomic per cent nickel consist of body-centered cubic (alpha) and face-centered cubic (gamma) phases, and the alloys containing from 24 to Ioo atomic per cent nickel consist of a face-centered cubic (gamma) phase. These investigators recognized that it was not possible to retain the gamma phase in equilibrium by quenching alloys containing less than approximately 25 atomic per cent nickel and that high-temperature X-ray methods were desirable to determine the gamma-phase solubility limit. In a later investigation of the iron-nickel alloys, Owen and Sulley3 determined the alpha-phase solid solubility limit to be 3.5 atomic per cent nickel at 600°C. High-temperature X-ray methods showed the solid solubility limit of the gamma phase to be 14 atomic per cent nickel at 600°C. Since the high-temperature X-ray method should reveal equilibrium conditions in these alloys better than the quench method of other investigators, the results of Owen and Sulley pertaining to the gamma-phase boundary are to be preferred. As the result of an X-ray investigation of quenched iron-silicon alloys, Greiner and Jette4 have shown these materials to consist of a body-centered cubic (alpha) phase containing from o to 26.4 atomic per cent silicon at 600°C. The alloys containing from 26.4 to approximately 50 atomic per cent silicon consist of two phases at 600°C.; namely, alpha and eta. The eta phase corresponds to the stoichiometrical formula FeSi (33.4 wt per cent Si)." The literature pertaining to the constitution of the nickel-silicon alloys has been reviewed by Ackerman,' who found disagreements in the results of various investigators on several parts of the system. Subsequent data on the constitution of the nickel-silicon alloys were reported by oSawa and okamoto.6

Jan 1, 1943

By F. N. Rhines, W. S. Pellini

In many of the otherwise well established alloy phase diagrams the solidus curves (temperatures at which liquid first appears upon melting) have not been located accurately, chiefly because the experimental techniques that have been most popular for determining solidus temperatures have been both cumbersome and subject to large errors. C. E. Homer and H. Plummerl have described a sensitive and at the same time a very simple technique for locating the solidus curves in a number of alloys of tin. Their method consists simply in noting the temperature at which a specimen of the alloy ruptures under the influence of a light bending force. Although this method is not new, it has been little used for this purpose in the past; nevertheless, it appears so attractive in its possibilities of speed, simplicity, and precision that the investigations presently to be described were undertaken to verify its merits. The redetermination of the solidus and eutectic temperatures of the lead-antimony system was employed as a medium of experimentation. New values obtained in this way are believcd to be sufficiently precise to warrant a revision of the currently accepted lead-antimony phase diagram (Fig. I). Determinations of the solidus of the lead-rich lead-antimony alloy series have been published by X. S. Dean2 and by E. E. Schumacher and F. C. Nix. Their points are represented in Fig. I. In their work the solidus was not located at antimony collcentrations greater than 2 per cent; the curve was presumed to meet the eutectic horizontal at an antimony concentration of about 2.5 per cent. In the present studies the solidus has been traced to 3.5 per cent, where the eutectic horizontal is intersected (Table I and Fig. I). Within the range investigated by Dean and by Schumacher and Nix the agreement with their values is good. H. Seltz and B. De Witt,4 on the basis of activity measurements, have calculated that the intersection of the solidus and the eutectic reaction horizontal should lie at 3.86 per cent of antimony. The following determinations of the eutectic temperature have been reported: Roland-Gosselin,5 228°C.; Ewen,6 228OC.; J. E. Stead,7 24g°C.; Campbell,8 228°C.; W. Gontermann,9 245' to 252°C.; R. Loebe,lo 245°C.; E. Heyn and 0. Bauer,ll 245°C.; H. Endo,12 250°C.; R. S. Dean,= 247' to 258°C.; E. Abel, O. Redlich, and J. Adier,13 245°C.; W. Broniewski and L. Sliwowski,14 250' to 252°C.; H. Seltz and B. De Witt,4 25o°C. A temperature of 247°C. appears to have been generally accepted in recent years; it is the value most frequently obtained by the method of cooling curves. Values below 247°C. have usually been obtained by inferior cooling-curve techniques; those above 250°C., by the method of heating

Jan 1, 1943

By J. H. Frye, J. W. Caum

One of the most important methods of increasing the hardness of metals is alloying. In spite of the widespread use of alloys, the fundamental mechanism of alloy hardening is little understood. This is true even of the simplest form of alloy, the primary substitutional solid solution in which solute atoms substitute for solvent atoms at random in the crystal lattice of the latter. A fundamental understanding of the mechanism of solid-solution hardening would be important, both because of the widespread use of alloys of this type and because of the light that might be thrown on the mechanism of hardening in more complicated alloys. The present investigation covers the hardness of primary substitutional solid solutions of zinc, gallium, germanium, and arsenic in copper. All of these are B subgroup elements from the third period of the periodic table. Cu, Zn, Ga, Ge, and As are in groups I, 11, 111, IV, and V, respectively, and lie just to the right of the transition elements. Because of their cost, it is unlikely that Ga-Cu and Ge-Cu solutions will ever be of commercial importance, but the intent of this study has been to discover some of the fundamentals of solid-sdstion hardening and it has been demonstrated that such a study is far more likely to be fruitful if alloys are made up on the basis of position of the constituent elements in the periodic table than if commercially important alloys are used. Many investigations have been made of the hardness of substitutional solid solutions, but lack of attention to purity of the metals, infrequent grain-size control, and the use of varying testing techniques have virtually invalidated any comparisons. The purpose of most investigations has been to solve immediate problems and not to solve the primary problem: Why do solid solutions usually have a greater hardness than pure metals? Previous Work Theories have been advanced to account for the hardness of solid solutions, but relatively little experimental work has been done. Perhaps the first experimental work of merit was that of Norbury1 on copper alloys. He showed that for several alloys there was a correspondence between the hardness of one atomic per cent solutions and atomic volume of the solutions. More recently Brick, Martin, and Anger2 have investigated the effect of various solute elements on the hardness of copper. They concluded that the hardening effect of these solutes depended "primarily on the difference in atomic volume of solute and solvent or, relatedly, upon the parameter change of the solvent or the extent of solid solubility." They also observed the effect of these elements on hardness and texture developed by rolling and by annealing of rolled material. Austin3 examined the hardness and response to heat-treatment of various iron solid solutions. Frye and Hume-Rothery4 measured the hardness of a number of silver solid solutions containing approximately 1 References are at the end of the paper.

Jan 1, 1943

By J. H. Frye, J. W. Caum, R. M. Treco

IT has been suggested that: "Insofar as the hardening due to a solute depends upon the increase of lattice parameter produced by it, it is reasonable to suppose that this hardening might be related to the resistance which the pure solvent would offer to increase in its parameter."' It was further suggested that this hypothesis might be examined by comparing the hardnesses of analogous silver and copper alloys, since the stress necessary to produce a given lattice expansion is quite different in the two metals. Suitable data2,3,4 are now available on these alloys, and we shall proceed to an examination of the hypothesis quoted above. Hardness, Lattice Parameter and Ionic Overlap Increase in ultimate Meyer hardness has been plotted against increase in lattice parameter in Figs. I and 2. It is believed that most of the values are accurate within the limits indicated by the rectangles. These data are also presented in Table I. Ultimate Meyer hardness, P u, is defined by the equation: where L = load, D = diametei of an impression having the same diameter as the testing ball, which in this case is 4 mm. Increase in lattice parameter is defined as the difference between the lattice parameter of the solid solution and that of the pure solvent. The curves in Figs. I and 2 are based on equal solute concentration and an equal degree of plastic deformation pro duced by the testing ball. Hardnesses are corrected to a constant grain size for copper and silver alloys, respectively, and these two grain sizes are approximately equal. Furthermore, all solutes are from the same period of the B subgroup of the periodic table as their solvent. The question arises as to whether Or not lattice parameter is the only factor controlling the hardness of these alloys. There

Jan 1, 1943

By M. R. Pickus, I. W. Pickus

Ordinarily age-hardening is thought of as being associated with a limited solubility of one metal in another. Much less has been written about the type of age-hardening that attends the formation of superstructures. Solid solutions generally have a disordered or random arrangement of atoms; that is to say, in a unit cell, such as that of the face-centered cubic lattice, there is no distinction between atomic sites. Atoms of a given metal may occupy cube corners or face centers. Under certain conditions, however, some alloys develop what is known as an ordered structure. In this case, cube corners would be occupied by only one type of atom and face centers by another type. Associated with this ordering process are many interesting changes in physical and electrical properties. Moreover, in many instances the alloys become susceptible to age-hardening. From the evidence now to be described, it appears that age-hardening in 14-carat gold alloys is due to the formation of both a superstructure and a precipitate. Alloys of the metals gold, silver and copper were known in antiquity. The available knowledge regarding their constitution has been ably summarized and extended by Sterner-Rainer,' Jänecke,2 Carter,3 Wise,4 and Coleman.5 Despite the long familiarity with these alloys and the numerous investigations of their properties that have been made, there is still much that remains unexplained. It has been known for a long time that the hardness of these alloys is closely related to the rate of cooling. Similar changes have been observed in the binary gold-copper systemI6 one alloy of which corresponding to the formula CU³AU, has been the subject of a careful and competent report by the English investigators, Sykes and Evans.7 They have established the fact that the shift of atoms from the ordered to the disordered condition takes place in some critical temperature range. At temperatures above the critical range the structure is random, and at temperatures below it the structure is ordered. No difference between these two structures is revealed by the microscope. Both have a face-centered cubic lattice and complete solubility, so that there is no evidence to suggest that the changes in properties are associated with a phase change. The more slowly the alloy is cooled, the higher is the degree to which the ordering process proceeds and the more marked is the increase in hardness. As experimental data were accumulated on I4-carat gold alloys, several contradictions arose. Certain observations tended to confirm the existence of a superstructure, while other observations seemed to be inconsistent with such a transformation. Present Investigation As a focal point about which to develop this subject, it is expedient to consider first

Jan 1, 1943

By A. A. Smith, J. S. Smart

THe elements silver, cadmium, tin, antimony and tellurium either are found as impurities in commercial coppers or are intentionally added to produce coppers for special uses. When present in small quantities, each of these metals exerts a significant effect on the properties of copper, but despite considerable experience and investigation much remains to be learned about their specific behavior. The presence of extraneous elements, particularly oxygen, complicates the study of individual additions of impurities in the range o to 0.05 per cent, and the use of high-purity copper has been found extremely helpful in circumventing these difficulties. It has also been found that individual behavior can be satisfactorilv determined from measurements of two commercially important properties, conductivity and softening temperature, according to methods that have been described previously.1,2 Data of this type, obtained in the course of a general investigation of the effects of impurities on the properties of both oxygen-bearing 2nd oxygen-free copper are presented herewith. All samples except those containing cadmium were prepared as 3/8-in. continuously cast oxygen-free rod from pure copper and weighed amounts of a similarly synthesized master alloy. Composition was checked by chemical methods, which in every case verified the calculated analyses. Test wires were cold-drawn one B, and S. number per pass on a string-up machine using four 30-min. 600°C. anneals at 0.3125, 0.257, 0.204 and 0.162 in. and a final cold reduction of 75 per cent to 0.081 in. Some oxygen-bearing samples were produced directly from the 3/8-in. oxygen-free rods by diffusion from a surface scale at 850°C. and drawn to size as listed above, but most of the alloys were remelted in pure graphite and cast through air into a I-in. round mold. The slugs were then hot-rolled to 5/16 in., drawn to 0.162 in., annealed as listed above, and drawn to 0.081 inch. Conductivity wires were annealed for I hr. at 100°C. intervals between 300' and 800°F., using a hydrogen atmosphere for oxygen-free samples and purified nitrogen for the oxygen-bearing type. All samples were quenched from the annealing temperature in 10 per cent H²S04 and conductivity was measured on a Hoopes bridge that had been checked against a Kelvin bridge. The softening temperatures represent the half-hard stage of the annealing curve as determined by a standard procedure.' Effect of Silver Numerous excellent studies of the argentiferous coppers are found in the literature, and these have been adequately

Jan 1, 1943

By Clarence Zener

The internal friction of nonferrous metals vibrating at low stress amplitudes has so far always been successfully interpreted in terms of inhomogeneities of one sort or another. Examples are the fluctuation of stress across a specimen vibrating transversely,1,2,3 the stress inhomogeneities due to the elastic anisotropy and partial random orientation of the individual crystallites, localized weak regions introduced by cold-working,6'7 grain boundaries and possibly twinning planes.8'9 Perfect single crystals are, by definition, homogeneous. Actual single crystals usually, perhaps always, contains some imperfections. The present investigation was undertaken to determine whether the internal friction of single crystals may likewise be attributed to inhomogeneities. This study was made possible through the gift of a large single crystal of 70-30 alpha brass by H. L. Burghoff, of the Chase Brass and Copper Co. The specimen, 3.i in. in diameter and 10 in. long, was similar to samples previously described by Mr. Burghoff. Experimental Method The experimental method used has previously been described in institute papers.5'6'9 The measure of internal friction adopted here, I/Q, is X the logarithmic decre- ment, a measure used by some writers, and is also X the specific damping capacity, a measure used by other writers. In all measurements the stress level was kept so low that the measurements were independent of stress level. In all measurements in which the temperature was varied, observations were made as the specimen slowly cooled from its highest temperature. The specimen was vibrated transversely. Observations were made at the fundamental frequency and at the first overtone, of about 620 and 1710 cycles per second, respectively. No attempt was made to avoid acoustical losses. Experimental Results The specimen was annealed for several hours at 450°C. The temperature dependence of the internal friction was then determined from room temperature to 400°C. As shown in Fig. I, the internal friction increased by only a factor of 2 from room temperature to 300°C., then by a factor of 100 during the next Ioo° interval. These measurements are consistent with the view that the observed internal friction is the superposition of two distinct parts. One, dominant at room temperature, is nearly independent of temperature. This part may be accounted for by acoustical losses and by transverse thermal currents. It was not further investigated. The second part, when plotted in the manner of Fig. I, lies upon a straight line. Therefore it has a heat of activation H; i.e., it varies with temperature as Internal friction e-H/RT [I]

Jan 1, 1943

By Daniel R. Hull, H. F. Silliman, Earl W. Palmer

The brass-rolling industry has not had a great deal of experience with antimony in its product. There have been some recent excursions with antimony as a corrosion inhibitor in tubes, but in sheet brass it has been regarded with apprehension and generally avoided. This is not to say that contaminations have never occurred, and probably a great many brass mill men have had their own ideas on the effect of such contamination. Our own views were based upon certain experiences some years ago with strip castings that split lengthwise in the early stages of rolling. The nature of this splitting is shown in Fig. I, from a photograph taken in 1922 as a record of 20 bars of 65-35 common brass made with an antimonial brand of copper. These bars were cast 6¾ in. wide by I in. thick by 45 in. long. In the first pass through the rolls, 19 of the 20 split lengthwise throughout their length, while each half curved outward in a wide arc as it emerged from the rolls. In those days, if splitting was not a frequent occurrence, it was not unfamiliar. One can recall periods of short duration when large amounts of common brass would behave in this way. There was nothing imaginary about these spells. The affected metal would split lengthwise in the breakdown rolls, and no maneuvering of mill practice made any difference. The condition would descend like a plague, demoralize the mill for several days, and disappear. It is doubtful if anyone knew the cause—however many explanations may have been current. In 1921 a quantity of split brass was traced to the use of fired small-arms

Jan 1, 1943

By Cyril Stanley Smith

BeTa brass (consisting of approximately equal atomic proportions of copper and zinc) exists as a random solid solution at high temperatures, hut at low temperature< an ordered structure is stable, with the copper and zinc atoms occupying alternate sites on the body-centered-cubic lattice. On cooling, ordering commences at a temperature of 450° to 470°C., depending on the composition. The degree of ordering progressively increases at lower temperatures until it becomes virtually complete at about 100°C. The electrical resistivity of the alloy illustrates the changes clearly (Fig. I). This type of reaction has been a favored subject for study by physicists. An excellent summary of the theory is to be found in a paper by F. C. Nix and W. Shock1ey.l All published data on electrical conductivity, specific heat and other properties agree in indicating that the ordering reaction in beta brass takes place so rapidly that it cannot be prevented or even retarded by quenching&apos; With most ordered alloys, cold-working induces disorder and

Jan 1, 1943

By G. D. Cremer, J. J. Cordiano

Aluminum powder is a well-known article of commerce and in various forms has been marketed widely for use in paint, for pyrotechnic purposes and for exothermic mixtures. For a number of reasons, however, aluminum powder has not been employed extensively in powder metallurgy, although a great many proposals along this line have been offered. Aluminum and alumiuum-alloy powders oxidize readily upon exposure to air and the thin film of oxide (or hydroxide) thus formed is highly refractory, in that ordinary gaseous reducing agents such as hydrogen or carbon monoxide do not reduce the oxide to metal at temperatures below the melting point of aluminum. It has been thought that the presence of these films of oxide on aluminum particles would interfere markedly in powder metallurgical work and a number of suggestions have been made, either for preventing the formation of the film through the production of the powders in inert or reducing atmospheres, or for the removal of the oxide by means of powerful reducing agents, including "nascent" or atomic hydrogen released from metal hydrides. A second and more serious difficulty in the use of aluminum and aluminum-alloy powders in powder metallurgy resides in the fact that during compression such powders tend to adhere or cold-weld to the die walls, thus interfering with the formation and ejection of a compact. A third difficulty, which has been encountered only with aluminum-alloy powders, is their hardness when compared with elemental aluminum. Certain of these powders are susceptible to age-hardening, which further hinders the formation of strong green compacts. These conditions are particularly true of atomized aluminum-alloy powders. Even in the annealed condition, plastic deformation of alloy powders under pressure is low when compared with unalloyed powders. This fact, coupled with the lower corrosion resistance of the alloy powders. is probably the significant factor in our failure to obtain strong sintered pieces. Methods of Puoducing the Powder Many methods have been proposed for manufacture of aluminum powder, only a few of which are used commercially. Several of the more important processes include: (I) atomization of the molten metal; (2) mechanical pulverization and other types of comminution; and (3) graining, in which molten aluminum is stirred during freezing. For pigment and certain pyrotechnic uses aluminum flake powder is desirable, because of its greater proportion of surface to volume; and large quantities of such material are made by a procedure that involves stamping or ball milling. In making flake intended for use as pigment,

Jan 1, 1943

By Lawrence K. Jetter, Robert F. Mehl

Some advances have been made recently in the theory of the kinetics of precipitation from metallic solid solution despite the complexities of the problem, but there is surprisingly little quantitative information available on rates of precipitation with which to test present theory or upon which to build new theory. Attempts to measure rates of precipitation have been beset with difficulties which originate both in the anomalies that attend the changes in the properties selectcd for measurement, as, for example, in electrical conductivity or mechanical properties, and also in the complexities in the structural changes in some systems, as in the aluminum-copper system. If the functional relationship between the quantity of precipitate and the value of the selected property is uncertain, measurements of that property are obviously of uncertain utility in determining absolute rates of precipitation. If the precipitating system passes through one or more transition stages, the interpretation of measured rates lacks definiteness; in such cases, it is necessary to measure the rate of reaction in each separate stage, if the rate measurements are to have any significance from the kinetic point of view.* These difficulties cannot be wholly avoided, for at least in some measure they are characteristic of the process of precipitation from solid solution, but they can be minimized both by the selection of a simple system and by the use of a method of measurement relatively free from anomalous behavior. The present paper reports dilatome tric measurements on the rate of precipitation of silicon from the aluminum-rich solid solution in the aluminum-silicon system—a study that approaches the desiderata of simplicity. The aluminum-silicon system offers advantages from these points of view: there are no known anomalies in the property changes accompanying precipitation; there are no known transition stages; the precipitate is an element, not a compound, and both matrix and precipitate are cubic, and while the structures are not identical (the solid solution is face-centered cubic and the precipitate is diamond cubic), the system at least approaches the ideal case of a crystal precipitating from a matrix of the same crystal type—the ideal case which Becker6 assumed in treating the precipitation process theoretically. The dilatometric method, while not free from disturbing effects, as the subsequent dis-

Jan 1, 1943

By A. H. Geisler, R. F. Mehl, C. S. Barrett

The mechanism by which the supersaturated solid solution of 20 per cent silver in aluminum decomposes has been reported in two previous publications.1&apos;2 The analysis of streaks in Laue photograms showed that thin platelike particles (the so-called Guinier-Preston aggregates) form upon matrix planes in the early state of decomposition.1 The size of these particles is larger, the higher the temperature at which they form in accordance with nucleation theory;³ at all temperatures they increase in size with aging.2 When they have grown thick enough to afford three-dimensional diffraction, powder X-ray photograms show that the structure is not that of the equilibrium precipitate but that of a transition lattice . Sincc this is also platelike in shape and also lies upon the (III) matrix planes with the [IIO] direction in the matrix parallel to the [II.O] direction in it seems likely that the original platelet particles are merely in an early stage of formation, and thus finely dispersed. The atomic spacing and pattern on the (00.1) plane in y&apos; are identical with those on the (111) matrix plane to which it lies parallel, and since comparable directions in the two planes are parallel, the lattices are thus coherent at the interface; an analogous coherence has been found in aluminum-copper alloys.3 The structures y&apos; and y are both close-packed hexagonal and are oriented alike; they differ only in interatomic distances. Consequently, y&apos; is regarded as y strained from its ordinary dimensions by the lattice coherency between it and the matrix.2 The lattice movements that transform the matrix to the equilibrium precipitate appear to be very simple.2 The mechanism of precipitation in this system is simpler and is more precisely known than that in any other system hence the system should be a profitable one for the difficult task of correlating property changes with structural alterations. The present report provides additional studies on powder X-ray diffraction from alloys of 10 per cent, 20 per cent and 30 per cent Ag, and presents the correlation of crystallographic changes with changes in microstructurc, Brinell hardness and electrical resistivity of the three alloys. Preparation of Samples and Experimental Procedure The preparation of the 20.2 per cent Ag alloy has been described2 Alloys containing 9.9 and 29.7 per cent Ag were prepared from 99.97 per cent A1 and 99.99+ per cent Ag using a similar procedure. Rolled

Jan 1, 1943

By A. H. Geisler, R. F. Mehl, S. Barrett

The studies of the mechanism of pre= cipitation and of the resulting property changes in aluminum-silver alloysl-3 have presented some new concepts of the aging reactioxl—concepts that may be fundamental in establishing a complete quantitative theory of age-hardening. With both aluminum-copper and aluminum-silver alloys, thin platelike aggregates form parallel to the Widmanstätten planes of precipitation.l,4 These platelets grow in lateral dimensions and in thickness with aging time until they arc thick enough to produce an X-ray diffraction line pattern. Their structure is that of a transition lattice which is coherent with the matrix, since the atomic spacings in the matrix and the precipitate are the same on each side of their common interface.2,4 The equilibrium precipitate forms later from and at the expense of the transition lattice. Since age-hardening occurs during the formation and growth of the transition lattice, the major contributor to the hardening no doubt is the stress condition in the matrix resulting from the matrix holding the precipitate in the coherent condition. The development of these stresses also appears to be responsible for an increase in the electrical resistance superimposed on the normal decrease resulting from a change in the concentration of the matrix during aging.3 The two consecutive reactions constituting the aging process are accompanied by characteristic microstructural alterations. The initial precipitation process results in the formation of a Widmanstatten figure, while the later transformation of the transition lattice to the equilibrium lattice is accompanied by a coalescence, in the case of aluminum-copper alloys,5 and by the appearance of light areas at the grain boundaries with aluminum-silver alloys showing a structural rearrangement of matrix and precipitate.3 This latter reaction is similar microscopically to the so-called "discontinuoils precipitation." Possibly discontinuous precipitation is a process that often if not always follows true precipitation of a coherent lattice and during which the transformation of the coherent transition lattice to the equilibrium lattice takes place accompanied by matrix recrystallization.3 Expermental Procedure The alloys were made using 99.97 per cent A1 or distilled magnesium, with

Jan 1, 1943

By C. H. Mathewson, P.W. Bakararian

The greatcr part of the literature on the plastic behavior of magnesium dates back to that active period of research in crystal mechanics immediately following the widespread preparation of isolated metallic crystals large enough for the application of conventional methods of mechanical testing. These investigations, performed on single crystals, revealed an analogy between zinc and magnesium with respect to their fundamental mode of deformation. in the operation of glide and twinning, respectively, on crystallographically similar planes. Mathewson and Phillips (1928)&apos; by geometrical analysis identified the plane in magnesium as the twinning plane. Schiebold and Siebel (1931) confirmed this twinning planc, established the basal plane as the plane of slip, and a digonal axis I as the slip direction. They also rcported twin formation in a secondary role on the {IOI} plane. Schmid (1931)³ summarized and discussed the earlier evidence and presented the results of his own experiments on the effect of temperature and small amounts of soluble elements. From X-ray studies on extended wire single crystals, he concluded that slip along the basal plane in the direction of the digonal axis I closest to the stress direction was the sole slip system operating at atmospheric temperature. This conclusion was based on experiments with crystals of many different orientations relative to the stress axis. Special attention was directed to the basal plane and the digonal axis I, as the plane and direction of greatest atomic density. Determinations of resolved shear stress at the onset of plastic yielding-—i.e., the critical resolved shear stress—were also made; the average of these calculations showing 82.9 grams per sq. mm. This value varied only slightly up to 300°C. at which temperature it was found to decrease to 70.5 grams per sq. mm. The extension of his crystals at temperatures above 225°C. further disclosed the presence of new slip systems. After the origince specimens of circular section had been

Jan 1, 1943

By Welton J. Crook

Unless present, in considerable praportion, metals of the precious-metal group—other than gold and silver—are not readily detected by the methods of fire assaying usually applied to ores and metallurgical products. Platinum, when present in small quantity, will ordinarily be reported as silver unless special methods of parting are used. Other elements occurring in the gold itself are all fluxed and slagged in the assay operation and if analyses are made on bullions the melting and slagging operations to which the bullion has been subjected may eliminate most of the associated elements. On the other hand, the analysis of precipitate from the cyanide treatment of gold ores may reveal the presence of many unexpected elements, such as tungsten and molybdenum. It is uncertain, however, whether many of the elements present in the precipitate are derived from the ore gangue or from the gold itself. No very general survey of the distribution of metallic elements in gold seems to have been made. Rose and Newman,l in connection with the composition of native gold, say in part as follows: Gold is occasionally found alloyed with copper and sometimes also with iron, bismuth, lead, mercury, tin, antimony, palladium or rhodium. Rhodium gold from Mexico was found to be of the specific gravity 15.5 to 16.8 and contained 34 to 43 per cent of rhodium. The native alloy of palladium, gold, and silver from Porpez contains 85.98 per cent of gold, 9.85 per cent palladium and 4.17 per cent silver. Mal-donitk, from Victoria, contains gold 64.5 per cent, bismuth 35.5 per cent (Louis). Dana2 says that native gold is usually alloyed with silver in varying amounts, and that sometimes it also contains traces of copper and iron. Rare varieties contain palladium, rhodium and bismuth. Other authors, for instance Zeigler3 and Clark,4 give similar information. Most references on the subject agree that ordinary native golds contain, in common, the elements silver, copper and iron. After completion of the work of which this paper is a record, the conclusion is reached that all ordinary native gold probably does contain these elements and, although in certain cases other elements may be found to be present, that it is difficult to

Jan 1, 1943

By E. R. Parker, D. L. Martin

During the heat-treatment of silver specimens for tensile tests it was observed that the bars blistered and became brittle when heated in a hydrogen atmosphere. To check this unexpected result, a wide variety of commercial silvers were heated in hydrogen at 850°C. Only a few of the materials developed blisters, the most severe of which is the tube pictured in Fig. I. The microstructure of a cross section of the tube is shown in Fig. 2. The embrit-tlernent is extremely severe at the edge; the blisters result from the severe deformation of the surface material by large under- lying gas pockets. The effects resulting from hydrogen embrittlement of silver have been observed by numerous investigators over a long time l,2,3 although it was only recently that a clear explanation was offered.4 However, the damage resulting from hydrogen embrittlement has not been generally recognized; and it is of advantage to know more about this phe- 1 References are at the end of the paper.

Jan 1, 1943

By A. M. Hall

Sulphur, even in small amounts, may often be harmful to nickel and high-nickel alloys, causing impairment of mechanical strength and destruction of malleability and ductility, as shown by Merica and Waltenberg.l,2 It may act either in the form of nonmetallic inclusions produced in the liquid state during furnacing or as reaction products resulting from its diffusion into the solid metal. In recognizing the action of this element, ability to identify its various forms by means of the microscope is often of considerable importance, especially when direct quantitative methods are inapplicable. Of the sulphur compounds associated with nickel and high-nickel alloys, the sulphides that may be found in malleable nickel, Monelt and Inconel are an important group. These sulphides were investi- gated by metallographic methods in order to provide descriptive data by which to identify them. The nominal compositions of malleable nickel, Monel and Inconel are given in Table I. The term "sulphide" is employed here in a very general sense, to designate a substance in which sulphur and one or more metallic elements are combined. The term includes any combinations of compounds and solid solutions. Method of Investigation Three groups of small laboratory melts were made, one group to represent each of the three types of alloy under investigation. Within each group, a number of ingots with a sufficient variety of chemical analyses were prepared so that the effect of each of the elements entering the complete commercial alloy could be isolated and observed. In most cases, to facilitate metallographic study by exaggerating the number and size of the resulting sulphides, somewhat greater amounts of the minor elements were added than are present in the commercial alloys. Likewise, considerably more sulphur was added than is normal, but not enough to complicate the system. Transverse sections were cut at a point one third of the distance from the butt to the head of each ingot, polished and examined with an inverted stage metallo-graph equipped with a combination polar -izing-analyzing vertical illuminator. The light source was a tungsten-mercury vapor arc lamp.

Jan 1, 1943