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By D. Van Winkle, C. Zener, H. Nielsen

THe internal friction of metals has been studied frequently at elevated temperatures.1-4 In most cases it rises rapidly with increasing temperature. The notable exceptions are ferromagnetic materials, and lead.2 This paper describes an investigation of the general features of the high-temperature internal friction of 70-30 alpha brass. Experimental Method The internal friction of a metal is a measure of the rate at which it dissipates energy of vibration. The measure adopted here, I/Q, is (I/2p) times the specific damping capacity, a measure commonly used by engineers. In the measurements of this investigation, the stress level was kept so low that the observations were independent of the stress, The general method of making such measurements, and of observing temperature of a specimen during a measurement, has been described.5.6 The driver and detector coils were wound with wire insulated with glass thread, in order to withstand the high temperatures used. In previous work electrical eddy currents in the specimen served as the coupling between the mechanical vibration of the specimen and the electrical circuits of the driver and detector. The high values of the internal friction in the present investigation rendered this coupling insufficient. In order to increase this coupling, pole pieces cut from ordinary telephone diaphragms were attached to the specimen. A mixture of French chalk and water glass proved a satisfactory cement. All measurements were made at the fundamental frequency for transverse vibration, which lay between 600 and goo cycles per second. Specimens The measurements described herein were made upon a single cylindrical rod of brass, kindly furnished by Dr. Cyril Stanley Smith, of the American Brass Co. This rod was the specimen E of the set of alpha-brass rods described in an earlier paper.6 Successively larger grain sizes were obtained by annealing at .successively higher temperatures. A slice was cut off one end after each set of measurements. Grain counts were made on each slice by W. E. Lindlief, of the American Brass Co. Nine fields were viewed on each piece, located as shown in Fig. I. Results are given in Table I. The grain size is defined in the usual way; namely, Grain size = I/n1/2 where n is the mean number of grains per square millimeter. Experimental Results This paper is concerned exclusively with the part of the internal friction that be. comes dominant at high temperatures. It is thus desirable to separate this part of the internal friction from the part that is

Jan 1, 1942

By E. O. Kirkendall

The investigation reported herein was undertaken to obtain data to supplement those presented in an earlier paper,l particularly for longer times at a higher temperature. This information may further develop our knowledge of the mechanism of diffusion in substitutional solid solutions. Diffusion of solute atoms interstitially dissolved is not difficult to visualize: it can take place without much disturbance of the solvent atoms. The mechanism of diffusion of solute atoms substitutionally dissolved is not so easily understood. Many theories have been advanced. Rosen-hain,2,3 Frenkel,4 Smekal,5 Langmuir,3,6 Steigman, Shockley and Nix,' and Johnson8 all proposed theories to explain diffusion. Langmuir's proposed mechanism consisted of a simple cyclic interchange of atoms involving an interchange in lattice positions of four or more atoms. This mechanism, accepted by the author at the time of his previous publication,1 and apparently quite generally accepted, required a net exchange in positions of both solute and solvent atoms in equal numbers. In other words, the rate of diffusion of the solvent and solute atoms would be the same. That this cyclic interchange in lattice positions of solute and solvent atoms in equal numbers is the only true mechanism of diffusion is denied by the evidence presented in this paper. Experimental Procedure This modification of similar procedure1 will be outlined briefly. The method consisted of the following steps: I. A pure Muntz metal (60.6 per cent Cu, 0.1 per cent total impurities) that was almost all beta brass at 780°C. was chosen. 2. The brass was turned between centers in a lathe to a diameter of 0.5965 inches. 3. After the brass was cleaned, it was electroplated with pure copper to a diameter of about one inch. 4. The sample was heated slowly to 400°C. under reduced pressure and held at that temperature for 4 hr. to remove occluded gases. It was then cooled to room temperature. 5. The sample was heated to 780°C. ± 3°C. and held at that temperature for different lengths of time; then quenched. Samples were cut off each time after quenching. Metallographic samples 1/4 in. thick were removed at I hr., 6 hr., 24 hr., 96 hr. and 701 hr. After 96 and 701 hr. samples of about I in. were removed for X-ray analysis. 6. The metallographic samples were polished on the cross section and photomicrographs were taken. 7. The I-in. samples were polished and etched on both ends. With the aid of a microscope each was carefully mounted in a four-jaw chuck in a lathe, so that they could be accurately bored for an arbor. 8. Turnings were taken for each X-ray sample. After each set of turnings, the sample was heated in an oil bath for about 1/2 hr. at 300°C. It was then etched in 25

Jan 1, 1942

By Cyril Stanley Smith

On the 6th of February 1684, Dr. Martin Lister mentioned at a meeting of the Royal Society1 that "brass is magnetical," and promised to give an account of that assertion at some other time. He repeated his promise but never fulfilled it, and it was left for William Arderon2 to show, in 1758, that brass could be made magnetic by hammering and that it would retain polarity after magnetizing. Twenty-seven years later Caval103,4 examined the matter in great detail. Working with cast calamine brass, he showed that it could be made magnetic by hammering and nonmagnetic by subsequent annealing at a red heat. He found that annealing at a very high temperature caused the samples to lose their magnetic quality permanently, even after subsequent cold-working, but that remelting and cold- working restored it. He encountered some samples of brass that could not be rendered - magnetic by any treatment. Experiments in which these were remelted with iron additions gave negative results, and Cavallo concluded that iron impurity was not the cause of the magnetism. He worked with 50-grain (3-gram) samples melted under the blowpipe, hence cooled very quickly. Bennet5 made whole crucible charges from copper and zinc, and found _ the resulting brass ingots to be magnetic only when iron had been added and then only after cold-working. All these observations applied to material in the cast condi- tion, in which coring would produce a continuous spectrum of composition and cooling would result in varying degrees of precipitation. This knowledge of the subject seems to have been forgotten in the nineteenth century. The older brass was made by the calamine process and frequently contained iron in amounts of 0.5 per cent or more, absorbed from the impure ore with which the copper and charcoal were heated in making the brass. When metallic zinc became available in commercial quantities, calamine brass gradually disappeared, and with it the knowledge of its curious magnetic properties. Only when sensitive apparatus replaced the compass needle of the earlier investigators could the effects be detected in relatively pure metal. The effect of cold-working in inducing ferromagnetism was rediscovered by Bitter8 in 1930 in a sample of impure copper, and this was confirmed by Lowance and Constant: Honda and Shimizu, l0,11 and others. In the same year, Tammann and Oelsen12 showed that copper-rich copper-iron alloys after certain heat-treatments could be rendered ferromagnetic or made more strongly ferromagnetic by cold-rolling. Kussman and Seeman13 showed that the change of susceptibility of relatively pure copper on cold-working was associated with the iron content, and concluded that actual precipitation of iron was caused by cold-working, which is a satisfactory theory until one considers the improbably high rate of diffusion that this would involve. When studying precipitation phenomena in

Jan 1, 1942

By R. G. Treuting, R. M. Brick

Despite the basic importance of slip in the plastic deformation of metals, and the considerable experimental investigation, thought, and speculation that have been devoted to the fundamental nature of these processes, surprisingly few data have been reported regarding the microscopic appear- ance and distribution of slip lines,‡ the external manifestation of the slip process. Photographs hitherto reproduced in the literature are in general at low or unspecified magnifications with no correlation to the prior shear. A single-crystal cylindrical tensile specimen of alpha brass about 1/2 in. in diameter, one of many previously prepared by H. L. Burghoff,1 was available for study. A plane about 3/16 in. wide, parallel to the specimen axis and normal to the plane containing the slip direction and the specimen axis, was ground and metallographically polished along the entire 5-in. gauge length. Heavy etching produced a surface free of both scratches and flow. The specimen was strained in tension until slip markings first became visible on the polished surface (Figs. 1 and 2). Re-stressing the crystal caused additional markings to appear at an initially lower stress than previously was required. Stretching the specimen to produce a dense concentration of slip lines caused such variations in level in the polished surface (normal to the slip direction) that microscopic study at higher magnifications became impossible. After annealing 15 hr. at 850°C, the specimen recrystallized to form two grains with a boundary approximately normal to the specimen axis and about midway along its length. Each was X-rayed, and two planes were again polished along the length of the specimen, in this case each parallel to the slip direction in one of the two crystals. A light longitudinal scratch parallel to the specimen axis was drawn down the center of each plane. A Huggen-berger extensometer was attached to the crystal A, whose slip plane would have the higher resolved shear stress of the two, and the specimen was again strained in tension.

Jan 1, 1942

By William B Price, Ralph W. Bailey

Arsenic, antimony and phosphorus are now used in the brass industry as standard inhibitors in preventing dezincification in condenser tubes. This subject has been thoroughly covered by Barry,l who de- scribed the testing procedure by total immersion of suitable specimens in a I per cent cupric chloride solution at definite temperatures. Effects of dezincification were then determined by loss in tensile strength and elongation of the test specimens after definite periods of immersion. In the crystallography of the chemical elements as tabulated by William Hume-Rothery,2 phosphorus (metallic), arsenic, antimony and bismuth are placed in group V-B and the type of crystal lattice for arsenic, antimony and bismuth is given as rhombohedral. The Metals Handbook3 lists them as 'rhobomhedral hexagonal," with the additional notation that for arsenic this is the ordinary form at 20°C.; other modifications known or probable at other temperatures. In view of these statements and of the fact that phosphorus, arsenic and antimony are effective in increasing the resistance to dezincification, it was natural to assume that bismuth would act in the same manner. A series of tests was therefore carried out employing the methods described by Barry. Much to our surprise, bismuth did not inhibit dezincification, but rather seemed to accelerate it. Tensile-test speci-

Jan 1, 1942

By H. l. Burghoff, E. C. Bohlen

The work reported in this paper was carried out to supplement the existing information concerning directional properties and recrystallization textures of annealed brass sheet and strip. These characteristics are of direct interest when the forming and drawing properties of such material are being considered. Among those who have made contributions in this field are Bass and G1ocker;l Bauer, Göler and Sachs;2 Phillips and Samans;3 Pratt;4 Price;5 Cook;6 Richards;7 Brick;8 and Brick and Williamson.9 These investigators have found, in general, that in brass strip that shows directional variations in properties, tensile strength has a minimum value and elongation has a maximum value at 45' to the rolling direction. The most pronounced directional properties have been found in material given the greatest reductions in rolling followed by high annealing temperatures. Recrystallization texture of brass has been variously reported as (II3)[II2], (ooi)[ioo], and a combination of (II0)[II5] and traces of the primary rolling texture, (110)[112]. The directional studies have been very informative, but actual tests appear to have been confined to material in its final condition. Tests at intermediate stages have received little attention although previous history of some materials has been partly considered. Perhaps the most comprehensive investigation was made by Cook,' who studied the directional properties of 70-30 brass strip for which the final and penultimate, or next to the last, anneals and the final reductions were varied. He found that, for any given combination of penultimate anneal and final reduction, the tendency toward the development of directional properties was reduced as the temperature of the final anneal was decreased. In addition to drawing cups and making tensile tests of the finished material at various angles to the rolling direction, he measured the frequency and the angles of twins in grains for several specimens. Plots of his twin counts showed directionality for the materials that produced eared cups. Test Materials and Equipment For this investigation, one commercial heat of 68-32 brass was cast in the form of bars for cold-rolling, I31/2 in wide and I1/2 in. thick. The analysis was as follows: 68.83 per cent copper, 0.04 per cent lead, 0.01 per cent iron, 31.12 per cent zinc (by difference). The bars were so processed to the final thickness, 0.020 in., as to obtain on this thickness all possible combinations of the variables listed below except those involving the sequence of 84 per cent penultimate reduction and 84 per cent final reduction: I. Penultimate reductions of 37 per cent, 50 per cent and 84 per cent; 2. Penultimate anneals at 800°, 900°, 1050° and 1200°F.; 3. Final reductions of 37 per cent, 50 per cent, 69 per cent and 84 per cent;

Jan 1, 1942

By Earl W. Palmer, Cyril Stanley Smith

StKip of any of the metals used for deep drawing operations occasionally yields cups that are defective because of a rim that varies in height around the cup in a wave-like manner. Some such defects are traceable to tools or other press factors, but when the protuberances formed (usually four in number on brass and other copper alloys) are symmetrically disposed with respect to the rolling direction of the strip, they are invariably attributable to the metal. The effect is known as "earing" and the protuberances are called "ears." Other terms frequently heard are "tips," "scallops," and "corners." It is recognized that the effect is most commonly a result of a directional crystal structure produced by rolling and annealing operations in the manufacture of the metal strip. Numerous papers dealing with various aspects of the earing effect have appeared in the literature, those listed in the references1 being especially interesting and valuable. An investigation of the factors influencing earing of brass cups has been in progress in the laboratories of the American Brass Co. for several years, and it was thought desirable to make some of the results generally available in summarized form. The present paper discusses many factors that do and do not contribute to ear formation. In addition, a section is devoted to methods of minimizing the earing tendency of brass sheet by proper selection of the cold-rolling and annealing schedule by which it is produced. In the space available, it is impossible to quote detailed experimental procedures and numerical results. However, the authors make no statement that they do not believe to be properly substantiated, either by experimental evidence obtained under laboratory conditions or by experience in the actual production of deep-drawing brass in the brass mill. Mechanism of Ear Formation It must be clearly understood that the formation on cups of symmetrical ears, four or more in number, is attributable solely to the strip metal, and results from the strip having different deformation characteristics in different directions. The tools used in the drawing process, or the type and completeness of lubrication of the strip, have nothing to do with the problem of ears, although they do, of course, greatly affect the "drawing quality" of the strip and the general appearance of the cup. A single tip may be drawn up on the rim of a cup because of misalignment of the tools, or because the gauge of metal varies from side to side of the strip. The two-ear form that sometimes appears is also traceable to gauge variations. However, the four-ear and six-ear symmetrical forms that we are concerned with here are caused by factors inherent in the structure of the metal itself.

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 W. A. Johnson, F. N. Rhines, W. A. Anderson

The rate of the high-temperature oxidation of pure copper has been measured repeatedly by numerous investigators. It appears to be generally agreed: (I) that at constant temperature, after the initial stages of oxidation have been passed and the scale has attained a substantial depth, the film thickness increases in proportion to the square root of the time of oxidation; and (2) that for any given period of oxidation the logarithm of the square of the film thickness is proportional to the reciprocal of the absolute temperature of oxidation.' These relationships are explained upon the basis that the rate of diffusion of copper to the external surface of the film is the controlling factor in establishing the rate of growth. Extensive studies have been devoted also to the mechanism and rates of the early stages of oxidation. There is thus available a reasonably well established theory of the oxidation of pure copper upon which to construct an explanation of the more complex oxidation of copper alloys. Few general principles have as yet emerged from the chaos of observations that have been reported in the field of the oxidation of alloys.2 It is evident, however, that the copper alloys may be divided into two main groups, whose oxidation characteristics are distinguish- able. The first group, composed of the alloys with the noble metals, forms substantially pure copper oxide scales; the alloying element is concentrated within the residual metal, and sometimes particles of almost pure noble metal are found in the scales completely surrounded by copper oxide. In the second group, composed of the alloys of copper with the baser metals, the alloying element appears as an oxide in the scale, often in greater concentration than in the alloy itself and sometimes to the exclusion of copper oxide. The oxide scales of the latter class have been found to be made up of one, two, and sometimes more distinguishable layers of which the innermost is often metallic in character, composed of particles of the oxide of the alloying element embedded in essentially pure copper and known as the subscale or zone of internal oxidation. The need for a thorough quantitative study of these modes of oxidation is evident. Since it is apparent that several mechanisms must be cooperating to produce the complex oxide scales found on copper alloys, the analysis of the process into its several simple operations should prove instructive. Fortunately, it is possible experimentally to produce internal oxidation in the absence of an external scale; this permits the isolation and intensive study of one of the steps in the oxidation process. In the present research the rates of internal oxidation of an extensive series of dilute solid solution alloys of copper have been measured and a theory has been developed to predict the observed

Jan 1, 1942

By Walter R. Hibbard, Cyril Stanley Smith

IN 1929 one of the authors1 determined the constitution of copper-silicon-manganese alloys contailling over go per cent copper. Through a combination of circumstances the presence of the copper-silicon kappa phase was overlooked in both binary and ternary systems. In the binary system the omission has already been rectified.2,3 To establish the limits of this phase in the ternary system, the samples that had been heat-treated at the time of the original research have now been re-examined, using more careful technique. Full details of the compositions used and the temperatures and times of heat-treatment are to be found in the earlier paper.2 The etching reagent now used to distinguish the kappa phase had the following composition: hydrogen peroxide (30 vol.), 2o c.c.; water, 25 c.c.; 20 per cent potassium hydroxide solution, 5 c.c.; ammonium hydroxide (0.90 sp. gr.), 50 c.c. 'I'able I lists the newly observed structures. In virtually every case the constituents are the same as those previously recorded, except where kappa is now shown to be present as a result of the improved etching technique. X few other changes will be noted (No. 138 at 450°C., No. 147 at 550°C., Nos. 153 and 149 at 75o°C.). The change from liquid to beta in equilibrium with kappa in No. 137 at 800°C. is based upon newly heat-treated samples. The alloy is very near the solidus at 800°C. and probably there was a slight error in the old heat-treatment temperature. The isothermal phase diagrams shown in Figs. I to 6 were reconstructed on the basis of the new studies. The presence of manganese does not greatly change the composition limits of the kappa phase or cause the K-a + Y change to occur at a markedly different temperature. There is some uncertainty regarding the range of existence of beta, for alloys were not spaced very closely in composition. The proposed diagrams, however, are in accordance with the available experimental data and with the dictates of the phase rule. Theoretically necessary fields with no experimental points are delineated by dotted lines. The alpha boundaries at all temperatures are shown together in Fig. 7. This includes also some additional points on the alpha boundary at 300' and 350°C., which were obtained as a result of electrical-conductivity measurements. Two series of seven alloys with increasing manganese content but with silicon constant at 1.90 + 0.03 per cent or 2.42 ±. 0.05 per cent were cast in ingots of 3-in: diameter. These were hot-rolled, homogenized and drawn to wire, finished at 0.08-in. diameter with a 61 per cent reduction of area following annealing at 700°C. Conductivity determinations were made before and after annealing for 30 days at 300°C. or 21 days at 350°C. Figs. 8 and 9 show the change of conductivity produced by this annealing, plotted against manganese

Jan 1, 1942

By Alan U. Seybolt

In examination of some cold-rolled copper and cupronickel that contained a little columbium, it was discovered that these alloys were unusually resistant to annealing. This effect was suficiently pronounced to warrant some investigation of the annealing characteristics of such compositions. Experimental Procedure The alloys were made from cathode copper, electrolytic nickel, and a special copper-columbium hardener alloy furnished by the Electro Metallurgical Corporation. This hardener alloy contained 10 per cent columbium, with tantalum, aluminum and iron as major impurities. The melting was carried out in a clay-graphite crucible in a high-frequency induction furnace! under a charcoal or electrode carbon cover. No deoxidizing additions were made. The 7-lb. copper heats were poured into a steel mold, hot-rolled to 1/4-in. thickness, and annealed for 56 hr. at 760°C.; the cupronickels were annealed I hr. at 815°C. The material was then cold-rolled to a 50 per cent reduction in thickness and annealing tests were carried out on this 1/8-in. hard-rolled strip. A little silver was added to copper-columbium alloys 402 and 403 to find out

Jan 1, 1942

By Ralph Hultgren, Louis A. Carapella

When F. Heuslerl found in 1898 that certain alloys containing only copper, manganese, and tin were ferromagnetic, the discovery excited a great deal of interest and led to numerous investigations. It was early found that tin could be replaced by aluminum, arsenic, antimony, bismuth, or boron without destroying the ferromagnetic nature of the alloys.2 Copper may also be replaced by silver.% All these alloys have come to be known as "Heusler alloys." The aluminum alloys apparently were the most magnetic and have been most extensively investigated. However, no agreement has yet been reached as to the source of the ferromagnetism arising from these nonferromagnetic elements. Absence of reliable quantitative data makes speculation hazardous. The value of much of the earlier work was vitiated by lack of necessary precautions against contamination, and by lack of close control of heat-treatment. It was only recently established that in aluminum Heusler alloys4 the ferromagnetism arose from a single phase, an ordered body-centered-cubic structure. With modern methods of preparation, heat-treatment, and X-ray examination, it is possible to prepare these alloys without contamination, to heat-treat them intellgently, and to determine what phase or phases are present in the finished sample. In the present investigation, a series of pure alloys in the comparatively neglected copper-manganese-tin system have been prepared, which consist of a single, body-centered-cubic structure (the beta phase) and whose compositions vary within wide limits. The magnetic saturation values of these single-phase alloys have been quantitatively determined, so that considerable data on the effect of composition on the ferromagnetism have been made available. In the course of the investigation some information on the extent of the stability of the beta phase and the nature of phases in adjacent regions of the ternary diagram has been accumulated. Anomalies in earlier data. have been explained, and alloys have been prepared that are much more strongly magnetic than any previous Heusler alloys. Previous Work In the original work of F. Heuslerl and coworkers,2 a maximum magnetic saturation value of I = 107 was found at the composition Cu6Mn3Sn, while a value for CusMnAl of I = 443 was early measured. Ross and Gray5 found a second maximum at the composition Cu2MnSn, which was much more magnetic than Heusler's original alloy. F. Heusler6 hen reinvesti-gated the system, confirmed their results,

Jan 1, 1942

By Alfred H. Hesse, Edwin T. Myskowski

The development by the U. S. Bureau of Mines of a process for purifying manganese by electrolysis has stimulated interest in manganese alloys. While recent publications have shown some alloys of manganese and copper to possess rather unusual properties, none have included information on tensile properties, which have an important bearing on the usefulness of the alloys. Manganese-copper alloys can be heat-treated, since the single phases that exist at high temperatures may be retained by quenching. According to Persson,1 when quenched alloys containing from about 30 to nearly IOO per cent manganese are reheated, alpha manganese is precipitated (Fig. I). Calculations based on Persson's X-ray data indicate that this decomposi-tion is accompanied by a change in volume of as much as ; per cent. The reason that this large volume change has not been noted probably is the slow rate at which equilibrium is reached by these alloys. In an investigation on hardening by cold-work and heat-treatment, Dean and Anderson3 found that quenched alloys increase in hardness with manganese content and that high-manganese alloys harden very slowly with cold-work, while high-copper alloys harden much more rapidly. Heat-treatment has little effect on manganese-copper alloys containing less than 40 per cent Mn, and affects those alloys containing more than 40 per cent in accordance with their manganese content and heat-treating temperature. Dean and Anderson4 also found that cold-work increased electrical resistance of alloys containing from 50 to 80 per cent Mn, and that heat-treatment of alloys containing from 40 to 96 per cent Mn altered the electrical resistance considerably. Dean, Anderson and Potter6 have shown that the high vibration damping capacity that characterizes manganese-copper alloys containing 40 to go per cent Mn is affected by cold-work and heat-treatments. Highest vibration damping capacity at low stresses was obtained by heating for 2 hr. at 450°C. (842°F.) after quenching from solution temperatures. Preparalion of Alloys.—The alloys for these tests were melted in a 17-lb. basic-lined high-frequency induction furnace using electrolytic manganese, grade A ingot copper and a 70-30 CU-Mn master alloy (69.80 per cent Cu, 0.12 Fe, 0.04 Si, 0.006 S, 0.07 C, balance Mn). The manganese was heated slowly to expel excess dissolved gases and melted before the addition of copper. No fluxes or covers were used. The melts were cast in tapered iron molds and the ingots were reduced go per cent when forged to 1/2-in. rounds. These rods were given 2-hr. solution treatments at temperatures that depended upon the composition (Table I). Tensile Tests.—The tensile specimens, 0.313-in. diameter (1.25-in. gauge length),

Jan 1, 1942

By K. R. Van Horn, L. W. Kempf

Plastic deformation of most commercia1 metals within a sufficiently low temperature range results in profound changes in structure and properties, of which the causes and effects are not completely understood. One of these effects is the presence of internal residual stresses and strains, which ordinarily do not appear to require specific consideration in most structural applications but which may be quite undesirable in particular instances. For example, in heavy sections that require considerable machining before assembly, residual stresses may be undesirable because of the distortion they cause when their balance is disturbed by machining or otherwise. In addition, the distribution of stresses may be such that it acts in the same direction as the applied load, thus bringing about premature failure or reducing the load-carrying capacity of the member. One source of residual stress in metal structures is the plastic deformation that may occur during rapid cooling from relatively elevated temperatures, as in the cooling of a casting in the mold or the quenching of a heavy section from elevated temperatures during heat-treatment. These residual stresses are usually undesirable because their direction of operation and magnitude cannot be controlled well enough to permit utilization of the changes in properties of the metal that they may bring about. The most convenient manner of controlling such residual stress is by proper selection of the cooling rate or by reheating to a temperature at which plastic flow can take place, resulting in relief of the residual stresses and strains. Both of these methods of control, however, may cause a reduction in the optimum properties obtainable from the previous operation. A compromise must be struck, and if it is to result in the best possible combinations of properties, specific information must be available regarding the magnitude of the stresses and the rate at which they are affected by variations in cooling rate or in reheating temperature. The complete quantitative estimation of residual stress in complicated metal shapes is exceedingly difficult, if not impossible. In simple sections, however, relatively quantitative analysis may be applied and useful cstimations of stress distribution may be made. This paper is concerned largely with the rate of relief, upon reheating, of internal residual stress in simple aluminum-alloy structures. Since even with simple structures quantitative estimation of residual stresses is laborious and costly, an attempt was made to find other means of collecting data upon which commercial heat-treatments might be based. Incidentally, a few data were collected bearing on the problem of relaxation of aluminum alloys. Determination of Residual Stresses The magnitude and distribution of residual stresses in simple aluminum-alloy shapes rapidly cooled from elevated temperatures has been discussed in a previous paper.' Fig. I reproduces some of the data

Jan 1, 1942

By P. W. Bakarian

Previous determinationl,2,3 of the texture of magnesium and its alloys have shown only slight variations in the principal features of the structure. This investigation presents pole figures for magnesium and two of its alloys, in which differences of some magnitude will be shown. Schmid and Wassermann have considered the texture of magnesium in analogy with that of zinc—also a hexagonal lattice. Whereas the zinc texture is said to be derived primarily through basal slip and secondarily through {IO2}† twinning, the {102} twinning is considered impossible at the later stages of the rolling in magnesium because of its smaller axial ratio. This state of affairs appears reasonable for pure magnesium, but for alloy textures the situation is more complex. A double orientation similar to that found in zinc has been reported by J. D. Hanawalt,4 and the addition of small amounts of calcium to magnesium and its alloys to produce a double texture was noted by J. C. McDonald.5 The pole figures of this investigation, using an improved X-ray technique, show these various textures. The dependence of directional properties of rolled sheet on modifications of texture is well recognized. Correlation of physical properties with existing texture should be even more significant if quantitative valuations are attached to the various areas on the pole figures. Such a quantitative technique is developed herein. Experimental Method Two alloys were used, besides high-purity magnesium. In each case, the metal was extruded to bars 1/2 in. thick and hot-rolled to a thickness of about 0.075 in. It had been established previously that such a reduction was more than sufficient to eliminate the extruded structure. The rolling proceeded in the same direction as that of the extrusion, without any cross rolling. The temperatures corresponded to normal commercial practice, averaging around 600°F. A unique method of preparing the sample was developed in this work. Instead of using a flat specimen, a stem of the metal was cut out of the rolled sheet in the desired direction (rolling direction) as shown in Fig. I. From a sheet of 0.075 to 0.065-in. gauge, the stem was cut to a square cross section with a jeweler's saw, rounded with a file and polishing paper to a diameter of 0.060 in. and evenly etched in dilute hydrochloric acid to a diameter of 0.038 + 0.001 in. In this way, a cylinder of the original sheet with its axis in the desired direction was produced. By using this type of specimen for the pin-point pictures, any variance in the absorption of the diffracted beam at the various angular settings of the specimen, was completely eliminated.*

Jan 1, 1942

By J. D. Hanawalt, C. E. Nelson, J. A. Peloubet

The subject of the salt-water corrosion resistance of magnesium alloys is somewhat like that of the pitting of stainless steels, in that it involves a relatively small. percentage of the applications but receives a much greater proportion of the publicity. Actually magnesium alloys are in use in many exterior applications as well as interior, with no trouble from corrosion. Magnesium and its alloys have a striking stability against atmospheric attack, being far superior to iron. Specimens exposed unprotected to atmospheric weathering for Io Years show only a superficial surface-film formation. The basic nature of magnesium and of its important alloys is that they are also resistant to the attack of salt water even in an unprotected state, giving substantially no loss in weight after one year of alternate immersion in 3 per cent NaCl solution (Fig. 1). This basic behavior is often masked because of the extreme sensitivity of these alloys to certain impurities and combinations of impurities. It is known, and the subject of increasing emphasis, that higher purity leads generally to greater stability for many materials, non-metallic as well as metallic. However, a review of the literature on the corrosion factors in magnesium alloys shows that almost all researchers worked with base metal in which metallic impurities varied in uncontrolled amounts. The major factor, that of metallic impurities, Probably greatly overshadowed the effects of minor ones such as flux inclusions, nonmetallic impurities, porosity, metallographic state, which these researchers presumed to study. In the present investigation the first observation of interest is that whereas magnesium of commercial purity (99.9 per cent pure) has a corrosion rate in alternate immersion in 3 per cent NaCl solution at room temperature of anywhere from 5 to Ioo mg. per sq. cm. per day, the corrosion rate of high.purity magnesium is 0.15 ± 0.05 mg, per sq. cm. per day. The principle followed in the experiments was to add to such base magnesium other elements, singly and in inin in controlled and known amounts and to observe the corrosion behavior of the resulting alloy. These experiments show the existence of what may be called tolerance limits" of magnesium and some of its alloys for certain impurities. The extremely small percentages of impurities involved and the sharpness of the corrosion discontinuities appear to be quite unpredictable, In order to carry on this work, it was necessary to develop an analysis technique suitable to the problem. In some cases it was necessary quantitatively to analyze impurities to less than 0,001 per cent. The experimental data to be presented are based on observation of about 5000 alloy specimens and on more than 50,000 quantitative analyses. while the primary purpose of this paper is to present the experimentally obtained data on corrosion rates as a function of composition, and particularly to demon-

Jan 1, 1942

By J. E. Burke, C. W. Mason

In attempting to study precipitation from a tetragonal lattice, using solid solutione of bismuth in tin, it was found that although a Widmanstätten pattern is observed1,4 only a qualitative analysis of the orientation relationships is possible, because of the unusual structural changes that accompany the precipitation process. Microscopical Studies Alloys were made from Chempur tin (Standard samples 42b and 426, National Bureau of Standards), and bismuth (Kahl-baum C.P.) by melting weighed quantities together under palm oil, stirring well, and castilig in a heated graphite mold. The polishing and etching techniques employed largely govern the visibility of the structural changes. The preliminary surfacing operations were similar to those recommended by Villela and Bergekoff,5 through Behr-Manning 3/0 abrasive papers, lubricated by a solution of paraffin in kerosene. A rough metallographic polish was next given, using a thin cotton cloth charged with relevigated alumina (maximum particle size of about 4µ) and soap solution; repeated etching and polishing served to remove disturbed metal. For high-power examination better preparation was necessary. It was found that on such soft metals the threads of the fabric, rather than the abrasive, cause most of the scratching. Cotton outing flannel, which had been brushed so that the nap lay down, was fairly satisfactory, but a heavy grade of silk velvet (not the noncrushable kind) was found to be better, especially after some use. A better procedure was as follows: The metal lap was warmed slightly, and a 4-in. circle of woolen broadcloth was cemented to its center by a thin film of melted paraffin. The broadcloth was then moistened with water, and a 30 to 40 per cent solution of sodium hydroxide heated to about 50°C. was poured over it, allowed to stand for I to 2 min. and then washed off. It was neither necessary nor desirable to remove all the sodium hydroxide from the cloth, since its etching action aided in the removal of the flowed layer from the sample. The cloth was then charged with a paste of the relevigated alumina in water. Since this lap did not remove deep scratches, it was necessary previously to polish the specimen on some material such as the silk velvet. The sodium hydroxide softens and partly gelatinizes the woolen lap covering, permitting a scratch-free polish, but its action continues, and the cloth deterioratcs after about 24 hr. This is not serious, because a new lap can be prepared in about 5 min., and only small pieces of cloth are used. Etching with a strongly acid solution of ferric chloride was found satisfactory for removing the flowed layer. For the final etching, the most satisfactory reagent was that of Tafls,7 the formula for which is: FeC13.6H2O, 2 grams; HC1, 5 c.c.; H2O, 30 c.c.; C2H5OH (95 per cent), 60 C.C. This etchant reveals differences in com-

Jan 1, 1942

By Gerhard Derge, Arthur H. Grobe, Harold Markus

The high corrosion resistance possessed by tin under most circumstances, combined with its generally satisfactory appearance and useful physical properties, has led to many and varied uses for the metal. These uses have been partly limited by the fact that tin is an expensive metal, therefore many applications have been developed in which tin has been employed in combination with lead, either by coating, as in tin-lined collapsible tubes, or by the formation of alloys containing various proportions of tin-rich and lead-rich phases, as tcrne plate. A detailed knowledge of the corrosion characteristics of the tin-lead couple therefore is of general interest and has become specially important at the present time, when every effort is being made to conserve tin as much as possible. The present study has been limited to carbonate solutions with a pH range from 8.4 to 11.2 so that the results may be related to earlier work on the corrosion of tin and its alloys. 1-3,6 In these papers, the effects of a number of anion and cation additions to these solutions have been observed. Apparatus and Method The electrodes for the corrosion cell were cut from rolled sheet about 1/16 in. thick. The length of all specimens was held constant at 7 in., while the width was varied from M to 2 in. These electrodes were fastened to brass electrode supports, which were attached to rubber stoppers fitting into tall-type one-liter Pyrex beakers that contained the electrolyte. The lead electrodes were prepared from Omaha pig* and the tin was rolled from a slab of Chempur.† After cutting to size, the sheets were polished with No. I emery paper and cleaned with carbon tetrachloride. The edges, back and upper parts of the specimen were coated with a synthetic lacquer, which was supplemented with beeswax for the lead electrodes. The binding posts were coated with beeswax after the electrodes had been clamped. The pH of the electrolyte was controlled by adjusting the ratio of carbonate to bicarbonate. Approximately 600 ml. of electrolyte was used in each beaker. The entire assembly was placed in an oil bath thermostatically adjusted to operate at 30°C. + 0.1". Potentials were measured against a saturated calomel electrode connected to the cell by an agar-agar salt bridge. The carbonate solution used in the salt bridge was the same as that used in the corrosion cell. Currents were measured with a milliam-

Jan 1, 1942

By F. N. Rhines, A. H. Grobe

At elevated temperatures the oxide of silver is unstable in the air at atmospheric pressure, consequently no external oxide scale forms upon pure silver under conditions of high-temperature annealing. When small quantities of certain alloying elements are present in the silver, the formation of a thin external scale is possible1 and in addition there may form a subscale composed of the oxide of the solute element precipitated within the body of the silver. Norbury2 and Leroux and Raub3 have reported internal oxidation (subscaleiormation) in alloys of silver with 2, 7.5, and 30 per cent of copper. The presence of the subscale is believed to be responsible, at least in part, for the objectionable "fire mark" in Sterling silver.4 Several other alloys of silver, after oxidizing heat-treatments, are known to exhibit undesirable polishing characteristics that may be the result of internal oxidation. Except for the absence of an external scale of silver oxide, it is to be anticipated that silver alloys will prove to be very similar in their oxidation behavior to the alloys of copper, the oxidation characteristics of which have been studied in some detai1.5,6 The present research confirms this anticipation. The oxidation of a series of 20 dilute alloys of silver has been studied metallographically; some types of subscale not encountered among the copper alloys have been found. Instances of internal oxidation in alloys of most of the metals of the 1-6 and VIII groups of the periodic system are on record, but evidence of this type of oxidation in alloys of the metals of the intermediate groups is lacking. A number of the metals of the intermediate group, among them cadmium, lead, tin, and zinc, appear to provide the conditions essential to subscale formation; i.e., they form oxides with a relatively low negative free energy of formation, they dissolve other metals that form more stable oxides, and, presumably, oxygen will diffuse through them. In a study of 40 alloys of these white metals only a few cases of internal oxidation have been found. The probable reasons for this difference in behavior will be discussed presently. Experimental Procedure Silver.—The silver alloys employed in the oxidation studies were prepared in heats of 30 grams each from high-purity silver (99.993 per cent Ag)* and the purest avail-

Jan 1, 1942

By A. William Johnson

It was pointed out in an earlier paper1 that our understanding of the atomic mechanism by which diffusion occurs in metallic alloys is scarcely in an advanced state. This unsatisfactory condition is the result not of any lack of interest, but of the difficulty of designing experiments that .will yield suitable data. The diffusion coefficient of an alloy, measured in the usual way, is simply a number specifying the rate of homogenization of a nonhomo-geneous metal; this number, of itself, can furnish neither the rate at which the individual atoms move nor information as to the mechanism by which they move. It does not necessarily follow, however, that such information cannot be obtained, even if the path to be followed is still not clear. Much success has been attained in the study of diffusion in ionic crystals. A number of experiments, for which there are few counterparts in connection with metals, yield information often indicating a detailed mechanism by which diffusion probably occurs. From such work, quite acceptable theories of lattice imperfections have been developed by Wagner, Schottky, Frenkel, Jost and others.2 It is postulated that real crystals of stoichiometric composition contain, in equilibrium, certain imperfections of which the most importarlt types are: (I) vacant cation sites, with an equal number of interstitial ions; (2) vacant anion sites, with an equal number of interstitial ions; (3) equal numbers of anions and cations in interstitial positions; (4) equal numbers of vacant anion and cation sites. The classification of a particular crystal according to this scheme then follows from studies of the variation of electrical conductivity with pressure of the electronegative component surrounding the crystal, with ion size, and with temperature; other physical phenomena, such as the Hall effect, have aided in establishing the classification. The relative mobility of the anion and cation may be determined by chemical analysis of the salt at the electrodes following electrolysis. With such information, and knowing that one ion never occupies the lattice site normally belonging to an ion of opposite sign, it is usually possible to ascertain the diffusion mechanism. It is clear that the same experiments are not applicable to metal crystals, and substitute experiments that yield as much information have not yet been devised. Much can be learned, however, about the mobilities of the two* kinds of atoms in alloys by the use of radioactive metals as indicators. Only one such experiment has been performed in the past. In 1933, Seith and Keil,3 in an effort to explain the great difference between the rate of diffusion of gold in lead and of lead in lead, measured the rate of diffusion of radioactive lead in 3 gold-lead

Jan 1, 1942