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By D. L. Martin

The study of cobalt-platinum alloys has been of interest since they represent a class of permanent-magnet material in which the disorder-to-order transformation plays a controlling role. The magnetic properties of alloys in the range 40 to 60 at. pct have been found to be greatly influenced by composition and heat-treatment. The peak properties of 4700 coercive force and 9,000,000 gauss-oersteds energy product were obtained by controlled cooling and aging. These high values combined with ductility and machin-ability give the alloys useful characteristics although their high cost limits their application. THE cobalt-platinum alloys have been of interest in the study of permanent-magnet materials ever since the discovery by Jellinghaus that they had unusually high coerceive-force values.' The high coercive force was associated by Jellinghaus with the disorder-order reaction which occurred in these alloys. This was later verified by Gebhardt and Koster in a detailed study.2 An investigation of the structure, mechanism, and kinetics of the disorder-order transformation and resulting property changes in cobalt-platinum alloys has been in progress for some years. Certain phases of this study related to equilibrium rela- tions, and to the mechanism and kinetics of the ordering reaction have been published previously.3-5 In this paper, the results of the processing and heat-treatment studies on 40 to 60 at. pct CO alloys are presented. The magnetic properties have been found to be influenced greatly by the composition, by the cooling rate from the disordering treatment, and the final ordering time and temperature. Coercive force values, Hc, of 4700 oersteds and energy values, (BH)m, approaching 9,000,000 gauss-oersteds have been obtained by controlled cooling and ordering. PROCESSING OF THE ALLOYS The composition range of interest for permanent-magnet properties centers around the equiatomic composition Copt. In this region the alloys are dis-

Jan 1, 1959

By R. G. Charles, E. A. Gulbransen, S. Barnartt

KINETICS of the reaction of zirconium with pure oxygen at elevated temperatures have been studied by several workers for periods of time up to 6 hr.1-1 In two cases,3-4 . the experimental values of oxygen uptake, w, as a function of time, t, were best fitted to the parabolic rate law w2 = kPt + constant. In others,3,4 the cubic rate law w3 = kot + constant, showed better agreement. The most recent data of Gulbransen and Andrew4 indicate that the choice between the parabolic and cubic laws for empirical representation of the data will often be arbitrary. This is particularly true if the first few minutes of the reaction with a clean zirconium surface is attributed to a different oxidation mechanism, for deviations from either rate law were found primarily during the initial period. Thus, the kinetics of this reaction have been too uncertain to permit safe extrapolation to oxidation periods of practical interest (many hundreds of hours). The data to be described are of interest, for they indicate that the cubic rate law applies over long oxidation times. The reaction of zirconium with oxygen at 1 atm pressure was followed at 350" and 450°C for 500 and 200 hr, respectively. Abraded test specimens of pure zirconium sheet' 3.0 X 2.0 X 0.012 cm in size were oxidized by the procedure previously described,3 which included periodic cooling to room temperature for weighing. The surfaces were polished to a 4/0 finish using polishing paper wet with kerosene, then wiped with petroleum ether and washed in redistilled acetone. Fig. 1 shows plots of log ? vs log t. Each curve represents the average of duplicate measurements, and deviations from the average were generally less than 3 pet. The cubic rate law (slope = 1/3) is closely followed. The rate constants, 5.2, x 10 -6 and 2.4, X 10- (mg cm-2)3 per hr at 350" and 450 oC, respectively, are plotted as log k, vs 1/T in Fig. 2, together with cubic constants calculated from the data of Gulbransen and Andrew4 for abraded specimens from the same lot of zirconium. Their data refer to runs of 6-hr duration at a pressure of 0.1 atm 0 and under conditions of uninterrupted heating. In spite of these differences, the latter data yield a straight line which appears to apply equally well to the new extended time data. The energy of activation for the oxidation process, calculated from the slope of this line, i.s 38 keal per mole. This may be compared with the value of 47 keal per mole found by Belle and Mallett3 at higher temperatures. It may be concluded tentatively that extrapolation of short-term oxidation data for zirconium to obtain the long-term behavior is best done through the cubic equation ?3 = kpt + constant. References ' E. A. Gulbransen and K. F. Andrew: AIME Trans., 1949, vol. 185, p. A.515; JouRNal OF Metals, August 1949. 'D.p. Cubicciotti Journal Amer Chemical August1949.Soc., 1950, Vol. 72, P. 3 V. Belle and M. W. Mallett: Joulnal Electro chemical Soc., 1954, ' E. A. Gulbransen 339.and K. F. Andrew: Oxidation of Zirconium Between 400" Gulbransenand 800'C.and AIME Trarzs.. 1957, vol. 209, p. 394; JOUR-Nal of Metals, April 1957. IS Barnartt, B G. Charles, and E. A. Gulbransen: Oxidation of 50 weight pet uranium-zirconium alloy, Journul Electrochemical SOC., 1957, vol. 104, p. 218.

Jan 1, 1959

By W. D. Robertson, R. E. Reed-Hill

Slip on (11221 planes, which do not contain a close-packed direction, has been identified on crystals strained at —190°C. Evidence is also presented to show that (1071) pyramidal slip is a mode of deformation at 25ºC in a limited orientation range. PYRAMIDAL slip (l011) <1120> in magnesium at elevated temperatures has been established for some time.1-2 More recently, Burke and Hibbard reported this mode of deformation at 25ºC, but their results were questioned by Craig.&apos; Also, as far as the present authors know, slip in magnesium on pyramidal planes of the second order, Type II (1122)) has not previously been reported, although Gilman"," identified (1122) slip in another hexagonal metal

Jan 1, 1959

By J. W. Freeman, J. P. Rowe, R. F. Decker

HEAT-to-heat variations in properties of an alloy of constant nominal chemical composition have been a perplexing problem to the metallurgist. These heat-to-heat differences have been especially baffling in high-temperature metallurgy. In order to establish fundamental reasons for these heat-to-heat variations, the National Advisory Committee for Aeronautics has sponsored and financially assisted an extended research program on heat-resistant alloys at the University of Michigan. As part of the program to find the contribution of processing variables, Frey, Freeman, and white&apos; studied effects of heat treating on nickel-base alloys and Ewing and reeman&apos; investigated effects of hot-working practice on N155 alloy. To extend the program to the study of effects of melting practice on high-temperature properties, a 55 Ni-20 Cr-15 Co-4 Mo-3 Ti-3 pct A1 composition was selected for experimentation. The objective of this program was to establish the melting-practice variables which influenced the hot-working characteristics and creep-rupture properties and, at the same time, establish the metallurgical mechanisms for the effects. During the course of the investigation of practices using vacuum melting, it became increasingly evident through chemical analyses supplied by industrial concerns that a major variable was melt reaction with the crucible. This paper is devoted to the results of this phase of the melting-practice study. EXPERIMENTAL PROCEDURES Experimental 10-lb heats were induction melted in the University of Michigan vacuum-melting unit with the melting practices outlined in Table I. Aim analysis for the basic alloy, in wt pct, for all heats was as follows: Cr Co Mo Ti Al 20.0 15.0 4.0 3.1 3.1 Mn Si C Ni 0.12 0.12 0.08-0.15 Bal. Small amounts of boron and zirconium were added to certain heats as listed in Table I. These additions

Jan 1, 1959

By S. Kado, G. Derge, L. Yang

Self-diffusion coefficients of silver in molten silver have been measured by means of the capillary-reservoir method in the temperature range 1002" to 1105°C. The results can be .represented by the equation D = (7.10 i 0.06) X 10-4 exp [(—8150 ± 1130)/RT]. The heat of activation agrees within the limit of experimental uncertainty with that for the viscous flow. The validity of the Eyring and the Stokes-Einstein equations are examined on the basis of the self-diffusion coefficients obtained and the known viscosity data of molten silver. MEASUREMENT of the self-diffusion coefficient of silver in molten silver was made in the temperature range 1275° to 1378°K, using the capillary-reservoir method and &"&apos; as the radioactive tracer. The experimental arrangement is shown in Fig. 1. Silver of 99.99 pct purity (fine silver), was melted and degassed in vacuum in a graphite crucible situated inside a McDanel vacuum jacket. The crucible (4 in. tall and 1 in. ID) was protected both at the top and at the bottom with graphite shields and contained about 220 g of silver. The sample holder was a piece of graphite rod (1 in. long and 1/2 in. diam) with 4 capillaries drilled longitudinally into it. The holder was screwed onto a long graphite rod (12 in. long and 74 in. diam) which was connected to a steel disk hanging on a nylon string through a glass pulley. The steel disk kept the sample holder at the center of the McDanel tube and was heavy enough to overcome the buoyancy when the holder was lowered into the molten silver. By turning a handle connected to the pulley through a tapered glass joint, it was possible to raise or lower the sample holder without breaking the vacuum. Two such arrangements were constructed, sitting side by side in 2 Kanthal furnaces. One with non-radioactive silver in its crucible was used for the diffusion run and the other with radioactive silver in its crucible was used for filling the capillaries. To fill the capillaries with radioactive silver, the sample holder was degassed first and then lowered into the radioactive molten silver in vacuum. Purified argon gas was then admitted into the system to push the liquid silver into the capillaries. After cooling in argon, the filled capillaries were polished on emery paper to expose the top of the rod and used immediately as samples for the diffusion run which was carried out at the same temperature as that used for filling the capillaries. During the diffusion run, the samples were degassed in vacuum and lowered slowly into the nonradioactive molten silver before purified argon was admitted into the system. After a predetermined period of time, the samples were raised out of the melt and cooled in argon. The temperature of the melt was measured before and after the run with a chromel-alumel thermocouple inside a McDanel protection tube. Another chromel-alumel thermocouple attached to the outside wall of the McDanel vacuum jacket was used to indicate any fluctuation in the temperature of the furnace during the run, which was found to be less than ± 2°C for the longest run made (93 min). The temperature gradient inside the molten silver was found to be negligible. No significant difference was observed in the results obtained whether the melt was stagnant during the run or was stirred by raising and lowering the sample holder slowly a few times a minute for a distance of about 1/4 in. inside the melt.

Jan 1, 1959

By R. L. Fleischer, B. Chalmers

In order to observe size effects associated with a grain boundary, aluminum single crystals and bicrystals of various cross-sectional dimensions were deformed in tension. Typical stress-strain curves are presented in conjunction with measurements of the effects of changes in crystal dimensions. Some effects of the growth rate used in preparation of crystals are also described. It is indicated that the macroscopic constraints at a grain boundary are responsible for the most prominent grain-boundary effect, the production of multiple slip. Two measurements of the width of the region of double slip are in agreement. It is concluded that the yield stress of aluminum is affected markedly by the inherent oxide coating. THE general problem to be examined is that of dimensional effects in the plastic deformation of metal crystals. These effects will be termed "size effects" and are here defined as follows: A size effect occurs in a series of crystals if their plastic-deformation properties are a function of crystal dimensions. Clearly then size effects depend on the nature of the boundary conditions imposed on the crystal. Crystal boundaries can be of three types: interphase, inter-crystalline, and free surface. Such deformation effects as are caused by distribution of phases, grain size, lineage structure, and single crystal external geometry are specific types of size effects. This discussion will be confined primarily to grain-boundary and single-crystal size effects, though in practice most "single crystals" not only have a number of small angle boundaries but also have one or more surface phases, so that the boundary conditions appropriate to a free surface do not necessarily apply. Hence, to this extent interphase size effects will be considered. The question of size effects associated with grain boundaries (called here intercrystalline size effects)

Jan 1, 1959

By C. M. Schwartz, A. E. Austin, W. B. Wilson

High-temperature X-ray diffraction studies were conducted with Th-U alloys with up to 10 wt pet U. The solid solubility of uranium in thorium as a function of temperature was determined by the method of lattice parameters. Thorium will dissolve up to 2.5 wt pet U at 950°, 4.5 wt pet U at 1150°, and 7.5 wt pet U at 1250°C. Determinations were made of the temperature of the transition of thorium and of the effect of uranium upon the transition. The a to ß transition for thorium was observed to occur at 1330&apos; ±20°C. Mean coefficients of expansion were calculated for thorium and two alloys, and for ThO2 in contact with the thorium, using X-ray lattice-parameter data. Values obtained at 950° C for thorium and Tho2 were 12.1 and 9.40 X 10-6 per OC, respectively. Impurities obtained during the X-ray exposure were identified by diffraction and were essentially Tho2 and ThC, with two additional unknown phases being detected. The effect of the impurities upon the results is discussed. DIRECT investigation (i.e., high-temperature X-ray diffraction studies) of the phase diagram of thorium-rich uranium alloys has been shown to be necessary since recent work1 - has disclosed the presence of an allotropic transformation near 1400°C in pure thorium with the room temperature face-centered-cubic phase transforming to a body-cen-tered-cubic structure at the elevated temperature. The effect upon the transition of the addition of uranium to thorium and of the solubility of uranium in thorium at high temperatures remained unknown, yet was of interest in understanding fabrication procedures and elevated temperature use. The present work was undertaken to provide information in this area by determining the transition temperature, the effect of uranium on the transition temperature, and the solubility of uranium in thorium as a function of temperature. Experimental Work The high-temperature diffraction data were obtained using a camera especially designed for the purpose3 and capable of reaching temperatures in excess of 2000°C at pressures as low as 1 x 10." mm Hg. Temperature regulation was provided by regulating the power input to ±0.1 pet variation, and by regulating the water flow through the camera jacket to provide a constant thermal load. The X-ray sample was a rod nominally 80 mil diam, which was further turned down to 20 mil and then etched to 18 mil over 1/2 in. of one end. This was placed in the sample holder and mounted on the camera so that the smaller part was surrounded by a cylindrical tantalum-sheet radiation-type heating element. Diffraction from the sample was recorded on film after passing through a slot in the heating element and radiation-baffle shield and through beryllium vacuum windows. The X-ray film mounting was of the Straumanis type4 with a camera diameter of 114.59 mm. Since previous work of Chiotti&apos; indicated that impurities considerably alter the transition temperature, chemical analysis of the arc melted iodide crystal-bar thorium samples was obtained prior to testing. The analysis disclosed the material to contain as low as 0.001 ±0,0002 wt pet H and 0.007 ±0.001 wt pet 0. Carbon was 0.003 wt pet and nitrogen less than 0.002 wt pet. This material was sealed in mild steel in an inert atmosphere and subsequently hot rolled to 3/8-in. diam rods at a temperature of 732°C. Following removal of the jacket, the material was pickled and cold swaged to 1/8-in. rods, from which the diffraction samples were prepared. The alloys were similarly prepared, with the uranium being added during arc melting. The uranium analyses of the alloys prepared appear in Table I. The experimental procedure for diffraction examination of the three samples of high-purity thorium differed from those of the Th-U alloys. The original practice, later modified, consisted of pumping down the camera with the diffusion pump on and then admitting liquid nitrogen to the cold trap of the system. This was modified for the Th-U alloys by maintaining liquid nitrogen in the cold trap at all times before and while the diffusion pump was heated. This minor change produced a reduction in the amount of carbon pickup by the sample during exposure to the diffusion-pump vapors. The sample was brought to the desired test temperature and exposed for 21/2 hr at pressures which were usually 2 x 10-6 mm Hg, or lower. Exposures were made at

Jan 1, 1959

By W. R. Hibbard

Evidence is presented which confirms previous findings that models of solution strengthening depending solely on lattice parameter changes are incomplete. Direct evidence for the Suzuki interaction of chemical effects was obtained from alloys with constant lattice parameter, for which solution strengthening was nearly independent of temperature from 300° to 20°K. SOLUTION hardening principles have been reviewed recently by Parker and Hazlett.&apos; In addition, the interactions of dislocations and solute atoms were reviewed by Cottrell.&apos; It is not proposed to review this information again here, but to refer only to those details which are pertinent to the developments which have occurred since these papers were published. Literature Survey To set the stage, it has been known for some time that solid solutions are stronger than the pure parent metals, and that the strength increases with increasing amounts of alloying element. One of the most extensive earlier investigations was that of Lacy and Gensamer,3 who reported that the solid solution strengthening of iron is a power function of the composition, that the relative strengthening is a function of the solubility limit, and that the rate of strain hardening is a function of the amount of solution hardening. Thus, the slope of the plastic portion of the stress-strain curve increases with increasing yield strength. An approach to the development of principles resulted from work by Gulyeav,4 who reported that the strengthening effect of solid solution alloys is periodic in character when plotted as a function of the atomic number of the solute. A more quantitative approach was to relate the amount of solution hardening to the lattice parameter of a solid solution. This was done quite early by Norbury,5 and later by Brick, Martin, and Angier,6 Frye and Hume-Rothery,7 and French and Hibbard. This relationship is only approximate in character. The next development was to relate the amount of solution hardening to lattice stress, as proposed by Frye and co-workers.9 They calculated what they called ionic overlap from the lattice parameter changes represented as a change in volume, using Bridgman&apos;s hydrostatic compression equation. The resulting correlation was somewhat improved as compared to the simple correlation with lattice parameter. The next step was carried out by Dorn, Pietrow-sky, and Tietz,10 who suggested an effect of valence differences in addition to the effect of lattice parameter. Their proposed parameter shows flow stress as a single valued function of the concentration and a relationship involving these two atomic variables. In addition, they contributed new data on the temperature dependence of solution hardening which indicated that it was a strong function of temperature for aluminum alloys. Allen, Schofield, and Tate11 carried the valency effect even further by reporting data indicating that with a given solvent element the stress-strain curve is a function of electron density, entirely neglecting the size factor, which varied by a factor of two. This evidence led to a quantum mechanical calculation by Cottrell, Hunter, and Nabarro,12 based on the formation of a dipole around an edge disloca-

Jan 1, 1959

By D. A. Stevenson, T. Alden, J. Wulff

A portion of the liquidus curve has been determined for the binary alloy systems Ni-Pb and Cr-Pb. The solubility of nickel is 0.53 atomic pet at 372° and 18.63 atomic pet at 1200°C. Chromium shows low solubility, 0.634 atomic pet at 1210°C. Molybdenum and tungsten were also studied and found insoluble in lead, less than 0.005 atomic pet at 1200°C. INCREASED use of liquid metals of low melting X point for heat transfer, coating, joining, and other purposes has renewed interest in the solubility of structural metals in these liquids. A study of Hansen1 and current literature indicates that few liquidus curves at the low melting end of the binary diagrams have been accurately delineated. This statement applies particularly to the binaries of lead. The present paper is limited to nickel, chromium, tungsten, and molybdenum in lead. In early studies2, 3 of the lead end of the Pb-Ni system, a monotectic at 1340°C was established. Tammann and Oelsen&apos; determined the solid solubility of nickel in lead at 20°C to be 0.023 wt pet. Recently Pelzel5 determined the liquidus curve from the eutectic temperature of 327° up to 727°C using a segregation method. In the present paper this part of the curve has been checked and extended to 1244°C. The Pb-Cr system was first studied by Hindrichs.6 He pointed out the existence of a monotectic at 1470°C and indicated a tentative liquidus. Recent corrosion studies of Fe-Cr alloys in lead suggest that chromium is more soluble than iron in lead.7-8 The solubility of tungsten in lead according to Inouye8 is about 30 wt pet at 1200°C. Appreciable solubility of molybdenum in lead might therefore be expected. Experimental Various experimental techniques have been employed in the determination of solubility in liquid metals. For low solubility, thermal analysis is unsatisfactory. A segregation method was used by Pelzel3 in his study of the Pb-Ni system. In this procedure separation of liquid and solid is possible due to difference in density. In the technique of Kleppa10 a single piece of material is maintained in contact with the liquid metal in evacuated Vycor vials. After equilibration, solid and liquid are separated by tilting. Keck and Broder" measured the weight of a piece of the solid solute before and after immersion in a pure solvent bath; the weight loss was a measure of the solubility. All of the above procedures are time-consuming since they permit only one determination per run. Numerous samples for analysis may be taken from the melt in the method described by Gurinsky and CO-workers.10 The rate of extraction of samples is limited only by the time required for equilibration. In the present work, a modification of this method was employed. A 150-g charge of analytical reagent grade lead and the added metal* were contained in an Alun- dum crucible. It rested on firiely divided silica at the closed end of a 45 mm Vycor tube, 500 mm long. The top of the tube was provided with an inlet and

Jan 1, 1959

By J. C. Danko, R. D. Stout, A. H. Holtzman

The deformation characteristics of pearlite have been studied by light and electron microscopy.1,2 In the electron-microscopic work, deformation was found to take place by 1) ferrite slip which is parallel to the lamellae, 2) slip transverse to the lamellae with both cementite and ferrite deforming, and 3) ferrite-cementite interfacial slip. The transverse slip gives a step-like appearance to the lamellae in light microscopic work. It was thought that spheroidization of deformed pearlite would commence at the regions of maximum cementite deformation, the "stepped" areas. Although there is no possibility for seeing slip in the microstructure if the specimen is polished after deformation, the step-like appearance of the lamellae clearly indicates the transverse deformation. Thus, the areas of cementite deformation are apparent after polishing and the effect of deformed areas on spheroidization may be studied by the usual metallographic techniques. This note reports the result of a metallographic investigation which substantiates that spheroidization begins in the "stepped" areas. An AISI 1080 steel was normalized, re-austeni-tized at 1040°C, and isothermally transformed at 700 ± 4°C for 4 hr. Cubes, 5 mm to a side, were compressed between parallel plates to strains of 20, 40, and 50 pct. After deformation, specimens were heated to 600, 650, and 700°C; withdrawn at increasing time intervals and examined metallo-graphically for the percentage and distribution of spheroidite. The percentage of spheroidite was determined by lineal analysis. A micro structural region considered as spheroidized was one in which a lamellar skeleton was not distinguishable. Table I gives the times necessary for 95 pct spheroidization for each condition of strain and annealing temperature. Fig. 1 shows the microstructure of coarse pearlite compressed 20 pct, then polished and etched. Here the lamellae form a step by bending at two

Jan 1, 1959

By A. S. Yue, A. G. Guy

A study was made of the effects of a prolonged flux of zinc atoms through the a solid solution of zinc in copper. The experimental arrangement consisted essentially of a copper disk about 0.01 in. thick, at one of whose surfaces a gaseous atmosphere containing zinc atoms was maintained, and at the other surface a gaseous atmosphere with a minimum of zinc atoms was maintained. During prolonged theothersurfaceexposure at high temperatures the zinc content of the copper disk gradually built up to the steady-state concentration distribution and then remained at this value. The concentration-distribution curves for various conditions were determined by chemical analyses. The results showed that the condition of steady-state diffusion was achieved. The diffusion coefficients calculated from the experimental data, although not of high precision, agreed with the values obtained by other workers using unsteady-state methods. Relatively slight porosity developed in the specimens in the course of diffusion. A LTHOUGH most diffusion studies have been made under unsteady-state conditions, it is known&apos; that the steady-state method is often superior with respect to the directness and accuracy of interpretation of the data. Steady-state diffusion of gases through metal diaphragms is well known. Also, Harris&apos; and Smith" have used the steady-state method in studying the diffusion of carbon in aus-tenite. The accepted mechanism in this system involves the motion of the interstitial carbon atoms in the rigid framework of the lattice of iron atoms. Thus, there is little difficulty in visualizing the steady flow of the small carbon atoms through the austenite. The situation in substitutional diffusion is quite different. Here the atoms are comparable in size, and it is not evident how a steady flow of one of the atoms through the solid solution might be achieved. At the time the present research was started, it was known that a previous exploratory attempt to produce steady-state diffusion in a substitutional alloy, the Au-Ag system,&apos; had been unsuccessful and had indicated that perhaps there were basic difficulties that could not be ovei-come. Therefore, the present research began as a study of the effect of a prolonged flux of metal atoms through a substitutional solid solution. Eventua.lly, it was possible to produce actual steady-state diffusion in the system chosen for study, the a Cu-Zn alloys. Experimental Procedure The aim in the experiments was to maintain a high zinc content, about 30 pet, at one surface of a copper sheet, and to maintain a low zinc content, near 0 pet, at the opposite surface. The zinc would then diffuse into and through the copper, first building up to the steady-state concentration distribution and then maintaining this distribution. The three types of specimens that were used are shown in Fig. 1. In type A specimens the copper disk through which diffusion occurred was welded to the top of a cylindrical molybdenum tube, the bottom of which also was sealed by welding. At the diffusion temperature the brass chips in the molybdenum container were the source of the zinc vapor which maintained the lower surface of the copper disk at 30 pet Zn. The upper surface was maintained at 0 pet Zn by the vacuum in which type A, and also type B, specimens were diffused. Since the molybdenum container was impervious to zinc vapor, it was intended that the only path of escape for the vapor from the brass chips would be through the thin copper diffusion disk. However, it was found that small leaks often developed at the welded joints during the diffusion treatment, and in most specimens some of the zinc was lost in this manner. Although even small losses of this kind were a serious handicap in attempting to determine the flux through the disk, they did not prevent the maintenance of satisfactory boundary conditions for the attainment of the steady-state condition. Type B specimens differed from type A in having a weight of about 300 g supported on the copper disk by 15 to 20 short quartz rods. This change was made when it was observed that the copper disk was being bowed upward by the difference in the pressures acting on its two surfaces. Since the grain-boundary cracking which occurred in the bowed specimens could be attributed largely to the accompanying creep,3 it was desirable to minimize this effect. The counterweight was effective in significantly decreasing both bowing of the disk and cracking at grain boundaries. Type C specimens differed considerably from the others in that the low-zinc atmosphere at one sur-

Jan 1, 1959

By O. K. Miniato, L. Massé, K. Nobe, J. S. Aronofsky, W. F. 213-000-000-016 Seyer

MUCH work has been done dealing with the effect of mechanical stress on electrode potential in an electrochemical system. The contradictory nature of the experimental results indicates the complexity of the problem although thermodynamic considerations show that a simple relationshir, should exist. In those systems where a gas was the electromotive active substance satisfactory agreement between theory and practice has been found. Des Coudres&apos; found this to be so even when the active substance of the electrode, in this case mercury, was in the liquid state. In contrast, attempts to correlate theory and experiment for the solid state have met with a very limited success. The early workers in this field, Andrews,2 Walker and Dill3 used iron, certainly one of the most reactive of metals. Others have made use of less active metals such as copper and nickel. Recently Fryxell and Nachtrieb4 investigated the electrochemical behavior of gold and silver under both tensile and compressive stresses and concluded that it was doubtful whether true stress potentials could ever be measured. Much of the lack of success to measure the thermodynamic stress potential can be ascribed to the presence or formation of a complex film on the metal surface in contact with the electrolyte. Further, the theoretical stress potential is very small and therefore difficult to measure directly. Thus the calculated emf between a 24 B & S gage cold-drawn copper wire stressed with a weight of 1 kg and an unstressed portion of the same wire is only 2.60 X 10"7 volts. This is very small compared to that which can be produced by chemical reactions at the metal electrolyte interface which in turn can be so large as to mask completely the stress potential. Hence in this type of measurement all chemical side effects must be eliminated or reduced as much as possible. It was for this reason that the system copper-sodium chloride solution was selected for study. INSTRUMENTATION In the many preliminary experiments conducted, two major difficulties were encountered. The first was to measure the small electro-potentials to be expected and the second to obtain a suitable electrode surface. The conventional potentiometric method was found to be unsatisfactory for measuring the small emf expected. However, by using an L & N No. 2290 galvanometer having a resistance of 915 ohms consistent measurements were possible. The reference electrode was always the unstressed one made from the same sample of wire. The steady current flow was approximately 10-8 amp. Lewis and Randell5 have stated that for currents of the order of 10-8, if there is no sensible polarization, the measured emf may be taken as a reversible one. To check the galvanomenter readings an alternative method was devised to measure the potential difference between the wires. This involved a Liston-Falb d-c breaker amplifier model 10, an L & N k-2 potentiometer and a moving-coil galvanometer having a sensitivity greater than 0.1 µv (microvolt) per mm. To increase further the output voltage of the amplifier a d-c amplifier, model B. L.-932 was introduced into the circuit. This amplifier was in turn connected to a Brush recorder which had been calibrated previously by the test signals from the Liston-Falb instrument. These test voltages employed took into account the impedance of the input current. Unfortunately, this method had too low a sensitivity for measurement below 10 µv. Above this value the voltage agreed reasonably well with those obtained directly by the simple galvanometer method. The main advantage of the amplifier setup was that one did not have to wait until no deflection occurred on the galvanometer in the circuit when first exposing the wires to the solu-

Jan 1, 1959

By K. U. Snowden, J. N. Greenwood

EARLY studies by Gough and sopwith&apos; have shown that the fatigue resistance of certain metals increased when the test was carried out in a partial vacuum; lead showed this effect to a marked degree. This communication describes surface deformation differences between high-purity lead fatigued in air and in a vacuum of approximately 5 X l0-3 mm Hg. Both air and vacuum tests were carried out by the same alternating flexure machine at a frequency of 500 cpm. Flat cantilever-bend specimens with tapered sides were cut from strip, annealed at 100°C, and chemically polished.

Jan 1, 1959

By O. J. Huber, P. D. Frost, H. A. Robinson

URANIUM is a (ß-stabilizing, eutectoid-forming element when alloyed with titanium. Udy and Boulger1 have reported that an alloy of 48.6 pet uranium in titanium retains ß-phase when quenched from the ß-region, while compositions of approximately 30 pet uranium transform to martensite during such quenching. Since the eutectoid reaction is rather sluggish, titanium-uranium alloys should be capable of being strengthened by the ß — a trans-

Jan 1, 1959

By S. B. Twiss, P. R. Basford

The relationship between areas of iron powders, briquettes, and sintered compacts and tensile strength has been determined. It has been found necessary to distinguish between two types of areas which exist in such powders—a macroscopic area due to the shape and size of particles and a microscopic area due to pores and cracks in the surface. Only the macroscopic area, specifically the area due to particle irregularity, contributes to tensile strength; the microscopic area cannot be forced into contact with adjacent particles ond does not participate in bond formation. Of the two methods of area measurement employed in this study—permeability to liquids and gas-phase adsorption—only the former is useful for determining the roughness factor. A measure of this roughness, (area measured by permeability to liquid) -f- (orea of powder with the same size distribution, but made up of spherical particles), is shown to be uniquely related to tensile strength at constant density. The other important factors in determining the strength of sintered-metal compacts are the density and presence or absence of surface oxide. THE manufacture of metal parts by the process of powder metallurgy is an important and rapidly growing industry. Progress has been rapid and continuous, largely because of the excellent research in the field. Nevertheless, the process remains inherently complex and empirical. Several investigators have shown that the properties of the final compact must depend on many variables; namely, shape,&apos; size distribution,"-" nd compositiona of the original particles, the pressure necessary to compress to the desired density, the density of the compact, the time and temperature of sintering, and so on. Through the application of some new techniques to the study of powders and compacts, and the correlation of a number of observations of known variables, the present paper attempts to clarify and simplify the underlying theory of the powder-metallurgy process. Any theory must start with the obvious fact that the strength of a compact, its most useful property, is due to the formation of welded areas between adjacent particles, and attempt to deduce what effect other variables will have on (a) the area and (b) the intrinsic strength of these welds. Such welded areas can be demonstrated by electron micrographs, as in Fig. 1. It was believed that (a) could be most directly studied by means of surface-area measurements on the original powders and on the compacts made from them; the area decrease should be related closely to the welded area. A representative group of eleven iron powders from commercial sources, and made by a variety of processes, was chosen for this study. In addition to the surface-area measurements, correlations were established between the tensile strength and all the known variables which might possibly affect it. The results are quite unexpected. They indicate that the situation is much simpler than the authors had anticipated. The strength of the sintered compact is determined, indeed, by no more than three variables; viz., the irregularity of the original particles, the density of the compact and, in exceptional cases, the amount of surface oxide. All three had been recognized previously as having some effect on the tensile strength, but in the absence of the special techniques and interpretations to be developed here, there could be no suspicion that they were the only relevant variables. Materials and Methods Material—All the iron powders were commercial products obtained from the Amplex Division of Chrysler Corporation. Powders A, B, C, and J were very pure electrolytic iron. Powder D was made from oxidized scrap reduced by heating with an excess of cast iron. Powder E was a high-grade iron ore reduced by hydrogen. Powder I was prepared by atomizing molten cast iron in an air blast, quenching the droplets in cold water, and crushing the coarse powder. Mill scale (oxide) is added and the mixture heated to reduce the high carbon content. The other powders were all prepared by reduction of iron oxides, such as mill scale. They

Jan 1, 1959

By J. L. Walter, W. R. Hibbard

A GREAT deal of work has been done on the rolling of single crystals of iron. Barrett and evensoon studied end orientations of heavily cold-rolled iron crystals and found that some crystals maintained a sharp single orientation during rolling. Others rotated into two or more orientations, and some fragmented and approached the entire polycrystalline texture depending on the original orientation of both the normal and rolling directions. Barrett, Ansel, and Mehl2 studied iron-silicon alloys and found that the addition of silicon to the iron had little effect on heavily rolled polycrystalline material. Dunn3 has extensively studied the cold-rolling and recrystallization of silicon-iron single crystals. Dunn found that for single crystals having initial orientation between (110) [001] and (111) [112], the principalcomponent of the cold-rolled texture is (111) [112]. Koh and Dunn4 studied the cold-rolled textures of single crystals having initial orientations in the range (001) [110] to (111) [IT01 and found that these are stable end orientations. They also found that all orientations having a [110] direction parallel to the transverse direction rotate to either the (001) [110] or the (111) [112] stable end orientation except for orientations near (112) [11], which divide and produce a final texture consisting of (001) [110]and (111) [112] components. Crystals having a (111) <112>-type texture re-crystallized to a (120) [001] or (110) [001]-type texture. Crystals having orientations with a range of (001) to (335) in the rolling plane and [110] in the rolling direction recrystallized5 to a wide spread of the initial orientations resulting from a multiplicity of 30-deg rotations about several (110) poles. The present study was undertaken to relate other orientations of crystals of silicon-iron to their cold-rolling and recrystallization textures, so that one might rationalize polycrystalline recrystallization data on the basis of the known deformation texture and the behavior of single crystals in these orientations. PROCEDURE Samples were obtained from a cylindrical ingot of 3 pct silicon iron prepared as follows: Armco iron was melted with high-purity silicon flakes under an atmosphere of argon to minimize oxidation. The alloy was poured into a special mold to form an ingot which consisted partially of large columnar crystals. Plates were cut from the columnar portions of the ingot with the longitudinal direction parallel to the columnar axes and ground to 0.040 in. thick. The plates were heavily etched to a thickness of 0.032 in. to remove the cold-worked surface. Orientations of seventeen crystals were determined by Laue back-reflection techniques keeping the mean columnar axis as the reference direction. The plate was then cut in two, parallel to the columnar axis. One portion of the plate was rolled at room temperature parallel to the columnar axis to a reduction in thickness of 84 pct. The remaining portion of the plate was rolled also at room temperature across the columnar axis to a reduction of 66 pct, at which point the crystals began to separate at the boundaries. After rolling, nine individual crystals were removed from the strip by cutting along the crystal boundaries with a jeweler&apos;s saw. Fig. 1 shows the original orientations of the six crystals that were straight-rolled and of the three crystals (4, 7, and 8) that were cross-rolled. Each rolled crystal was carefully etched to approximately 0.002 in. thick. Textures of the cold-rolled crystals were determined by use of the diffractometer with a non-integrating sample holder. The pole figures were made for the (200) poles using molybdenum Ka radiation and were plotted by an automatic stereographic projection recorder.&apos; Spurious poles were determined by rerunning portions of the pole figures using strontium oxide to filter out the Ka radiation. The central portions of the pole figures have not been determined. The pole figures were completed to about 55 deg from the periphery at which point the sample holder interfered with passage of the beam. Following the determination of the cold-rolled

Jan 1, 1959

By J. Doig, A. A. Bauer, F. A. Rough

AN investigation of the phase relationships between the 6 phases of the uranium-molybdenum and uranium-titanium systems was conducted by studying alloys ranging in composition from uranium-31.5 at. pct Mo to uranium-34 at. pct Ti. A ternary cut showing these phase relationships is presented upon the basis of thermal-analysis data obtained and upon the basis of metallographic and X-ray examination of heat-treated and quenched specimens. Isothermal ternary sections, inferred from phase relationships determined between the two 6 phases, are presented for the uranium-molybdenum-titanium system. In the compositional range investigated, a y-ura-nium solid solution exists at elevated temperatures. At about 900°C the 6-U2Ti phase, with limited molybdenum solubility, forms. Epsilon, a molybdenum-titanium-rich solid solution appears at the same temperature and appears in all phase regions that exist below this temperature except in the terminal 6-phase regions. The y phase is stable to approximately 660°C in titanium-rich alloys; the y and 6-U,Ti phases decompose at this temperature to a uranium in a peritectoid reaction. The y phase in molybdenum-rich alloys of the ternary cut studied decomposes in an apparent eutectoid reaction, at about 593°C, to the 6-uranium-molyb-denum and a-uranium phases. The e phase while present, presumably plays a negligible role in these reactions. Titanium was found to markedly decrease the stability of retained y in these alloys. Age-hardening characteristics developed in titanium-contain ing uranium-molybdenum alloys quenched from 900°C and aged at 500°C are ascribed to decomposition of Y to the a and E phases. INTRODUCTION Alloys of uranium with molybdenum, titanium, and zirconium, respectively, are of great interest because of their potential use as reactor fuels. As a result, this interest extends to the constitution of these alloys, particularly in view of their uniqueness of constitution. In these systems, alone, among known uranium-alloy systems, an intermediate phase forms by direct decomposition of the high-temperature y-uranium phase. As a prelude to possible future alloy development, an investigation has been undertaken of the phase relationships that occur between the intermediate phases of these systems. These phase relationships have already been reported for the intermediate 6 phases of the uranium-zirconium and uranium-titanium systems.&apos; The results of an investigation of the phase relationships between the 6 phases of the uranium-molybdenum and uranium-titanium systems are reported here. The phase relationships that occur in the binary systems pertinent to this investigation are shown in Fig. 1. Phase nomenclature appearing throughout this report is as shown in these diagrams; the crystal structure of the phase is given in Table I. EXPERIMENTAL PROCEDURE Alloys were cast and fabricated to flat plate. Specimens were heat treated and examined metal-

Jan 1, 1959

By A. A. Bauer, F. A. Rough, G. H. Beatty

AS a result of recent studies, the constitution of the zirconium-uranium system has been fairly well defined. A diagram for the system is shown in Fig. 1. However, both oxygen and nitrogen are known1-3 to have a pronounced effect on the limits of both ß- and e -phase regions. It has been shown that small amounts of oxygen severely constrict the compositional limits of these phase regions in the ternary zirconium-uranium-oxygen system. A previously published tentative diagram shown in Fig. 2 illustrates the ß-phase constriction resulting from oxygen additions. Generally, iodide zirconium has been used in constitutional studies of zirconium-uranium alloys. While this is the highest purity material available, cast iodide zirconium-uranium alloys will generally average from 200 to 300 ppm 0 and from 50 to 60 ppm N. Thus, while the constitution of the zirconium-uranium system is fairly well defined, it must be realized that this definition applies to alloys containing in the vicinity of 250 ppm 0 and 50 ppm N. The present investigation was undertaken to accurately determine the boundary between the ß-plus-P and ß phases at a single temperature in the binary zirconium-uranium system by quantitatively

Jan 1, 1959

By L. O. Brockway, W. C. Bigelow, J. A. Amy

Specimens of Inconel-X alloy solution-treated at 2050°F and aged for periods of 1, 10, 100, and 1000 hr at 1200°, 1400°, and 1600°F have been examined by electron microscopy and by electron and X-ray diffraction. Four minor phases were identified: titanium nitride, niobium nitride, an M23C6 complex carbide, and the intermetallic ? phase. The two nitrides were found in all of the aged specimens and in the solution-treated alloy, the y&apos; phase formed at all aging temperatures, while the M23C6 carbide formed only on aging at 1200° and 1400°F. Variations in the hardness, rupture strength, creep strength, and yield strength of the alloy have been shown to be related to variation in the size and distribution of the particles of the y&apos; phase within the matrix grains of the alloy, with maximum values of these properties occurring when there is a maximum amount of the phase present and a fine state of dispersion of the particles prevails. THE nickel-chromium alloys containing titanium and aluminum are widely used in applications requiring high strength at elevated temperatures. Studies on relatively simple ternary and quaternary alloys&apos;-4 have indicated that the favorable high-temperature properties of these alloys are related to the precipitation of an intermetallic ?&apos;-phase having a structure based On that of the Ni3A1 phase of the nickel-aluminum system. The present investigation was undertaken to identify the minor phases and to study the microstructural changes occurring in one of the more complex commercial alloys as a result of aging in the service temperature range, with particular emphasis on investigating the role of the ?&apos; -phase. The microstructural changes were studied by electron microscopy and the minor phases were identified by X-ray and electron diffraction. MATERIALS AND METHODS Inconel-X alloy was selected for this investigation because the previous studies of Frey, Freeman, and white6 provided extensive information on the variations in metallurgical properties of this alloy resulting from high-temperature aging treatments. Specimens aged 1, 10, 100, and 1000 hr at 1200°, 1400°, and 1600°F were made available for the present use. These were taken from 1-in. round-bar stock of a commercial heat having the following weight composition: 0.04 C, 0.56 Mn, 6.59 Fe, 0.007 S, 0.38 Si, 0.03 Cu, 73.22 Ni, 14.97 Cr, 0.78 Al, 2.38 Ti, and 1-02 Nb. They were solutjon-treated at 2050 for 4 hr and then water-quenched prior to aging. Powder X-ray diffraction patterns were obtained from insoluble minor phases which were separated from the alloys by digestion in the reagent of Mahla and Nielsen.6 Back-reflection patterns were obtained from electrolytically polished surfaces of the bulk search to detect the ?&apos;-phase&apos; Cu-K a radiation was used in both cases. In the electron-diffraction studies, the general method developed by Heidenreich, Sturkey, and

Jan 1, 1959

By M. Metzger, T. A. Read

The strengthening effects of hydroxide and synthetic plastic films in the creep of cadmium crystals were studied. The results were broadly consistent with the naive mechanical model. The dislocation-film reactions and the significance of the macroscopic stresses associated with certain films are discussed in the paper. ALTHOUGH a number of studies have been made of the strengthening of metal single crystals produced by surface films usually less than Ir in thickness, the mechanisms underlying this phenomenon are still not well established. Roscoe&apos; first noted the critical shear stress and the stress-strain curve of cadmium-crystal wires to be raised markedly by the presence of oxide films. Subsequent investigators2-&apos; have confirmed the effect for several metals and films including a number of plated poly-crystalline metal films. Harper and Cottrel1" with a thin film on zinc presumed to have formed as a result of etching and washing treatments) did not detect a strengthening at a rate of extension of 10 &apos; sec-&apos; although at lo-&apos; sec-&apos; the film raised the flow stress by 7 pct at 0.0005 extension and by 22 pct at 0.01. The marked strengthening at moderate strains thus appeared to be the result of a dynamical effect dependent on the rate and amount of plastic flow. Other observations&apos;. " are consistent with this view. The large effects of films on the tensile creep rate of single crystals were demonstrated when the observation of Andrade and Randall," that the creep rate of cadmium crystals increased on immersion in aaueous solutions of certain cadmium salts. was shown&apos; * to hold only when a film was present initially and was explained by the attack of the solution on the film and the removal of its strengthening effect. Changes in the creep rate interpretable in terms of the removal or formation of various films have been observed by other investigators.3,8,10,31 Certain other experiments have been reported in which surface films or liquid environments have affected the plastic behavior of metals, but these are not within the scope of the present work which deals with the effect of solid films on single-crystal slip. Possible Mechanisms—The film does not significantly reduce the load on the crystal in the elastic range (the elastic moduli of film and crystal are not too greatly different and the area of the film is so small that its share of the load is negligible) so that the initial operation of internal Frank-Read sources is not affected. However, as Fisher" has pointed out, a source terminating on the crystal surface requires only half the critical stress for activation as an internal source of the same length and a relatively strong film (even a very thin one) would pin the free ends of the surface sources so that, if surface sources are responsible for plastic flow in a clean crystal. such a film would increase by roughly a factor of 2 the stress necessary for generation of dislocation loops at a given rate. The other general possibility is that the film resists the passage to the crystal surface of internally generated dislocations. If the film is adherent and if the specimen is to exhibit slip of the same general character as a film-free specimen, the film must deform or fail in shear at the active slip planes. The naive mechanical model, where shear-stress relaxation across the active slip plane in the metal transfers load to the film until it deforms and slip can

Jan 1, 1959