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By D. Turnbull, J. E. May

THE (110) [001] texture in silicon iron is of considerable interest both from the technological and scientific points of view. Its occurrence was reported more than 20 years ago.1-4 The texture develops by means of secondary re crystallizatjon5 and can be very strong, that is, greater than 90 pct alignment even thouh the primary re crystallization texture is weak or complex. This behavior is in contradistinction to the face-centered metals which develop their strong secondary recrystalliza-tion texture from a strong primary recrystalliza-tion texture.', The microstructural changes accompanying the (110) [001] texture formation in silicon iron are as follows: When properly prepared cold-rolled sheet (i.e., 0.015 in. thick) is annealed at about 800°C, primary recrystallization occurs and a fairly stable fine-grained primary recrystallized matrix of about 0.02-mm-diam grain size is produced. The material at this stage does not have the strong (110) [110] texture. As the temperature is raised to about 900°C, relatively large grains appear in the finegrained matrix and they grow at the expense of the smaller grains to many times the sheet thickness. In time the complete sample is consumed by these large grains. This process of the growth of relatively few grains (about one in 105 primary grains) at the expense of many grains is called secondary recrystallization. Since all the secondary grains are of essentially (110) [001.] orientation, the strong texture is developed by this secondary recrystallization process. Theories of the (110) [001] texture in polycrystal-line silicon iron have been proposed by Decker and Harker and by Dunn.Decker and Harker have shown that grains initially in the (110) [001] orientation will upon annealing after cold-rolling, re-crystallize back to the initial orientation. To account for the sharp texture in silicon iron they propose that (110) [001] grains become more highly strained than grains in other orientations and therefore recrystallize first. They are then the lowest energy grains and can consume their higher energy neighbors. Grains in orientations other than (110)

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 &"' 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 D. Turnbull, R. E. Cech

Small particles, 10-20 microns diameter, of a 28.6 atom pct nickel, balance iron alloy, have been supercooled 186 C with respect to bulk alloy M, temperature. Particles exhibit a marked mechanical shock sensitivity while being held in a supercooled state. The tendency for shock to induce martensitic transformation appears to be a maximum at —140 to —160°. Slow cooling of particles in mechanical contact with one another results in extensive martensite formation. This is prob-ably the same effect as the catalytic effect observed in polycrystals where martensite formation in one grain induces transformation in other grains. AS a result of extensive research over the past decade on the martensitic transformation, a much better though not complete understanding of the transformation has resulted. Recent reviews by Bilby and Christian' and Kaufman and Cohen2 have

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' ±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' 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.' In addition, the interactions of dislocations and solute atoms were reviewed by Cottrell.' 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'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' 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 E. Gregory, C. G. Goetzel

The outstanding elevated temperature properties of materials made from sintered aluminum powder have been well established in recent years.1,2 and considerable investigation has been carried out on the structures which appear to be responsible for this type of strengthening.2,3 The maximum operating temperature of such materials is severely limited, however, by the low melting point of the aluminum matrix; and, therefore, considerable interest was aroused in methods of introducing the

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' 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' 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,' 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' 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 A. U. Seybolt

The pressure-temperature relations required to maintain the existence of Si3N4 in silicon-iron of 0.44-11.7 pet Si have been partially explored. The critical data obtained have allowed the calculation of some thermodynamic quantities, and have shown evidence of an order-disorder two-phase field extending at 800°C from about l pet to 5.5 pet Si. THE presence of silicon nitride in electrical sheet, nominally about 3 1/4 pet silicon, balance iron, has been described by several authors'" but there has been some discrepancy among them regarding the identity of the nitride. Also, little has been reported on the quantitative thermodynamic prop- erties. In the work to be reported here, the nitride has been found to be more stable than described by Corney and Turkdogan." Several silicon nitrides have been described in the past, including SiN, Si3N4 and Si2N4 (see, for example, Abegg6 and Pascal7). However, the literature on nitrides other than Si,N, is all very old. No recent investigators using the more powerful tools available today have reported the presence of any nitride other than S3,N4. W. B. Hicke and L. R. Brantley8 in 1930 determined the dissociation pressure of Si3N4 which they made by reacting nitrogen

Jan 1, 1959

By J. D. Livingston, J. J. Becker

A MAJOR difficulty in the experimental study of precipitation-hardening is the measurement of particle sizes too small to be easily resolved with the microscope. It has been shown recently, however, that magnetic measurements on copper-cobalt al- loys in the aged state can be used to determine the average volume, total volume, volume distribution, and shape of the ferromagnetic cobalt-rich particles, even though the particles are submicroscopic in size. r' These alloys also are known to exhibit considerable precipitation hardening. This paper reports some results on the dependence of the mechanical properties of such an alloy on the particle size, determined magnetically. It further illustrates the use of other magnetic measurements in interpreting structure changes occurring during deformation.

Jan 1, 1959

By C. D. Wiseman

THE concept of alloying to increase the strength of metals originated during the bronze age. However, at the present time there is no single theory capable of explaining all of the observed strengthening effects of alloying elements on the mechanical properties. In general, it may be said that solid solutions are stronger than the pure metal and that the strengthening effect increases with increasing alloy content. Various theories for solution hardening have been proposed, the first of which was presented by Rosenhain who suggested that the alloying elements roughened the slip planes, thereby requiring a higher stress to initiate slip. Recent work by French and Hibbard2 confirmed Norbury's3 conclusion that those alloying elements which cause a greater change in lattice parameter have larger effects on hardness. However, a given change in lattice parameter produced by different alloying elements does not cause the same change in hardness. A further refinement was suggested by Dorn, Pietrokowski, and Tietz4 who considered differences in valence between the solute and solvent with the change in lattice parameter to explain the plastic properties of aluminum alloys. Allen, Schofield, and Tate5 further investigated the valency contribution to solution strengthening by testing some copper-base solid-solution alloys having constant electron densities. Tensile tests performed on these alloys gave identical stress-strain curves even though the atomic size effect, which varied by a factor of two, was neglected. The advent of dislocation theory6-8 provided a new and powerful tool capable of explaining many phenomena of plastic deformation and indicated new approaches to solution hardening. The basic con- cept of recent theories is that solution hardening is not due to stresses associated with randomly dispersed solute atoms, but rather to a nonuniform distribution of the solute. This conclusion was reached by consideration of the effective tension present on each dislocation line and the ability of a dislocation to pass an obstacle. cottrell suggested the possibility that the internal stresses due to randomly distributed solute atoms would offer essentially no resistance to the passage of dislocations. He reasoned that an edge dislocation may be considered as a rigid line discontinuity. As the dislocation moved through a crystal, the random stress fields would be equally distributed along its length. Since half of the stress fields would be acting to move the dislocation forward and the other half trying to move it back, the net effect on the dislocation would be zero. Thus the randomly distributed solute atoms would not contribute appreciably to solution strengthening. Mott and Nabarro10 considered the dislocation as a flexible, rather than a rigid, discontinuity. They obtained a simple model for a dislocation moving in a lattice having precipated particles, where the dislocation would actually bend around the obstacle until it would loop back onto itself to rejoin and then continue onward. Their work indicated that the minimum radius of curvature of the dislocation line, under the action of an external stress and in the region of an internal stress, would be such that the dislocation would be unable to pass through a matrix containing small closely spaced precipates by the looping process. The dislocations would tend to remain rather straight, approaching the condition of Cottrell's rigid dislocation. Hence, the strengthening must not be due to random solute atoms; however, it might be due to the concentration of atoms, either as clusters of like atoms or as short-range ordered regions, or to the concentration of solute atoms around dislocations. To date, four mechanisms of solution strength-

Jan 1, 1959

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

EARLY studies by Gough and sopwith' 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,' 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 R. A. Meussner, R. T. DeHoff, F. N. Rhines

ZINC diffuses through copper more rapidly than does tin. Accordingly, when a ternary diffusion couple is made, by bringing an 0 copper-zinc brass into contact with an a copper-tin bronze at fixed high temperature, it is to be expected that zinc will diffuse into the bronze faster than tin diffuses into the brass. Adjacent to the brass side of the couple the total alloy content (zinc plus tin) should diminish, therefore, while next to the bronze side the alloy content should increase. Since the path of compo- sition change must be continuous, in a single-phased alloy, it should follow a curved and, in general, an S-shaped course. The realization of this prediction is demonstrated in Fig. 1, where the composition paths of two ternary diffusion couples are plotted on the appropriate isotherm of the copper-tin-zinc phase diagram. The diffusion couples were both made from a binary copper-tin alloy analyzing 5.0 pct tin placed against binary copper-zinc alloys analyzing 18.9 and 29.3 pct Zn, respectively. These alloys were produced from electrolytic grades of copper and zinc and a pure grade of straits tin, melted under borax in clay-graphite crucibles and cast in a vertical iron mold. Cylindrical pieces 1 in. in diam and 1 % in. long were machined from the casting and were faced by metallographic polishing to good matching end surfaces. Pairs of the cylindrical pieces were held

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. L. Lytton, J. E. Dorn, L. A. Shepard

Single aluminum crystals were subjected to creep in simple shear on the (111) planes in the slip direction. The activation energies for creep were calculated from the effect of small abrupt changes in temperature on the creep rate just before and immediately following the temperature change. The results definitely establish the fact that creep of single aluminum crystals occurs by-three unique processes, characterized by thethree distinct and isolatable activation energies: The 35,-500-cal-per-mole activation energy obtained at the highest temperatures was ascribed to a dislocativationtion climb process; the 28,000-cal-per-mole activation-energy process, occurring over the intermediate-temperature range was attributed to a cross-slip mechanism; and it was suggested thot the 3400-cal-per-mole process observed below 400°K may be the Peierls energy. THE most pertinent question regarding the phenomenon of creep in crystalline materials is concerned with the identity of the crystallographic mechanisms of deformation that control the creep rate. For many years slight progress was made in uncovering the basic mechanisms for creep. Over the past 10 years, however, two parallel lines of investigations have contributed to a more definitive understanding of the processes involved in creep. The extensive development and maturing of dislocation theories for deformation of crystalline materials&apos; proved to be of paramount importance for this progress. And second in importance was the replacement of the former prosaic methods of creep testing by new techniques&apos;." which were especially

Jan 1, 1959