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By E. Hornbogen

The deformation mechanisms of a iron-phosphorus alloys were compared at 20oand —196°C. Alloying with phosphorus increases the resistance to slip, but has little effect on the resistance to twinning. The stress for onset of twinning is nearly independent of temperature, but there is an increasing tendency for cleavage along (112) twin boundaries with decreasing temperature and increasing phosphorus content. FIVE iron-phosphorus alloys and one high-purity iron (0.004 pct C, 0.004 pct N, 0.05 pct O) were vacuum melted and cast, then homogenized for 6 hr at 1100oC and water-quenched. Single crystals were cleaved from the coarse grains produced in this manner. The hardness was measured* on polished (100) surfaces of the crystals at 20" and -196°C. Laue back-reflection patterns indicated a deviation of not more than 3 deg from coincidence of the {100} plane with the surface. The deformation mechanisms were studied by relief effects on the polished surfaces. Yield points in compression (0.5 pct offset) were measured with polycrystalline material. At 20°C the addition of phosphorus to a iron leads to a change from slip to twinning as the main deformation mechanism, Figs. 1(a), (b). Between 2 and 4 at. pct P slip and twinning occur simultaneously. In alloys with more than 4 at. pct P twinning is the main deformation mechanism and slip was observed only in the neighborhood of twin intersections. All cracks at 20oC were on (100) planes, some initiated by twins.' From measurements made at-196oC, hardness and yield points of all the alloys were nearly constant and the same as the hardness of high phosphorus alloys that deformed by twinning at 20°C, Figs. 2 and 3. In the high-purity iron, plastic deformation at -196°C occurred by both slip and twinning, but deformation in the iron-phosphorus alloys appeared to be entirely by twinning. In the high phosphorus alloys a large number of cracks formed along the (112) twin boundaries and at intersections of twins, in addition to the (100) cleavage, Fig. 1(c). DISCUSSION In , iron, plastic deformation can occur either by slip or by twinning, depending upon composition,

Jan 1, 1961

By D. W. Levinson, L. E. Tanner

DURING the course of an investigation of the zirconium-iron-tin system the zirconium-iron system was reexamined up to 55 pct* Fe. The alloys pre- visible melting3 and X-ray diffraction studies were made of samples of the alloys. The ferromagnetic properties of ZrFe2were determined by Professor P. W. Selwood* using a modified Faraday balance.4 The zirconium-rich portion of the phase diagram is presented in Fig. 1 and compared with the work of Hayes et al.1 The maximum solubility of iron in ß is somewhat decreased while the eutectic temperature is raised. There seemed to be no change in the eutectic composition of 16 pct Fe. Since the base material was so low in iron content, it was possible to establish the maximum solubility in a between 0.017 and 0.025 pct Fe at the eutectoid temperature. The observation of fine ZrFe, particles in the micro structure of a specimen of 0.012 pct Fe alloy quenched from 700°C indicated that the solubility drops below this composition at 700° C and lower. Further study was made of the intermediate phase ZrFe2. wallbaum5 identified the compound initially as ZrFe2 with a C 15 (MgCu2) structure, placing it at 55 pct Fe stoichiometrically. Hayes et al.1 believed they found the phase at about 47.2 pct Fe and called it Zr2Fe3 but reverted to ZrFe, in the discussion of their paper.6 Jordan and Duwez7 confirmed Wallbaum's work as well as finding the same single-phase structure to about 62.3 pct Fe or Zr0-61 Fe2-18. In order to establish the ternary phase relations in the zirconium-iron-tin systema the exact position of this phase had to be known. This was accomplished by X-ray diffraction, visible melting, and metallographic techniques. Elliott8 obtained a single-phase ZrFe2 X-ray diffraction pattern from an alloy of about 55 pct Fe. This was confirmed in the present study with an alloy of 54.81 pct Fe. However, extra lines (attributable to a or ß zirconium) were found in diffraction patterns of the 47.42 and 49.83 pct Fe alloys. The melting characteristics of these same alloys were studied by suspending 47.42, 49.83, and 54.81 pct

Jan 1, 1960

By H. P. Stüwe

HE recent papers of Aust and Rutter112 have again brought to mind the importance of certain "special" orientation relationships between the lattices of two fcc crystals on the mobility of the grain boundary separating them. No theoretical treatment of this problem has been offered till now. The only principle published so far that has given an indication why certain orientation relationships should be "special" is the counting of "coincidence sites" according to the suggestions by Kronberg and Wilson.3 The "coincidence plots" published by these authors show, for instance, that two fcc lattices rotated by 38 deg around a common (111)-axis have 1/7 of their lattice sites in common. Such an orientation relationship is also characteristic for high boundary mobility. The accuracy of the orientation relationship needed for high mobility is not too rigid. Deviations up to 10 deg from the ideal orientation seem to be tolerable as can be gathered from the experimental data.'j4 The auestion arises, then. how the density of coincidence sites will be affected by a deviatioi from mathematical accuracy. This can be checked by a simple model. Two sieves are prepared, the arrangement of the holes corresponding to lattice sites on a (111)-plane in a fcc crystal. They are placed upon each other, Fig. 1. One is kept fixed, the other is rotated around an axis pushed through one hole in common to both. The light falling through holes of both sieves is then a measure for the density of coincidence sites. If the diameter of the holes is very small, light intensity is contributed only by holes the centers of which coincide "exactly." If the diameter of the holes is rather large, some intensity will be contributed by

Jan 1, 1962

By J. P. Neumann, L. Raymond

At temperatures near 1000°C, only the (112) (111) slip systems are operatire in tungsten. Therefore, the substructure introduced into the billet upon rleforming a single crystal by rolling at 1000 "C can be controlled by proper selection 01. processing ral'iubles. Using a reduction of 10 pct pel- pass, the (001)[110] and the (110)[001] crystals will deform by duplex slip rip to a 50 pet reduction in thickuess. These rolled single-crystal sheels are characlerized by anisotropic hardening, retention of ductility with warm working, lattice bending which is related to the conlacl (angle, and macroscopic dimensional changecs in the length bid not the width of the billet. When several slip systems become operative, a greater degree of work hardening is itztvoducetl into the crystal. This rolling- condition is characlerized by isotropic hardening, loss of ductilily with warm working, complex lattice distortions, and macro-scopic dimensional changes in both the length rind Width of the billel. IN tungsten, the {1 10}(111) slip systems are operative below room temperature,' while above 700°C only the {112{ (111) slip systems are observed.2,3 In the transition region, i.e., room temperature. both systems appear. It is the purpose of this investigation to show that tungsten single crystals deformed by rolling at a temperature where only one slip system is operative generate dislocation substructure which depends on the crystal orientation. For a specific crystal orientation. the resulting dislocation substructure can be further influenced by modifying the rolling procedure. Crystals oriented for multiple slip display less substructural sensi- tivity to modifications in processing techniques than do single crystals oriented for duplex slip. Under simple slip modes of deformation, very little work hardening is introduced into a rolled single-crystal sheet. Mechanical properties such as room-temperature strength. ductility, and hardness are used to confirm the existence of the different work-hardened conditions generated within the crystal by modified warm-rolling techniques. EXPERIMENTAL PROCEDURE Material. Single-crystal billets of four different crystal orientations. grown by the Arc-Verneuil technique. were ground to a size of 0.25 by 0.375 by 3 in. In terms of their rolling plane and rolling direction, the billets had the following orientations: (1101 [001 ] (110) [110] (001) [110] (001) [100] The actual orientation of all crystals was within 5 deg of the ideal orientations. The typical impurity content of the crystals is given in Table I. Polishing and Etching. Polishing was done elec-trolytically in a 20 g per liter aqueous solution of NaOH at approximately 10 v. It was established by the Laue back-reflection X-ray technique that the surface damage due to grinding and cutting operations with a diamond wheel did not exceed 0.001 in. Therefore after each cutting or grinding operation at least 0.002 in. was removed electrolytically from the surface in order to eliminate surface effects. By lowering the voltage to 3 v, subgrain boundaries and individual dislocations are identified in agreement with Berlec 4 where the etch-pit traces on a cubic plane form a square. The etching time was about 5 sec at room temperature. Rolling. Rolling was carried out on a Loma 2-high mill (Model 600). The peripheral velocity of the 6-in.-diameter rolls was 500 in. per min, with the surface temperature of the rolls about 400° to 450° C The billets were heated before each pass for 30 min in argon to 1000 C. Oxidation of the crystals during rolling in air resulted in a thin layer of greenish-yellow WO 3 This oxide was removed after each pass by immersing the crystals for a few minutes in a boiling NaOH solution. Prior to the initial rolling pass, a surface layer of 0.001 in. was removed by polishing. The crystals were then annealed in vacuum (10-4 torr) at 2400 C for 30 min. All crystals were rolled in the same direction; i.e., the same end was always introduced into the rolls. The rolling program was conducted in

Jan 1, 1965

By F. N. Rhines, A. S. Nemy

The mode of high-temperature tertiary creep of 523-0 aluminum alloy was found to be strongly stress dependent. The occurrence of necking and/or fissures during tertiary creep exhibited a sequence with varying stress, wherein fissures with no necking occur at a minimum stress and necking with no fissures occur at a maximum stress. At an intermediate stress, tertiary creep begins without necking but with fissures in a region just beneath the external surface, followed by necking and the development of fissures along the axis of the specimen. The results are interpreted in terms of grain boundary gliding and the hydrostatic stresses produced by restraints to grain boundary gliding. THERE appear to be two possible reasons for the existence of a period of accelerating elongation prior to rupture during high-temperature creep in metals; namely, 1) a change in the structure of the metal itself, leading to a change in its response to loading, and 2) a reduction in the cross section of the metal resulting in a higher unit loading. Howe,' by annealing and retesting broken low-temperature creep specimens, found that irreparable damage is done once a metal is subjected to creep. Andrade2 first pointed out the association between the reduction in cross section and the increase in creep rate. The present research was designed to investigate both of these factors by retesting specimens machined from material which had been subjected to high-temperature creep testing short of rupture. EXPERIMENTAL METHOD An aluminum alloy, 52s-0, was selected for these studies because it is constitutionally simple, is strong enough to be relatively insensitive to mechanical damage during machining,3 and undergoes accelerating creep in a convenient temperature range. This alloy is hardened by 2.6 wt pct Mg in solid solution and is not subject to overaging effects; it has a very small quantity of an insoluble impurity phase, Mg2Si, finely dispersed throughout its micro-structure. Creep specimens, similar in design to ASTM 0.252-in. tensile specimens, were machined from 3/4-in. round stock and the surfaces were electro-polished. A 24-hr anneal at 500°C was then applied to stabilize the grain size to an average diameier of 0.27 mm. Subsequent heating for as long as 700 hr at the intended test temperatures produced no change in the tensile properties, indicating a well-stabilized state of the material. Corresponding to each of the typical testing conditions listed in Table I, one creep specimen was tested to destruction and this test was employed as a guide in the selection of times for subsequent tests. Duplicate creep tests were then run to various points along the creep curve to produce specimens which were used to determine changes in mechanical properties and microstructures. The latter were examined at the midsections of the specimens. Other specimens were tested to various stages of tertiary creep, after which they were remachined to new cylindrical test specimens, electropolished and re-tested in creep. RESULTS The major findings of this investigation may be illustrated by a comparison of the results of three sets of creep tests. These were run at 400°C at three stress levels, namely 750, 1000, and 1500 psi. In presenting these results in Figs. 1, 5, and 8, the creep curves are given in pairs: That curve of each pair which is drawn through filled circles corresponds to the initial test, and the curve drawn through open circles (and designated by - R) represents the result of retesting the same specimen after machining to a new cylindrical surface. The load was readjusted to the original unit stress at the beginning of each retest.

Jan 1, 1960

By Dogan E. Gücer

In the following note, with the help of a new parameter of strain hardening, the attention is drawn to the close relationship between the relative performances of steels under plastic range cycling and their strain hardening characteristics. If a cantilever beam of rectangular cross section is tested with the arrangement shown in Fig. 1 in reversed bending between constant deflection limits at the lever head, the longitudinal strain-deflection hysteresis shown in Fig. 2 is obtained. There is no lateral strain due to constraint at the rectangular test section.' If the absolute value of strain undergone between a maximum state of tension and maximum state of compression is called A, it will be seen that A decreases with cycling rapidly due to the strain hardening in the test section and the ensuing change in the bent beam profile. It will also be seen that A reaches an approximately stable value around 10th cycle. If we call the first cycle strain range, A,, and that of 10th cycle, A,,, then is an index of the strain hardening capacity at a particular deflection level. A plot of n vs ? is reproduced in Fig. 3 for two ASTM steels: A-302 and A-201. A-302 is a low alloy structural steel, A-201 a low-carbon steel. The specimens were first normalized at 1650°F for 75 min then grooved with a milling cutter; and the notches were ground to 50G finish. The final operation before testing was a stress relief at 1150°F for 75 min. The behavior of the two steels changes around ?1 = 0.8 pct or A,, = A, -n = 0.7. If these curves are compared with the endurance life curves given in Fig. 4, it will be seen that the relative performance of the two steels also change around A,, =. 0.70 pct. The steel with lower strain hardening capacity (7) at a certain strain level shows a longer endurance life, irrespective of their strength levels. Since the exponent governs strain hardening at lower strain levels than the Modulus, the relative values of both parameters also coincide with the change in n values and the relative performances of the two steels at different strain levels. These two observations indicate to the close relationship be-

Jan 1, 1962

By B. D. Cullity, S. S. Hsu

The stress distribution at the surface of a twisted cylinder is analyzed along the boundary of a slip plane of arbitrary orientation and this analysis is applied to the torsion of cylindrical crystals of magnesium. A criterion for slip is developed and the critical resolved shear stress of magnesium in torsion is found to be 0.038 kg per sq mm. The mechanism of torsional deformation in magnesium and aluminum is described, as well as the relaxation of a twisted crystal at elevated temperatures. THERE has been considerable fundamental study A of the mechanism of slip occurring during deformation in tension and compression but comparatively little attention has been paid to the mechanism of torsional deformation. This paper is concerned with the way in which a single crystal deforms in static torsion and with the phenomenon of untwisting which a twisted crystal undergoes during annealing. Particular attention is paid to the application of the critical resolved shear stress law to torsional deformation. Probably the most likely mode of torsional deformation that can be imagined consists of rotation of one part of the crystal relative to another on the active slip plane. Here the most interesting feature is the slip direction. If a cylindrical single crystal is twisted about its axis and if, to consider the simplest case, the active slip plane is normal to the specimen axis, then the direction of gross slip at any point must always be at right angles to the radius drawn to that point. It follows that the crystallographic direction of slip must be continually changing, in sharp contrast to slip in tension which occurs in a crystallographically constant direction. Extensive investigations of slip in torsion have been made by Gough and his associates.' They made torsional fatigue tests on metal single crystals belonging to a number of different crystal systems and observed, with a microscope, the appearance of slip lines on the surface and of strain markings on the transverse cross section of cylindrical specimens. They concluded that the critical resolved shear stress law was just as valid in torsion as in tension, in the sense that slip occurred on that plane and in that direction in which the resolved shear stress was a maximum. They also established that the operative slip planes and directions were the same as in tension. They did not, however, measure the critical resolved shear stress in torsion nor, in fact, did they establish that a critical value of the resolved shear stress was necessary for the initiation of slip. Their investigations were, moreover, restricted to torsional fatigue tests which necessarily involve small strain amplitudes. Wilman,' studying crystal growth and the abraded surfaces of crystals, observed crystal fragments

Jan 1, 1955

By R. L. Fullman, J. W. Cahn

A method is derived for obtaining the distribution of sphere diameters and plate thicknesses (or pearlite spacings) from size distribution functions obtained along randomly oriented lines. The method described offers several advantages over existing methods. IT is often of interest to measure not only the average particle size but also the distribution in sizes of particles dispersed in an opaque material, such as an alloy. Particles of a single size will exhibit a range of apparent sizes on the plane of polish. If the sample contains a distribution of particle sizes, the distribution of observed sizes on the plane of polish is related to the distribution of actual particle sizes by an integral equation, For example, a distribution of sphere sizes, N(r),

Jan 1, 1957

By R. S. Craig, W. E. Wallace, G. S. Kamath

The destruction of long-range order in Mg-Cd, has previously been thought to occur as a second order process. In the present work a variety of X-ray diffraction techniques are employed to show that in this case and in Mg-Cd alloys containing frorn 20 to 33 1/3 at. pct Mg the process more nearly resembles an ordinary first order phase transformation. It is found that the ordered alloy, which occurs as a single phase at lgw temperatures, transforms with increasing temperature into a Cd-enriched disordered (P) phase and an Mg-enriched ordered (a) phase. The interval over which these two phases coexist under apparently equilibrium conditiovs extends from 25" to 87°C content. At 33 1/3 at. pct Mg the two-phase region has disappeared. Measurement of the long range order parameter, s, for the ordered phase in MgCd, (from superlattice line intensities) shows that it disorders only very slightly before it is transformed into the p form. Kinetic experiments reveal that when the a phase is formed frorn the p phase by suitably quenching so as to suppress phase segregation, the transformation is essentially complete and the a phase has acquired its equilibrium value of S in less than 1 min. In an earlier investigation carried out in this Laboratory1 the rate of disordering of the MgCd3 superlattice was determined over an extensive range of temperature. The process was found to be first order and the rate constant, k, was established. At the lowest temperatures studied k was found to increase exponentially with temperature. At higher temperatures, however, it passed through a maximum and for the 100 deg interval below the point at which the superlattice was destroyed k was observed to decrease with increasing temperature. The various theoretical treatments1-3 of order-disorder phenomena lead to a negative temperature coefficient for k near the superlattice critical temperature but this region for MgCdB seemed unusually wide. Detailed analysis of the point indicated' that either the long-range order parameter, S, for MgCda varied with temperature in an anomalous way or the disordering in this instance is more complex than in the cases which have been treated theoretically. The original objective in the present work was simply to determine S vs temperature for MgCda to ascertain whether the disordering was in conformity with theoretical expectations.2° In an early stage of the work it was noted, however, that under equilibrium conditions ordered (a) and disordered (0) phases coexist in MgCd, over a considerable range of temperature. Since on thermo- dynamic grounds the coexisting phases must differ in composition, the investigation was enlarged to permit the compositions of the two phases in MgCd3 to be determined and to establish the extent of the two phase regions for alloys containing from 20 to 33 1/3 at. pct Cd.

Jan 1, 1963

By R. H. Hiltz, R. W. Douglass

Large-grain specimens of iodide titanium prepared metal-lographically were stain etched using the technique of New York University as modified by Watertown Arsenal Laboratories. Orientations of grains showing an abnormal response to stain etching were determined by back-reflection X-ray techniques. X-ray results showed that a-titanium grains, oriented such that their basal planes were parallel to the polished surface, have a slower reactivity to stain etching than any other orientation. Grains oriented such that their basal planes made small angles with the polished surface exhibited reaction rates between that of the true basal orientation and the normal rate. As the angle with the surface increases the reactivity increases up to a maximum angle of 14 deg. Basal planes making an angle with the surface of greater than 14 deg show normal reactivity to stain etching. These data, plus work on polycrystalline specimens, indicate that the oxidation rate of titanium might be reduced by correct alignment of crystal planes. ThE earliest observed phenomenon in the micrography of titanium was the occurrence of a grains which exhibited no birefringency. Even though a titanium possesses a hexagonal-close-packed structure and should be optically anisotropic, it can appear optically isotropic, when the crystal is so oriented that its intersection with the polished surface is perpendicular to the axis of symmetry. During the develoment of color staining techniques for titanium: it was noted that the a phase did not stain uniformly. Staining of specimens of commercially pure titanium resulted in a micro-structure of blue-colored grains, among which were randomly oriented a few grains exhibiting colors between the initial yellow and the final blue color. Under polarized light, these off-colored grains appeared to be optically isotropic. More intense study with polarized light, however, showed only the yellow grains to be isotropic. The intermediate colored grains exhibited weak birefringency, which at first glance is not detectable due to the strong birefringency of the surrounding structure. Aminoff2 and Straumanis3 have previously shown that in zinc the basal orientation is less reactive than other orientations. Leidheiser4 showed the same thing to be true for the hexagonal-close -packed configuration of cobalt. Thus, it would appear that the basal-plane orientation is responsible for the abnormality in stained titanium. Later work by Leidheiser5 on cobalt has shown that other planes besides the basal plane exhibited reaction rates slower than the normal rate. Reported planes were the (100), the (1011) and several planes making small angles with the basal plane. The last observance appears not to be due to the reactivity of the reported plane but due to the reactivity of the basal plane which is very close to being parallel to the surface. There are, then, two possible explanations for the range of colors observed in stain-etched a titanium. Since extensive research on the effect of orientation on surface reaction has failed to provide any definite trend, these two explanations are not adequate in themselves. Planes showing the retarded reactivity differ not only for different crystal structures but for metals of the same crystal structure and even for different reactions of the same metal. Tragert,6 Leidheiser,7 Tammann,6 and wagner9 have shown copper to exhibit retarded reactivity on the (111) plane. However, Leidheiser10 has shown that under other conditions the retarded reactivity of copper is associated with the (100)

Jan 1, 1960

By P. R. Gage, R. W. Bartlett

At high temperatues and reduced oxygen pressuves, molybdenum silicicles oxidize to form SiO(g) vathev than a passivating SiO2 film. This is a sevious problem for low-pressure applications of sili-cide-coated rejvactory tnetals. As oxiclalion pvoceeds, the higher oxidntion potential of silicon initially suppresses oxidation of molybdenum and silicon is depleted near the surface. Eventually, silicon depletion causes secondary passivation (SiO2) mid an active to passiue transition in oxidntion behavior at moderately low pressures. At very low pressures, silicon depletion continues until steady-state oxidation of both silicon and rnolyhdenum can proceed at rates propovtional to their initial stoicliiorrzetvies. Ohsel-vations of 'oxidatiou-rate belzcriliov at temperatures from 1101° to 1700°C and oxygen pressures from 10-7 to 1 at in were made using thermogravimetn'c, X-ray diffraction, and elect?*on-rtric?ro/,vobe techniqrres. The experimental results are in good agreement with calculated lirnits for the various types of behavior that were based on tlievtnochernicnl atzd dffusion rate data for the Mo-Si system. A protective oxide film normally forms during the oxidation of elemental silicon. However, at elevated temperatures and reduced pressures this film is not present and oxidation is rapid. wagnerl has shown that this behavior occurs because SiO(g) is more stable than SiO2. The behavior of the silicides at high temperatures is similar but more complicated. Molybdenum and several silicide compounds are involved and the chemical activity of silicon, or the equivalent silicon vapor pressure, can vary considerably in these phases. Also, diffusion in the silicides resulting from reactions in which a higher silicide is reduced to a lower silicide, or molybdenum containing dissolved silicon, must be considered. EXPERIMENTAL AND ANALYTICAL METHODS Isothermal oxidation experiments were conducted using hot-pressed MoSi2 and Mo5Si3 wafers. Each experiment was conducted at a fixed oxygen pressure by controlling the flow of oxygen in and out of the furnace chamber. Most of the experiments were conducted in a molybdenum-wound tube furnace. Special construction features, including use of a high-purity dense A12O3 refractory tube, permitted operation in high vacuum to 1500°C. Higher temperatures could be obtained at higher working pressures and with a sacrifice of tube lifetime. Temperature was measured with three Pt 6 pct Rh/Pt 30 pct Rh thermocouples and controlled with a proportional controller. Weight changes were monitored with a quartz spring balance. The few experiments, at higher temperatures and low pressures, were conducted in a cold wall vacuum chamber using induction heating with direct susceptance of the sample. Because of the variable levitation effect of the induction coil on the sample, weight changes could not be monitored continuously in these experiments. All samples representing both experimental methods were weighed before and after oxidiation and examined with a microscope and analyzed by X-ray diffraction. The analytical treatment assumes equilibrium at interfaces and uses existing thermodynamic data. For convenience, equilibria are expressed as chemical potentials or as vapor pressures of the gases involved. The resulting differences in equilibrium vapor pressure between adjacent interfaces and between the surface and external atmosphere drive diffusion processes in the solid and gas boundary film, respectively. These diffusion processes govern the rate of oxidation. A bibliography of the sources of thermochemical data for the reactions pertinent to the Mo-Si-O system is given in Table I. Reactions are listed with the sources of free-energy data referenced. Since all of these reactions involve one or more gas species, usually oxygen, a plot of the product-gas chemical potential, -RT In Pg, vs absolute temperature for each reaction is given in Fig. 1. These curves can be used to determine equilibrium vapor pressures or to compare the stability of different compounds in the various gases: O2, Si, SiO, and Moo3,. The data of Table I and Fig. 1 were used to determine the analytical results presented in this paper. EXPERIMENTAL RESULTS The weight changes for three MoSi, samples oxidized at 1500°C are plotted against time in Fig. 2. The treatments were identical except for the indicated variance of oxygen pressure and each curve represents one of three characteristic types of behavior that were observed. The upper curve is an example of passive oxidation, which is defined as

Jan 1, 1965

By M. van Swaay, C. E. Birchenall

Palladium has a large capacity for the dissolution or occlusion of hydrogen; the gas also diffuses very rapidly through the metal. Palladium thimbles are widely used in the laboratory for purification of hydrogen by diffusion. The use of palladium filters could be extended to several large-scale applications if greater stability of the permeation process could be attained. In this paper a number of aspects contributing toward this goal are discussed, and new data on solubility and diffusivity are given. Palladium sheets of 0.005, 0.010, or 0.020 in. thickness were prepared by three procedures: casting and rolling, sintering palladium powder, and sintering palladium powder to which 0.1 pct thorium oxide had been added. Half-inch diam circular specimens were cut and clamped in a stainless steel holder provided with knife edges to seal the palladium sheet with soft copper gaskets. The seals were tested for leaks at l0-5 mm Hg. No difficulties from this source were encountered even after many temperature cycles in the system. The holder was silver-soldered to Kovar-glass seals and attached to the system through glass ball joints. Each joint was sealed with Apiezon wax and was adjacent to a cold trap. In several experiments the holders were fused directly into the system, eliminating the ball joints, to show that the wax did not affect the filter. Three filter holders were supported in holes in a stainless steel cylinder, which also acted as a temperature equalizing block inside the resistance wound furnace. The measuring thermocouple was inserted in one of the holders. A potentiometric controller with control thermocouple on the furnace heater winding maintained ± 0.2oC. Electrolytic hydrogen was purified and stored as shown in the flow diagram, Fig. 1. It could be admitted to either or both sides of the palladium specimens. Only a mechanical pump was used, for even high pumping speeds would not bring the pressure on the off-gas side of the filter below 10 to 50p Hg owing to the rapid hydrogen flow through the filters. A series of steady-state permeability studies allowed identification of several conditions of permeability loss. A constant fore pressure was maintained while the low-pressure face was pumped. After enough time had elapsed for a steady flow to be established the pump was cut off, and the rate of pressure increase in a thermostated bulb was measured to determine the flow rate. The time delay method of Daynes1,9 was adopted since it offered the possibility of determining solubilities and diffusivities. For each measurement both sides of the filter were evacuated for 15 min, which gave about 10-4mm Hg residual pressure. Hydrogen was admitted to one side or the other of the filter at a fixed pressure. The pressure on the off-gas side was observed as a function of time. A

Jan 1, 1961

By K. J. Gill, P. Chiotti

Thermal, metallographic, and vapor pressure data were obtained to establish the phase diagram for the thorium-zinc system. Four compounds corresponding to the stoichiometric formulas Th2Zn, ThZn2, ThZn4, and Th2Zn17 were observed. The melting points of these compounds under constrained vapor conditions were found to be 1055°, 1105°, 1095°, and 1015°C respectively. Four eutectics exist in this system with the following eutectic temperatures and thorium contents in wt pct: 1040°C, 89 Th; 945°C, 79 Th; 1045°C, 55 Th; and 995°C, 35 Th. The standard free energy, enthalpy, and entropy of formation for the compounds were determined from zinc vapor pressure data. ALTHOUGH the thorium-zinc system has been of technical importance in the commercial production of thorium and more recently of interest to some proposed pyrometallurgical separations processes for reactor fuels or blanket materials no detailed investigation of this system has been made in the past. Some previous work has been reviewed by Hanssen.1 The existence of four compounds, Th2Zn17, ThZn4, ThZn2, and Th2Zn has been established and their crystal structures have been studied by X-ray diffraction techniques.2-4 Smirnov et al.,5 determined the solubility of thorium in zinc and investigated the two-phase region between Th2Zn17 and zinc. They calculated some of the thermodynamic properties for these alloys from emf measurements on the cells Th/ThCl4(fused)/Cl2, C and Th2Zn17(s)+ Zn (l)/ThCl4(fused)/Cl2, C. The possibility of reaction between the anode materials and fused thorium tetrachloride to produce a lower valent thorium salt would have to be resolved in order to evaluate the results obtained. The purpose of the present investigation is to establish the phase diagram for the thorium-zinc system and to determine the standard free energy, enthalpy, and entropy of formation for the compounds formed. MATERIALS AND EXPERIMENTAL PROCEDURES The metals employed in the preparation of alloys were Bunker Hill slab zinc, 99.99 pct pure and Ames Lalboratory thorium. The major impurities in the thorium in parts per million were oxygen—1250, carbon—350, iron—100, nitrogen-75, and silicon—70. The metals in the form of several small massive pieces, total weight about 30 g, were cleaned with acid, washed with water and acetone, and dried just prior to their use for alloy preparation. Tantalum containers were found to be suitable for all the alloys studied and were used throughout this investigation. The metals were sealed inside of small 1-in.-diam tantalum crucibles by welding on preformed tantalum covers. A small thermocouple well made from 1/8-in.-diam tantalum tubing was welded in the bottom of each crucible. These crucibles were enclosed in

Jan 1, 1962

By J. Gordon Parr, D. H. Polonis

The formation and subsequent decomposition of metastable phases in Ti-Ni alloys containing up to 11 pet (atomic) Ni have been studied. The decomposition of a completely retained ß phase and of a completely transformed 8 phase in a 6 pet alloy has been followed by X-ray diffraction and metallographic methods and by hardness determinations made during the process. The possible mechanisms of the reactions are discussed. PREVIOUS investigations of the Ti-Ni system have usually been limited to phase diagram studies; but little attention has been given to metastable phases and tempering processes. These are important, however, since equilibrium conditions are rarely achieved—nor, perhaps, are they desired—in practice. Up to the present time the available transformation data for titanium alloys appear to be restricted to isothermal transformation curves for selected binary and ternary systems. No quantitative studies have been made of the mechanism by which equilibrium is approached. Several independent investigations have been carried out to determine the Ti-Ni phase diagram. Early work by Wallbaum' and later by Long et al.' produced tentative phase diagrams which were not representative of true binary conditions, since the alloys were contaminated with oxygen and nitrogen. The most recent diagram (Fig. 1) is due to Margolin et al.," and a slight modification of the a + ß/ß boundary (shown dotted) has been proposed by McQuillan.' The structure of the phase Ti,Ni was shown by Duwez and Taylor" to be face-centered-cubic, with 96 atoms per structure cell. The formation of a martensitic ß phase (close-packed-hexagonal) in Ti-Ni alloys has generally been observed when specimens of low nickel content are rapidly cooled from the 0 (body-centered-cubic) range. Margolin et al. reported an increasing tendency for P to be retained in lump specimens as the nickel content increases. McQuillan' has studied the effect on the microstructure of delay time in quenching, and has reported the formation of pro- eutectoid a precipitate in a quenched hypoeutectoid alloy. In a previous study of Ti-Fe alloys," experiments were made on powder specimens produced by filing alloy ingots. Techniques were devised for the preparation and heat treatment of alloys, and X-ray diffraction methods were used both for structure determinations and phase ratio estimations. A similar approach has been made in this study of Ti-Ni alloys. Experimental Methods Ten alloys ranging from 0.25 pet to 18 pet Ni* * All compositions are in atomic percentages unless otherwise stated. were prepared from iodide titanium bar stock (hardness Rf 72) and Johnson-Matthey spectrographic standard nickel by levitation melting.' As a check

Jan 1, 1957

By R. J. Reynik, F. R. Meeks

IN the classical paper1 of Mehl and Rhines entitled "The Rates of Diffusion in the Alpha Solid Solutions of Copper", the authors state: "It has been mathematically demonstrated that the treatment of the data as though the diffusion were taking place between two flat plates instead of radially in a cylinder has no appreciable effect upon the results. Were the bars of a much smaller diameter, a modification of the analytical treatment would have been required." Unfortunately, the errors in the reported concentrations are much too large to neglect, as shown in the results below. A planar treatment of diffusion data assumes that the reference planes separated by a nominal distance (AX) have identical areas. An adjustment must be made on the concentration data should the successive diffusion planes differ in area. The Mehl-Rhines' diffusion samples were cylindrical with copper electroplated onto copper-based alloys. Successive surface areas through which diffusion occurs are in the ratio ri/r1, where ri is the radial distance between the center of the sample and the center of the i th shell to which the host (alloy) atoms diffuse, and r1 is the radial distance between the center of the sample and the center of the innermost (i = 1) experimentally reported shell from which the alloy atoms diffuse. Hence, ri/r1 (i = 1, ..., n layers) is a dimensionless correction factor to be multiplied by the reported concentration data before planar-data analysis is attempted. In the forty-seven samples reported, the original interface between the copper alloys and the electroplated copper was located at a mean distance of 8.255 mm from the center of the samples. The successive layers, machined off the samples, were approximately 0.0762 mm thick. The distance (xi) at which concentration (ci) was reported was always a distance measured with respect to the original interface, that is, with respect to the fixed distance of 8.255 mm. Hence, the as yet undiscovered Kirkendall Effect was precompensated. The values of ri and r1 are therefore given by ri = 8.255 + xi and Y, = 8.255 + x,. The illustrative table below lists the position xi (mm), ri (mm), the value of ri/r1, the reported concentration (ci) in weight percent (only valid for radial analysis of data), and the corrected concentration [c'i = (ri/r1)ci] in weight percent (only valid for planar analysis of data). Similar tables can be constructed for the remaining forty-six samples. The corrected data can be used to re-evaluate the diffusion coefficients for the reported systems.

Jan 1, 1965

By John J. Gilman

BECAUSE of their layerlike structure, zinc crystals exhibit strong anisotropies for almost all physical and chemical properties. This should, and indeed does, greatly influence the plasticity of zinc for various crystal orientations. At low temperatures, the investigator of this plastic anisotropy is plagued by the great variety of deformation modes that operate. However, at high temperatures (250° to 419°C) only two deformation modes predominate: basal (0001) and prismatic (1010) glide. Furthermore, since strain hardening is virtually absent at high temperatures, the plasticity for these two modes of deformation can be very simply described by means of two equations of state. It is the purpose of this paper to describe the experimental behavior of basal and prismatic glide in zinc crystals, and to interpret this behavior in terms of other physical properties (in particular, the thermal expansion coefficients and the elastic constants) using the theory of dislocations. Fig. 1 defines the two planes of the zinc structure that will be discussed. Glide occurs very readily on the basal planes at all temperatures, and there is a very large literature on this subject. Much of the literature has been reviewed by Schmid and Boas;' it will not be reviewed here. Kolesnikovl was the first to show that if basal glide is circumvented by stressing a zinc crystal parallel to the basal planes (giving zero shear-stress on the basal planes) then, at temperatures above about 320°C, glide on the first-order prism planes occurs. His results have recently been confirmed by Cahn, Bear, and Bell." These previous workers have established the existence and crystallographic elements of prismatic glide; the present paper is concerned with the stress, strain rate, and temperature relations of prismatic glide as contrasted with basal glide. Experimental Methods The crystals were square ones, 6x6 mm, that had been grown in precision Pyrex tubes by a method that is described in detail elsewhere.' Most of the crystals were 99.999+ pct Zn (New Jersey Zinc Co. CP grade). Some were alloyed with 0.1 -+-0.005 atomic pct Cd, and chemical analysis showed that almost all of the added cadmium persisted through the crystal-growing process. For measurements of nonbasal glide, crystals were oriented with their basal planes parallel to both the rod axis and one of the flat faces of the square cross section. However, the orientation of the close-packed directions [1210] with respect to the rod-axis was variable. For basal glide measurements, the angle between the basal plane and the specimen axis was 35". The orientations were measured by the Gren-inger back-reflection X-ray method. The problem of finding a suitable method of gripping the crystals was the most serious experimental obstacle that arose. Because of the large plastic anisotropy of zinc, the usual gripping methods were unsatisfactory. Some methods that were tried were: high melting-point solder, making heads on the ends by locally melting a crystal, and electroplating nickel on the ends to form enlarged portions. For all these methods, the regions of the grips were weaker than the crystals themselves. Finally, two methods were decided upon: bend tests and direct machining of tensile specimens. In the bend tests, specimens were loaded as simple beams so that gripping was not a problem. The beams were 1 in. long and the axis of bending was parallel to the hexagonal axis of the crystals. For the crystals that were machined into tensile specimens, brass bars with slots in them were used to support the crystals, and thereby minimize the distortions due to machining. The crystals were glued into the brass bars with plastic cement which was later dissolved away with acetone. See Fig. 2, left. No clamps were used near the crystals and the machining was done using a milling machine with a fly-cutter. The tool bit was very sharply pointed to minimize burnishing. The feed was less than 1 mil per cut. The depth of cut was 2 mil for roughing cuts, and % mil for the finishing cuts. This machining method produced surface layers of tiny recrys-tallized grains only 2 to 3 mil deep, and the bodies of the crystals were not measurably disturbed. After the crystals had been machined and removed from the brass holders, they were chemically polished until about 5 mil had been removed from all their surfaces. The polishing reagent consisted of equal parts of concentrated HNO,, 30 pct H3O and ethyl alcohol; it is described in detail elsewhere." A typical crystal is shown in Fig. 2, right. The I-shaped faces are normal to the hexagonal axis of the crystal; otherwise the projections at the ends would simply shear off when the crystal was loaded. The cross section in the 2?-in. gage length is 0.215x0.115 in. It was found that the polished

Jan 1, 1957

By E. S. Greiner

Germanium and silicon have been plastically deformed in torsion at elevated temperatures. Slip took place on the four {Ill} planes. Dislocations, revealed by etch pits on a (111) face, occurred in rows that were traces of operative slip planes. THE plastic deformation of germanium and silicon by bending and tension at elevated temperatures has been reported by Gallagher.&apos; Transla-tional slip during plastic flow in these materials, according to Gallagher&apos; and Treuting,&apos; occurs on (111) planes. Recent work by Treuting&apos; indicates the direction of slip to be <1l0>. The present paper describes the plastic flow characteristics of germanium and silicon deformed by torsion. Torsional deformation was accomplished by twisting 1/4x1/4x2 in. specimens held in molybdenum grips and contained in an atmosphere of helium in a transparent quartz tube and heated by an external resistance furnace. The angular displacements were measured on a graduated circle with a pointer attached to the movable grip. Temperatures were measured with a chromel-alumel couple; the hot junction was within the quartz tube and in close proximity to the specimen. Photographs of samples of germanium and silicon twisted at 850" and 1180°C, respectively, are shown in Fig. 1. The germanium was twisted 230" per in. and the silicon 80" per in. These deformations are larger than those used in experiments to be described later and are presented only to emphasize the extensive plasticity of these materials. Germanium A single crystal specimen of germanium (n-type, 7 ohm-cm resistivity) with a (111) plane normal within 3" of the torsion axis, Fig. 2, was chemically polished with CP-4 solution" and then twisted 9" during the twisting of these specimens of germanium, the slip lines from the (lli) plane should have appeared in the four lateral faces instead of in only two. Perhaps the absence of rotational slip is brought about by the square cross-section. A cylindrical specimen would have a more uniform stress distribution in torsion than one with a square cross-section, and may deform by rotational slip. A specimen of germanium (n-type, 5 ohm-cm resistivity) twisted less than 8" per in. at 550°C, was cut to expose the (111) face 19" 28&apos; from the torsion axis, Fig. 4a. This face, after metallographic

Jan 1, 1956

By E. C. Burke, W. R. Hibbard

Plastic deformation in magnesium single crystals was studied by tensile tests at room temperature utilizing an improved preparation and testing technique. Consistent critical resolved shear stress values for basal slip were obtained. The advent of pyramidal slip at room temperature was rationalized upon the basis of grip constraints. A bend-twinning hypothesis was advanced as an explanation of mechanical twinning which occurs as a complex stress-relief mechanism. INVESTIGATIONS of the plastic deformation of magnesium have been limited to the determination of the fundamental kinetics which may be summarized as follows: 1—Twinning on the {102).l 2— Slip on the (001) plane in the [loo] direction at room temperature.&apos; 3—Slip on the {101) or {102) plane in the [loo] direction above 225°C." 4—Critical resolved shear stresses for basal slip in tension at room temperature of 83 g per sq mm with a variation from 57 to 127 g per sq mm." Bakarian&apos; studied the compression of thin wafers of magnesium single crystals and classified the components of the deformation mechanisms as follows: 1—The Basal field: (001) at an angle of less than 20" to the compression surface. Fracture along {101} or slip on (001) followed by {101} fracture. 2—The prism field: (001) at an angle greater than 60" to the compression surface. Twinning on the {102) generally occurring during the early stages of loading, basal slip in the areas of original orientation and (001) slip within twins. 3—The central field: (001) at angles greater than 20" but less than 60" to the compression surface. Slip on the (001). 4—The critical resolved shearing stress for {101} slip above 225°C was 400 g per sq mm. Observations of mechanical twins in hexagonal close-packed metals have been summarized by numerous investigatorsb-&apos; emphasizing a lateral or rotational atomic adjustment, in addition to the pure twinning shear, and the importance of reorienting the basal plane to a position more favorable for continued slip, rather than the resulting small dimensional changes. Criterion for the operative twinning planes has not been clearly established. Schmid and Boas hurmised that an energy condition related to the atom movements is the determining factor. MillerQ bserved that twinning stresses in zinc crystals decreased as the amount of prior deformation increased. Preparation of Specimens Magnesium single crystals % in. in diam x 8 in. long were grown from the melt under an argon atmosphere in a gradient furnace similar to that described by Jillson." Magnesium containing 0.018

Jan 1, 1953

By R. A. Wood, R. I. Jaffee, H. R. Ogden, D. N. Williams

Strain-induced porosity has been found to occur in titanium and other materials at tensile strains greater than the uniform elongation of the material. Porosity in titanium increases with increasing strain and temperature, being most severe at 300° to 800°F. Strain-induced porosity is believed to be a normal part of the mechanism of deformation in ductile materials. DURING the past few years there have been numerous references to the occurrence of voids in laboratory test specimens of metals subjected to strain.l-7 These voids have been referred to as intercrystalline cracking, strain-induced porosity, intergranular cav-itation, voids, and porosity. They appear to occur at grain boundaries or interfaces, and are generally associated with large amounts of strain and have been found mostly in creep specimens and to a lesser extent in tensile specimens. Because the phenomenon does not occur unless the material has been strained,

Jan 1, 1960

By A Guinier

RECIPITATION in alloys is undoubtedly one of the most essential phase transformations in metallurgy and, besides, it is a phenomenon of great interest to physicists. It seems then that it can be chosen as a topic for an Annual IMD Lecture. Of course, the subject is a very wide one and I shall discuss here only a very restricted part of it. I should like to show why it is now considered that there is, at the beginning of the process, a stage distinct from the real precipitation, which is the pre-precipitation. We shall be chiefly interested in the atomic structure of the metal in this preprecipi-tation stage. Numerous reviews on this subject have been published recently.&apos;, &apos; The latest was given by H. K. Hardyh t the last meeting of the Institute of Metals in London. One of the most complete articles has been written by the late Dr. Geisler." I should like, at the beginning of this lecture, to pay a tribute to the memory of our friend Arthur Geisler. Some of the ideas which will be developed here are different from those advocated by him. But everybody knows the considerable progress in experiment and in theory which we owe to him and, personally, I deeply feel how fruitful have been the long discussions which we have had during many years. Experimental Basis of the Precipitation Problems Let us recall the essential facts pertaining to the problem of the precipitation. The starting point and the final one are well known. The initial stage is the supersaturated solid solution before quenching. The dissolved atoms replace some of the atoms of the solvent at the points of a definite lattice. It is generally considered that the distribution of the atoms is completely random, and that the lattice distortions are relatively weak. These assumptions are only an approximation. It has now beenproven", that, in some cases, the dissolved atoms have a tendency to segregate to form very small nuclei. These fluctuations of composition are greater than the normal statistical fluctuations in a purely random alloy. We shall see the role played by these nuclei later. The final state is obtained by a very long annealing at such a temperature that an equilibrium is reached in a reasonable time. The alloy is then composed of a matrix which is a saturated solid solution, much poorer than the initial one. Imbedded

Jan 1, 1957