Search Documents

By H. Conrad

The strain hardening associated with the creep of magnesium single crystals at room temperatu.Je was investigated by shear tests in which the direction of stressing was reversed a number of times after creep in a <100> direction. The strain hardening was strongly anisotropic; the largest amount occurring in the direction of flow and the least 180 deg to this. The time law for creep changed from a parabolic type to logarithmic for the first and subsequent reversals of stress. For a given stress the creep strain decreased significantly for the first and second reversals and then only slightly for subsequent reversals. The logarithmic creep constant a changed in a similar manner. A linear relationship was observed between the creep strain for a given reversal and the stress. The slope for the third reversal yielded a strain hardening coefficient 12 to 16 times greater than that observed for unidirectional flow. Al-though no recovery was observed upon resting at room temperature, the hardening resulting from stress reversals could be completely removed by heating to 450" C. PREVIOUS work1.&apos; indicated that the creep rate of magnesium single crystals tested in the temperature range of 78" to 364°K decreased with time. This was attributed to an increase in internal stress resulting from an accumulation of dislocations at internal obstacles. The object of the present investigation was to further evaluate the nature of this hardening by conducting tests in which the direction of stressing is changed after previous creep in shear in a given slip direction. Previous to 1950 three investigations indicated that a Bauschinger effect3 occurred for single crystals as well as polycrystals brass in tension compression,

Jan 1, 1960

By L. F. Porter, G. J. Dienes

The effect of netltron irracliation on mart ensite transformation in the iron-nickel system was studied by means of electrical resistance and magnetic induction measuremertts. Irradiation lowers the M8 temperature of the allay, causes changes in the electrical and magnetic properties of the high-temperature phase which indicate either an accelemtion of phase separation or a clustering of nickel, and enhances strain recovery on specimens partially transformed to martensite prior to irradiation. Possible mechanisms to account for the effects; are discussed. 1 HERE is a good deal of evidence to indicate that neutron irradiation is capable of affecting phase changes in metals and alloys. While the mechanism of the effect often is not well understood, such studies hold promise of improving our understanding not only of irradiation damage but also of the phase changes involved. To date systematic and detailed investigations have been made of the influence of nuclear radiation on order-disorder transformations in the copper-gold, nickel-manganese, and copper-zinc system, and on precipitation reactions in the copper-iron, nickel-beryllium, and copper-beryllium system.&apos; These solid-state reactions are diffusion controlled and the results can be explained largely on the basis of enhanced diffusion due to the presence of irradiation produced vacancies. Reversion of low-temperature eutectoid phases to the high-temperature phase has been observed in the fissionable uranium-molybdenum and uranium-niobium systems.2 Here it is necessary and logical to postulate a displacement spike mechanism to account for the effect. The only case of irradiation induced diffusionless transformation in metals is the allo-tropic transformation of p to a tin reported by Flee-man and Dienes. 3 They found that neutron irradiation markedly decreases the incubation time for transformation, but the mechanisnl is not well understood. Another diffusionless transformation which one might expect to be influenced by neutron irradiation is the martensite transformation. This transformation is known to be sensitive to strain, structural hardening, and the presence of imperfections.6,7 Since the transformation is diffusionless, one also

Jan 1, 1960

By R. S. Busk

Niels Engel (University of Alabama, University, Ala.)— In this paper it was pointed out that the electron-gas and energy-band theory accounts for the fact that the lattice parameters exhibit a sudden change when the electron concentration (number of bonding electrons per atom) exceeds a certain number around two. This statement is said to support and prove the electron-gas theory. But this theory is not able to account for a series of experimental data. Also several expectations, deduced from this theory, are not found to exist. In Figs. 6 and 7 the energy bands of the second and third periods are given as they must be assumed in order to account for the electrical properties of the elements in these periods. In Figs. 6 and 7 the electron-gas and energy-band theory is compared with the electron-oscillator hypothesis in accounting for the properties of the elements in the second and third periods. Fig. 6 shows the second period, The energy-bands are overlapping and separated to be in agreement with the electrical conductivity of the elements. The oscillator hypothesis explains conductivity due to electron vacancies. In graphite there is a closed s-shell in every other atom and two vacancies in the others. Conductivity is therefore only maintained by migration of s-electrons in graphite. In boron there are no s-electrons. The diatomic molecules of nitrogen and oxygen and the paramagnetism of oxygen can be accounted for by a similar behavior as the s-electrons of the bonding electrons. But this explanation will deviate too much for the purpose of this discussion. Fig. 7 shows the third period. In the energy-band picture about two s-electrons are assumed in magnesium and aluminum, but only one s-electron is assumed in silicon. The diamond lattice is assumed to be controlled by a sp3 hybrid. However the electron distribution develops ideally according to the oscillator hypothesis. Only sodium, magnesium, and aluminum exhibit electron vacancies and conductivity. To account for the insulator properties in Si, P, and S in the third period it must be assumed that the four last added p-electrons must be taken up in bands containing only one electron per band.&apos; (Compare the electron band picture in Hume-Rothery.&apos; Hume-Rothery does not consider the insulator properties of the nonmetals.) In the second period already the first p-electron must have entered a single electron band. Based on the energy-band picture in Figs. 6 and 7, the following questions must be asked: 1—Is it consistent with the energy-band idea that electrons of the same kind (p-electrons) can be divided into separated bands? 2—Is it consistent with the energy band idea that single electron bands can exist? 3—Why are the first two p-electrons (in boron and diamond) separated into two single electron bands in the second period, but overlapping in the third period (aluminum)? 4—Why are s-electrons and d-electrons taken up in continuous overlapping bands, while p-electrons are divided into single electron bands? 5—Why do the peaks and valleys (y and w and further x and z) of the energy band below four electrons per atom not show up in the electrical conductivity of alloys? For example consider the Li-Mg system or the alloys between Mg and three electron metals where the mentioned discontinuity in the lattice parameter is found. 6—Why does the beginning of the p-electron band (x) not show up in the lattice constants similar to the filling up of the s-electron band (z) ? In magnesium alloys the electron-gas theory postulates the first Brillouin zone to be filled at about two electrons per atom. This is claimed to explain the sudden change in lattice spacing and c/a values of several magnesium alloys when the electron concentration exceeds a few percentage points over two electrans per atom. This was emphasized in the paper by Busk. If the electron-gas energy-band theory is correct a sudden change in electrical conductivity and possibly other properties .should be expected when the same electron-concentration or temperature is exceeded. A sudden change in lattice spacing or other properties should also be expected when the filling degree is such that p-electrons are introduced into the p-band, for example at x in Figs. 6 and 7. Such phenomena are at found by experiment. and If the number of electrons should vary with the energy level depending on the average number of bonding electrons per atom, the electrical conductivity should be expected to vary in accordance with the energy band layout (Figs. 6 and 7) caused by different numbers of conducting electrons at different filling up degrees. Nothing indicating such a behavior is observed. In addition to these discrepancies between the electron-gas and energy-band theory and measured data, the theory violates the principles developed along with the Bohr theory of atomic structure. According to these principles a filled shell is saturated and therefore unable to form bonds. Therefore two S-electrons per atom should form a closed or saturated shell, which has been pointed out as accounting for the inability of helium to form bonds. Beryllium, magnesium, or calcium atoms with two s-electrons should be expected to form inert atoms with properties almost like the helium atoms. Several other inconsistencies and disagreements with measured data of the energy-band theory can be mentioned. Some of these are discussed with reference to other papers. 8 Because the electron-gas and energy-band theory seems to fail on several points, I have developed another theory which can account for all the phenomena the electron-gas theory is able to account for. This new theory is further able to account for things which are impossible to explain by the electron-gas theory at the present state.

Jan 1, 1953

By A. R. Elsea, E. E. Fletcher

This paper describes a metallographic investigation of the influence of tungsten or molybdenum additions upon the transformation and precipitation reactions occurring in Co-rich Co-Cr alloys. It is shown that tungsten has little effect upon the a-ß transformation temperature range, while molybdenum tends to raise it. Both elements tend to promote the formation of ? phase, molybdenum being more potent in this respect than tungsten. HIGH temperature alloys, that is, alloys which have load-carrying ability at elevated temperatures, have been developed at an increasing rate during the past few years. This has resulted from the requirements in the design of modern aircraft engines. Although many alloys of this type are available, they have been developed on an empirical basis. Metallurgists do not have a clear understanding of the phases or structures that are responsible for these high temperature properties. In order to determine why these alloys possess this particular ability, a project was started at Battelle Memorial Institute with the object of learning more about the fundamental factors which promote high temperature strength in alloys. This study was to include a correlation of microstructure and the high temperature properties of Vitallium, an alloy which is widely used for high temperature service. Vitallium is a complex material both from the standpoint of composition and microstructure. Consequently, it was necessary to obtain informa- tion regarding the phase relationships in this alloy. The Co-Cr binary diagram was determined as the first phase of this investigation.&apos; A second paper described the effects of iron, nickel, or nitrogen on the reactions occurring in the Co-rich end of this system.&apos; The present paper covers a continuation of this investigation in which the effects of tungsten or molybdenum on the reactions occurring in Co-rich, Co-Cr-base alloys were determined. Preparation of &apos;rest Materials Two series of ternary Co-Cr-base alloys, representing Co-Cr ratios of 80:20 and 68:32 ( Cr x 100 =20 and 32 ) , were prepared containing ( Co + Cr = up to 6 pct W and up to 12 pct Mo. Melting stock consisted of electrolytic Co, electrolytic Cr, 99.9 pct pure W, and 99.9 pct pure Mo. Table I lists the chemical analyses of these materials. The melting furnace was a vertical porcelain tube

Jan 1, 1952

By H. A. Domian, H. Biloni, G. F. Bolling

Jan 1, 1965

By E. Teghtsoonian, K. G. Davis

THE preparation of cobalt crystals offers problems: on cooling through 400°C a phase transformation takes place whereby the structure changes from face-centered cubic to the low temperature close-packed hexagonal form. There are a few references in the literature which describe the preparation of cobalt crystals for magnetic work1,&apos; where melt-solidification methods were used. Reasons will be given why such methods were found unsuitable for our purposes. The following techniques were tried: 1) Solid state methods. Any mechanical shaping of tensile specimens would lead to uncertainty with regard to residual strains. With this in mind, following Kaa, strain-anneal and grain growth techniques were extensively investigated. In no Case were useful single crystals obtained. The transformation boundaries, which are crystallographically similar to twin boundaries, are probably extremely stable and inhibit the grain growth. 2) Growth from the melt. Normal melt-solidification methods were tried, using recrystallised alumina crucibles, and also a osoft moldo technique in which cobalt rod was packed in alumina powder. Trouble was encountered with gas evolution on solidification of the melt, giving porosity. Some adhesion of cobalt to the alumina also took place. Only a small proportion of the runs gave single crystals. 3) Zone-refining. Much the best results have been obtained using an electron-beam floating zone refiner. The refiner, based on a design by Calverly et Al .5 had a single-turn tungsten filament. It was operated at 600 v with an emission current around 45 ma. Commercial cobalt rod 1/8 in. in diam was given one pass at a rate of zone travel normally 25 cm per hr, under a vacuum approximately 10-5mm of Hg. Over 50 pct of the runs gave long sections of single crystal. Crystals up to 2o Cm long with good uniformity of cross section and straightness have been grown in this way. Increase in the length of the molten zone resulted in higher single-crystal yields, but control of zone stability was reduced. Sub-boundaries in the zoned crystals were few, and Laue X-ray spots were sharp. The success of the method is believed to lie in two factors, namely i) the absence of crucible restraints during the transformation, and ii) extreme axiality of heat flow during cooling. The axes of the zoned crystals were clustered around the [ 1010] pole, the pole of the basal plane being at least 60 deg from the specimen axis. Crystals grown at lower rates of zone travel showed the same orientation range, Fig. 1. This orientation is similar to that for other hexagonal metals grown from the melt, which is a little surprising when the mode of formation of the hexagonal phase is considered. The preferred orientation is probably caused by anisotropy of heat conduction, i.e., that crystal which can most effectively conduct heat away from the transformation interface will be favored. Fig. 2 shows the area on a standard cubic stereo-gram in which there are no poles more than 60 deg from one of the four < 111> directions. This area

Jan 1, 1962

By John T. Norton

N order to attempt to arrive at a better under-Jl standing of the whole basic problem of sintering, these remarks will serve as an introduction for discussion that is included and will, perhaps, help to isolate specific questions which need to be answered or to suggest some definite avenues of investigation which should be followed. To bring some sort of logical order into the presentation, I will consider the various types of interaction between the metal to be sintered and the atmosphere which surrounds it, depending upon whether the phenomena are essentially chemical or physical in nature. For example, when the only necessary criterion for the satisfactory sintering of a certain powder is the removal of an oxide skin, then the problem of choosing a suitable atmosphere is primarily chemical; however, if a special surface condition as a consequence of the oxide skin removal is necessary for particularly effective sintering, then the problem becomes a physical one. Of course, the two aspects overlap considerably, but it may be possible to make a distinction in principle if not in practice. The chemical characteristics of the phenomena will be emphasized, since these are the better known. Metal-gas reactions involved in sintering are controlled primarily by the thermodynamics of the processes involved. In which direction will a reaction go and how far before it stops? The answer is to be found in the magnitude of the free energy change associated with the reaction. If a constituent is to be removed from the specimen as completely as possible or if a constituent is to be formed in the specimen as completely as possible, then one chooses conditions which are far from equilibrium so that the reaction is driven toward completion. On the other hand, if the composition is to be maintained at a desired value, then conditions are adjusted as closely as possible to the equilibrium point. This aspect of the problem is susceptible to quite precise analysis, provided, of course, that the significant reactions can be recognized and the required thermodynamic data are available. Conversely, if one asks how fast the reaction goes or how far it proceeds in a given time, the answer is frequently much more difficult to answer in quantitative terms. Yet the rate-con trolling factors of the reactions may be of primary importance in the success of a particular operation, especially where competing processes are at work. Both equilibrium and rate factors must be understood if a clear picture is to be obtained. For instance, in a process for carburizing titanium dioxide, is the difficulty of obtaining a stoichiometric Tic due to a true limitation of the equilibrium or simply to a very slow rate of reaction? An example of this appears in the work of Kalish and Mazza.&apos; They showed that the oxygen content of sintered iron compacts was lower when sintered in pure hydrogen than in the case where the hydrogen was diluted with either argon or nitrogen. The equilibrium oxygen content of the iron would be the same in the two cases, since it is determined by the ratio of the partial pressures of water vapor and hydrogen and this pressure ratio is unchanged by dilution. The rate of oxygen removal, however, under the conditions of a constantly replaced furnace atmosphere, depends upon diffusion and thus upon the concentration of hydrogen in the furnace atmosphere. Possibly the clearest way to illustrate the interplay of these two factors is to consider in more detail some of the typical metal-gas reactions. Adsorbed Gases It is common experience that fine metal powders with their very large surface areas often contain large quantities of gas. This gas, which results from exposure to air or perhaps from some step in the

Jan 1, 1957

By A. N. Holden, W. E. Seymour

DURING the last several years, the U-Zr system has been studied at many laboratories as one of the research programs sponsored by the Atomic Energy Commission. The equilibria in part of this system have been difficult to determine, although the phase diagram from 0 to 60 atomic pct Zr has been established with reasonable certainty. Existing diagrams of the system vary appreciably beyond 60 atomic pct Zr, particularly with regard to the existence of an intermediate phase. Most existing diagrams show a transformation or reaction horizontal near 600°C. In 1955, a collection of uranium phase diagrams&apos; was prepared at the Battelle Memorial Institute and the U-Zr diagram in that collection contained a questionable region in the vicinity of 60 to 80 atomic pct Zr. Summer-Smith" has published a phase diagram of the system that shows no intermediate phase. Summer-Smith did his work with powders and found only the uranium and zirconium eutectoid mixture from X-ray patterns of material annealed below 600°C. Mueller3 at Argonne National Laboratory did similar work with filings, and he found that initially there was a pattern of an intermediate phase, but on long-time annealing

Jan 1, 1957

By Y. C. Liu

Both the habit plane of martensite and the orientation relationship between the matrix and martensite platelets of different habit planes have been investigated in binary titanium alloys with molybdenum, chromium, and iron. The effect of the mode of deformation on the martensite habit plane was studied. A micrograph of an exposed mar-tensite platelet is presented. IN the study of martensitic transformation in Ti-Mn alloys,&apos; two martensite habit planes—{334), and {344)8—were reported. The {334), habit was also observed in unalloyed titanium upon transformation,&apos; although there is disagreement with respect to the exact indices. The other habit plane, {344),, has not been reported in martensitic transformation in any other alloys. The present investigation was made to determine whether other binary titanium alloys with P-stabil-izing elements would exhibit a crystallography of transformation similar to that of Ti-Mn alloys. Furthermore, since martensite platelets can be induced by deformation under certain conditions, it was of interest to investigate whether the mode of deformation, compressive or tensile, would influence the formation of martensite platelets on a specific plane in an alloy system which possesses two martensite habit planes. Experimental Procedure The material used for the preparation of the binary alloys of iodide titanium with molybdenum, chromium, and iron had the following purities: 99.99 pct iodide titanium, 99.9 pct molybdenum, 99.423 pct chromium, and 99.9 pct iron. The compositions of alloys listed in this paper are in nominal weight percentage. All specimens used were prepared and treated according to the procedure described in reference 1, unless stated. For the subzero temperature treat,ment the following experimental schedule was followed. After specimens had undergone the grain-growth treatment, they were quenched into an ice-water bath and were then metallographically examined. In specimens of higher alloy content, no martensitic transformation was observed. In those in which mar-tensitic transformation did occur, only specimens in which the martensite platelets existed as fine needles in localized regions were used. All specimens were reannealed 17 hr at 1200°C, quenched into ice water. and the capsule was broken. They were held in the ice water for from 5 to 10 sec, then transferred to a liquid-argon bath. This stepped quenching procedure was found to be more efficient than direct quenching into liquid argon. In the latter case, as soon as the hot specimen was immersed in the liquid argon, a protective, insulating layer of argon gas formed, and the specimen continued to glow vividly in the bath for some time. In the study of the habit behavior of martensite produced by deformation, specimens were deformed at room temperature either by compression, tension, or rolling. Martensite habit planes were determined by the two-surface analysis procedure described in reference 1. A stereographic net of 153/4 in. diam was used throughout the investigation. The method for determining the orlentation relationship between martensite and the matrix follows that used by Greninger and Troiano.&apos; A diamond-polishing table with its auxiliaries was used in order

Jan 1, 1957

By F. D. Rosi, C. A. Dube, B. H. Alexander

The slip and twinning planes have been determined in deformed crystalsof titanium by an X-ray method of analysis. The slip planes are of the type {1010} and {1011}, while the twinning planes are of the type {1072}, {1121}, and (1122). In the case of the predominant (1010) slip, a type I digonal axis of indices <1120> was the effective slip direction. Microscopic observations on the appearance of the three twin types disclosed a distinct difference in their shapes, and an attempt was made to correlate this difference with the amount of twinning shear. The slip mechanism was discussed on the basis of the difference in c/a ratios for the common hexagonal close-packed metals. IT is a general rule that slip in metals occurs most easily on the planes of greatest atomic density and of the largest interplanar spacing, and that the direction of slip is a close-packed direction. Thus, of the hexagonal close-packed metals which have been investigated by the German school in the decade 1925 to 1935 (cadmium, zinc, and magnesium), it has been found that slip occurs on the basal plane (0001) and in a <1120> direction.&apos; In the case of magnesium above 225oC, slip occurs on a first-order pyramidal plane (1011) as well as on the basal plane.&apos; The hexagonal metals, moreover, deform in part by twinning, and, again with the exception of magnesium at elevated temperatures, the twinning plane has always been reported to be a second-order pyramidal plane {1012).&apos; In view of this consistency in the plastic behavior of these metals, it has been supposed that the same slip and twinning elements would be operative in the other important hexagonal close-packed metals (titanium, zirconium, and beryllium), although there are some reasons why this may not be so. Referring to the tabulation in Table I of the axial ratios of the important metals in this structural class, it may be seen that they can be categorized into three distinct groups depending on the value of their c/a ratios. In the first group are cadmium and zinc with large positive deviations from the ideal ratio for closest packing. This expansion in the direction of the c-axis would be such as to accentuate the basal plane as the slip plane, because it increases the interplanar spacing. The second group includes cobalt and magnesium, which closely approximate the ideal ratio. In the third group are zirconium, titanium, and beryllium whose axial ratios are decidedly less than the ideal. The lattice of the elements in this group is compressed along the c-axis which, in effect, tends to make the basal plane less favorable for slip inasmuch as it reduces the interplanar spacing and the atomic density of this plane. Thus, for metals in the third group, it may be said that there is a certain indefiniteness about the glide plane, in that planes other than the basal plane may be expected to operate. The fact that magnesium begins to exhibit planes other than the normal slip and twinning planes at elevated temperatures may indicate that this behavior will become more pronounced in metals of lower axial ratios. For this reason it might be expected that the slip and twinning behavior of zirconium, titanium, and beryllium would be different from that found in cadmium and zinc. One indication that there is a difference is reflected in the recent work which has been done on the deformation textures of these metals."&apos; As will be shown later, there is a significant difference between the rolling textures of cadmium, zinc, and magnesium on the one hand, and zirconium, titanium, and beryllium on the other, and this difference suggests that the mechanism of plastic flow is not the same in these two groups of metals. From these considerations, therefore, it may be seen that there are good reasons why it cannot be concluded that titanium will have the same crystal-lographic elements of slip and twinning as those exhibited by zinc and cadmium. For the complete determination of these elements it would be most advantageous to have single crystals. However, much valuable information can be obtained by using coarse grained polycrystalline specimens, provided the grains are sufficiently large to permit X-ray

Jan 1, 1954

By Lawrence H. Van Vlack, Alfred S. Keh

The distribution of sulfur in iron was found to be dependent upon the time and temperature of the treatment as well as the chemical composition of the sulfide. With higher temperatures, the sulfide phase spreads more extensively between the iron grains. A complete network, however, does not form until approximately 1300°C (2372°F), ot which temperature the dihedral angle approaches zero. Silicon has little effect on this change. Aluminum, oxygen, and manganese all modify the temperature of sulfide network formation to a higher value. The microstructures which result and have significance in relation to hot-shortness are discussed. SULFIDE inclusions in steel were recognized by metallurgists before the turn of the century. Considerable attention has been paid to them, and numerous studies have been made on the working properties of steel as affected by them. It has been suggested that ho t-shortness of steel is due to the presence of an enveloping liquid sulfide film at the grain boundaries of the steel in the range of the hot-working temperatures. However, several facts have been observed in commercial steels which do not seem to be completely consistent with this explanation: 1) the frequent absence of continuous films of sulfide as observed under the microscope, 2) the absence of hot-shortness in some high sulfur and resulfurized steels, and 3) the limitation of hot-shortness to a definite temperature range. The role that manganese plays in steel to eliminate hot-shortness is well known, but the theory behind it is still under question. Moreover, the effect of de-oxidizers such as aluminum and silicon, and the effect of oxygen are still not clearly known. In this study, the effect of heat treatments and of additions of manganese, aluminum, silicon, and oxygen upon the distribution of sulfide inclusions in iron was investigated. Both the as-cast and the heat treated structures were studied, using microscopic and autoradiographic techniques. Part of the results were interpreted in terms of Smith&apos;s&apos; concept of microstructure. Review of Literature Metallurgists used to consider sulfide inclusions as suspended particles. It was Wohrman&apos; who first pointed out that sulfide inclusions are soluble in liquid iron. Many observed facts may be understood on the basis of this concept of solubility. Wohrman found that small castings contain small inclusions. and larger castings contain larger ones. Also, inclusion sizes are smaller near the chilled surface. For the same size ingot, the average inclusion size in a given heat of steel depends upon the rate of solidification. That is, with slow solidification, enough time for precipitation and agglomeration of these

Jan 1, 1957

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&apos;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.&apos;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&apos;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,&apos; 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 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.&apos; 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 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 S. W. Kennedy, M. Cohen, L. D. Calvert

A high-temperature X-ray diffraction method has been used to study the composition and the kinetics of formation of oxide scales at 800 °C on iron and pure iron-nickel alloys containing 25.6, 75, and 84 pct Ni. This technique has been combined with chemical analysis, and metallographic examination, and determination of weight-gain time curves. The 75 and 84 pct Ni alloys form a three-layer scale consisting of porous NiO next to the metal, a spinel layer, and a -Fe203 on the outside. The 25 pct Ni alloy produces a scale of spinel and Fe,O,, in which, however, traces of FeO and NiO are observed near to the metal. On all the nickel alloys the Fe20, is orieqted with the (107) plane parallel to the surfaces. The exposed surface of the Fe20, is in the form of needles whose axis is perpendicular to the specimen surface. Although the alloys show nonuniform oxidation rates as determined from weight-gain measurements, the X-ray data indicate that the total scale and individml scale layers grow uniformly and parabolically. Deep subscale formation is observed in the 25 pct Ni alloy only. This appeared to be associated with cracking of the scale and penetration of the oxygen along the grain boundaries. ALTHOUGH film formation has been investigated by high-temperature electron-diffraction techniques, for example by Gulbransenl and Hickman,&apos; there have apparently been no investigations of scaling by methods permitting study of the scale during formation at the reaction temperature. Methods involving quenching of scales are based on the working assumption that no significant changes take place on cooling. In general, however, compounds may disproportionate, and the different thermal expansions of constituents may cause disruption of the scale on cooling. In particular, some scales cannot be quenched without spalling. These difficulties are avoided by X-ray diffraction examination at the temperature of formation. High-temperature diffraction procedures also provide a method of determining the kinetics of formation of each phase separately in a multicom-ponent scale. The scaling of binary iron-nickel alloys Containing up to 30 pct Ni at a temperature of 800°C has been studied by Benard and Moreau using cooled specimen~,~ whilst Foley, Druck, and Fryxel14 made an electron-diffraction study of cooled oxide films formed on an iron 42 pci Ni alloy. In the present work the scaling of three iron-nickel alloys containing 25.6, 75, and 84 pct by weight of nickel, at 800°C in oxygen at atmospheric pressure was investigated by X-ray diffraction techniques using a Norelco Geiger-counter diffrac-tometer. The oxidation of iron was investigated for comparison. In addition normal metallographic examinations and chemical and X-ray analyses were made, and weight-gain time curves obtained. EXPERIMENTAL Materials Used—The analyses of the alloys were as follows: Percent by Weight Nickel 25.6 pct 75.4 pct 83.2 pct Aluminum 0.004 None found 0.002 Cobalt — 0.05 0.05 Chromium — — — Silicon — 0.01 None found Carbon All less than 0.05 pct The chemical analysis of the iron was: Al— 0.002 i 0.001 pct, C—0.007 pct, Cr less than 0.001 pct, Cu—0.002 ± 0.001 pct, Mn—0.003 ± 0.001 pct, N—0.0002 pct, 0-0.013 pct, P—less than 0.0002 pct, Pb—not detected, S—0.0017 pct, Si—0.0095 pct, Sn—none detected. This iron was the same as that used to make the alloys and was obtained from the same source-Vacuum Metals Corp. One specimen of pure iron from The British Iron and Steel Research Association was used for preliminary investigation. Specimens were machined to shape from cast rod, polished (the final polish being with 600 Sic paper), degreased in trichlorethylene, washed, and etched. The etching and neutralizing procedure adopted by

Jan 1, 1960

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 R. Stickler, A. Vinckier

An optical and electron microscope study was made on a commercial 302 stainless steel heat treated for massive carbide precipitation. Convincirg evidence was obtained that the grain boundary precipitate does not grow away from the grain boundary into the matrix, but grows as a network of large thin dendrites in between the grains. IN austenitic stainless steels the carbon in supersaturated solution precipitates when the steel is heated in the temperature range 450" to 1000°C. During such heat treatments the chromium-rich carbide occurs primarily at the grain boundaries and has adverse effects on the corrosion resistance and low-temperature ductility of the material. It has been shown that the morphology of the precipitated particles differs widely depending on the time and temperature of the heat treatment, the nature of the boundary, the misfit between the grains, and so forth.1"5 It was assumed by Mahla et al.,&apos; Streicher,&apos; and Mc Nutt&apos; that the carbide particles which nucleate in the grain boundary grow in various geometric or dendritic forms away from the boundary into the matrix. However, Kinzel,&apos; Hatwell et a, and Plateau et aL4 found that the particles nucleate in the grain boundary and grow as a network of thin dendrites in the grain boundary interface. We have made a comprehensive studyg of the precipitation occurring in a commercial 302 austenitic stainless steel heat treated for times ranging from 0.15 to 1500 hr at various temperatures from 480" to 1065"~. This study was made to elucidate the influence of heat treatments on both the mechanical and the corrosion properties of this steel. Part of this investigation which is pertinent to the morphology of the grain boundary carbides referred to above is separately reported here. We found that the particles which nucleated in the boundaries grew in the interface of these boundaries, thus supporting the viewpoints of Kinzel,&apos; Hatwell et al.,3 and Plateau et al.4 Furthermore, when carbide particles nucleated in the matrix very close to the boundaries, they possessed a morphology distinctively different from the particles growing in the grain boundaries. MATERIAL A study of metallographic samples and of fracture surfaces of a 302 stainless steel is reported in this paper. The composition and heat treatments are listed in Table I. Polished and etched samples were examined und813r the optical microscope, and carbon extraction replicas of etched micrographic samples and various fracture surfaces3&apos;8&apos;9 were examined under the electron microscope. RESULTS AND DISCUSSION A representative optical micrograph of the 302 steel, condition A, is shown in Fig. l(a). Particles can be seen on the grain boundaries but no traces can be found of particles which grow from the grain boundaries into the matrix. A carbon extraction replica of this sample shows numerous large thin dendrites, Fig. l(b). The lateral dimension of such carbide particles vary up to 100 p, and their thickness estimated from the amoun! of electron penetration i:; between 500 and 1000A. Such large dendrites are extracted from almost all grain boundaries and, if they had grown into the grains, they would definitely be revealed by etching traces in the matrix, Fig. l(a). The reason why these large dendrites on the extraction replica appear to be grown into the grain is due to the mechanism of the extraction replica process. Thus, these dendrites are supported by the carbon replica film only at the edges originally along the grain boundary trace A-A, Fig. l(b), in the polished metal section and have subsequently fallen over onto the carbon replica film during handling. Although such dendrites generally fall only to one particular side of the grain boundary trace, one finds occasionally that parts of a dendrite have fallen to both sides, as shown in Fig. l(b). Further evidence for the growth of carbide in the grain boundary can be obtained from the appearance of fracture surfaces. A small impact specimen of the 302 steel, condition A, was broken at liquid nitrogen temperature. The fracture path follows the

Jan 1, 1962

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