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By R. F. Mehl, C. E. Birchenall

SINCE Maxwell1 first considered the self-diffusion process in 1872 its importance in the kinetic theory of matter has been recognized. Until the discovery of isotopes in 1913, a direct measurement of this quantity seemed impossible. The only information that could be gathered indirectly was for gaseous systems for which the kinetic theory was well developed. When methods of direct observation be-came available, investigations on self-diffusion were carried out in condensed phases. In metals these data are presumably of potential importance in the study of recovery, recrystallization, creep, sintering, and related phenomena. Following the pioneer work of Von Hevesy2 and his collaborators, who determined the rate of self-diffusion in lead with the naturally occurring thorium B isotope, several metals have been investigated. Pb, Ag³, Au.6,5, and Cu6,7,8,9 are examples of isotropic crystals existing in only one phase modification. Anisotropy of diffusion has been demonstrated in Bil6 and Znll. This paper is a study of a single metal in two allotropic forms and also of self-diffusion in a body-centered cubic lattice. Despite the fact that the measurements in each of the papers cited on self-diffusion in copper seem to be internally consistent to about 10 to 15 pet, the curves reported by different authors differ by factors of 2 to 4 at the same temperatures. This uncertainty may account, in part, for the failure to establish a successful correlation between the self-diffusion rates and other physical characteristics of the metals. No satisfactory theory of metallic self- diffusion has as yet been proposed to account for all the existing data and to permit estimation in other metals. Experimental Part: Two units of radioactive iron were used in these experiments, each a mixture of Fe53 and Fe59 (12). Fe53 decays by K electron capture and the emission of an X ray with a half life of about 4 years. Fe59 emits two beta spectra, one with a maximum energy of 0.26 Mev, the other 0.46 Mev, and gamma rays of 1.1 and 1.3 Mev, with a half life of about 44 days. They were present in nearly equal concentration initially. The composite half life started at about 50 days and increased as the Fe59 decayed, leaving Fe55 relatively more abundant. After aging a year, the half life was too long to measure significant decay in a month. The absorption properties also changed with time. Because of the importance of the absorption coefficient in the diffusion calculations, it was necessary to determine this quantity frequently over the period during which these experiments were carried out. This correction was unsuspected at the time of publication of notesl3 on this work and accounts for the discrepancy in alpha iron and for part of the discrepancy in gamma iron.* * The data in the present paper supersede those given in the notes entirely. In one note the scale of log D was inadvertently reversed. In addition to the correction for the drift in absorption coefficient, the D values for gamma iron at low temperatures were high owing to insuficient correction for diffusion occurring during heating and cooling through the high temperature part of the alpha range at a rate much slower than that employed in the runs reported here. The high temperature alpha rates are much higher than the low temperature gamma rates and correspond to large equivalent times at these temperatures. These experiments were discarded and new measurements taken. Independent experiments with the same activity units indicated a radioactive contaminant in the iron, but exhaustive attempts to isolate and identify it chemically failed. These experiments? indicate † These experiments will be discussed in a later publication from this laboratory. that the contaminant represented only a trace of little importance in the diffusion results. The active iron was plated from an iron chloride solution. Enough of the solution was dropped on a 1% in. square of filter paper to wet it thoroughly.

Jan 1, 1951

By R. F. Mehl, C. E. Birchenall

R. E. Hoffman and D. Turnbull—The authors have presented evidence which they have interpreted as indicating that the rate of self diffusion is not intrinsically more rapid at grain boundaries than within the grain. Grain-size effects which apparently exist are attributed rather to impurities concentrated at the grain boundaries. In view of our own experiments and the existing evidence, we believe that the support for this hypothesis is not convincing. We have in progress an investigation in which the rate of self diffusion of silver is being measured over an extended temperature range in both single-crystal and polycrystalline specimens. The results of the single-crystal experiments and some preliminary data on fine-grained polycrystalline specimens have already been reported:' and it is anticipated that a complete report will be published in the near future. The self-diffusion coefficient of large-grained polycrystalline silver (1 grain per sq mm) has previously been measured by Johnson" between 730" and 940°C. The diffusion coefficients which we have measured in single crystals (210 plane normal to diffusion direction) agree within experimental error with values calculated from an extrapolation of Johnson's curve down to temperatures as low as 500 °C. However, it has been demonstrated that the overall self-diffusion rate in fine-grained polycrystalline specimens (initial grain size of 0.003 cm) becomes measurably larger than the overall rate in a single crystal at a temperature of 600°C, and the discrepancy between the two rates becomes greater as the temperature is further decreased. In fact, it has been possible to obtain satisfactory penetration curves for polycrystalline specimens using the sectioning technique at temperatures as low as 400°C. At this temperature, the penetration is 50 to 100 times greater in the polycrystalline specimens than in a single crystal. Fisher" has developed an analysis whereby the ratio of the rate of the unit diffusion process at the grain boundary to the corresponding rate within the grain can be calculated from the penetration curves and an assumption as to the width of a grain boundary. This analysis applied to our data indicates that the unit process at the grain boundary is faster by a factor of 10' at 475°C when the grain boundary width is taken to be 5. The silver used in most of these experiments was obtained from the Handy and Harmon Co. and listed as 99.97 pct pure. Preliminary experiments on 99.999 pct silver from the Jarrel-Asch Co. indicate a grain-size effect of the same order of magnitude as in the less pure silver. Nominally, these purities are as good, at least, as that of the carbonyl iron used by the authors, but of course if an impurity effect does exist its magnitude might be very dependent upon the nature of both major and minor constituents. The authors have cited the work of other investigators who have found no grain-size effects. Neither Steigman, Shockley and Nix" nor Maier and Nelson8 were able to correlate self-diffusion coefficients of copper with grain size. However, all their measurements were performed at or above 750°C; and on the basis of our work with silver, no grain-size effect would be expected at temperatures above about 0.7 of the absolute melting temperature unless the grain size were exceedingly small. Likewise, in the investigation of the self diffusion of lead by Seith and Keil,14 the lowest temperature at which the diffusion coefficient was measured in polycrystalline specimens was 207°C, which is still sufficiently high so that the lack of a grain-size effect is not surprising. Finally, in those experiments on iron from which they concluded that there was no grain size effect, Drs. Birchenall and Mehl seem to have no information as to the actual grain sizes immediately prior to and following the diffusion anneal. Without this information, we believe that their own experiments offer little support for their hypothesis. F. S. Buffington, I. D. Bakalar, and M. Cohen—The results given in this paper agree in order of magnitude with those tentatively reported by us.27 However, significant differences exist in the two sets of data, and it may be well to make an explicit comparison. The diffusion studies at M.I.T. were conducted on somewhat higher purity iron (99.98 pct Fe) than the grades used by the authors, but this is undoubtedly not the answer. Fig. 4 shows the diffusion results of both laboratories for the gamma phase, omitting the authors' data on the commercial steels, while fig. 5 presents a similar comparison for the alpha phase. The divergence is much more marked in the latter case than in the former. In connection with the M.I.T. determinations, all of the runs in the gamma range and those above 800 °C in the alpha range were conducted with specimens having a relatively thick (0.002 cm) electrodeposit of radioactive iron. This practice minimizes any possible error due to extraneous diffusion that may occur during the heating to and cooling from the operating temperature. An exact solution of Fick's law for these boundary conditions was used in calculating the diffusion coefficients. At a later time, three runs were made below 800°C, using very thin electrodeposits similar to those of the authors, and the points fell considerably below the values expected from the extrapolation of the results based on the specimens with the thick deposits (compare dash-dot line in fig. 5). However, in the runs with the thin deposits, deviations of 100 pct were found between the individual specimens, whereas the maximum deviation with the thick deposits was less than 25 pct. Accordingly, it is not known at the moment whether the M.I.T. points below 800 °C should be given as much weight as those above 800°C. If this were done, the frequency factor would be of the order of 400 cm2 per sec, which is quite high. In other metals, the frequency factor for self diffusion lies between about 0.1 and 10 cm2 per sec. As the points below

Jan 1, 1951

By R. J. Borg, C. E. Birchenall

The self-diffusion coefficients for a iron have been deternzined between 980° and 1167° K using Fe55 as the tracer. With decreasing temperature the diffusivity was found to decrease more rapidly than predicted by the Arrhenius equation in the region of the Curie temperature. The diffusion coefficients obtained well above the temperature of the magnetic transformation are more precise ard differ substantially from all the previously reported values. In the temperature region beginning at least 50" above T,, the diffusion coefficient is given by D = 118 (±2) exp 1 HE self-diffusion coefficients for a iron have been reported previously as the result of four independent investigations The general lack of agreement and the poor precision of most of the previous work prompted the redetermination by the present authors. The possible effect of the onset of ferromagnetism upon the diffusivity5 provided an additional impetus for this investigation. The earlier measurements of Birchenall and Mehl1 gave low values for the diffusion coefficient at temperatures below the Curie temperature, Tc. However, the precision of these measurements is not sufficient to establish an indisputable correlation between the low values and the magnetic transformation. The results of this investigation along with all the previous ones are shown in Fig. 1. EXPERIMENTAL Small rectangular samples, approximately 1 by 0.5 by 0.3 cm, of high-purity iron (Vacuum Metals Corp., "Ferrovac") are first heated in hydrogen at 900°C for24hr in order to remove possible trace amounts of dissolved carbon and oxygen. The small

Jan 1, 1961

By S. J. Rothman, A. L. Harkness, L. T. Lloyd

Self-diffusion in Y uranium has been measured using U235 as the tracer isotope. The diffusion coefficient fits an Arrhenius-type equation D = 2.33 x 10 -3 exp (- 28,5000/RT) cm2/sec The values of Do and Q are unusually low and are not consistent with the values expected from theories based on a simple vacancy mechanism of diffusion. CYLINDRICAL samples, 1 cm in diam and 1/2 to 1 cm long, were prepared from high-purity uranium containing 0.0343 pct u235, Table I. The samples were water quenched from 690°C (the a-ß transformation is at 668°C) to remove preferred orientation, and annealed at 450 "C to minimize residual stresses. One end of each cylinder was polished on a 1-µ diamond lap and electropolished in a phosphoric acid solution. After a final cleaning by cathodic sputtering, a 1- to 3-µ thick layer of the tracer isotope, uranium containing 93 pct u235, was sputtered onto the sample.' To prevent contamination during the diffusion anneal, the diffusion couples were placed in a tantalum cup and covered with another piece of uranium, and the whole assembly was sealed off in an evacuated quartz tube. Annealing temperatures were constant within +2.0°C. The samples were heated and cooled slowly between room temperature and the ß-? transformation (774°C) in order to minimize distortion of the sample surface that might arise from aniso-tropic thermal expansion and density changes during phase transformations. After machining off 1/16 in. from the radius to

Jan 1, 1961

By P. G. Shewmon

Radioactive MgZA has been used to study the rate of self-diffusion in oriented single crystals of magnesium in the temperature range 468O to 635OC. The diffusion coefficients parallel and perpendicular to the c-axis are: Dl, = 1.0 exp (—32,200IRT) cm2 per sec and Dl = 1.5 exp (—32,500IR T) cm Qer sec. The ratio Dl/Dll was found to vary from 1.13 at 468 to 1.24 at 575 C. Assuming a vacancy mechanism, an explanation of this aniso-tropy of diffusion follows from a consideration of the difference in the saddle points for diffusion in and out of the basal plane. RECENT discovery of radioactive Mg2"'-' has made possible the study of self-diffusion in magnesium. The experimental procedure and the results of a study of diffusion in polycrystalline magnesium have been described in an earlier paper.V he present work is an application of the same techniques to the study of self-diffusion in oriented single crystals of magnesium. In the general diffusion problem the diffusion coefficient is a second order tensor relating the two vectors, the diffusion flux, and the concentration gradient. In a hexagonal lattice, such as magnesium, the complete determination of the diffusion coefficient D as a function of direction in the lattice requires a knowledge of D,, and D,, i.e., the diffusion coefficients parallel and perpendicular to the c-axis, respectively. It can be proven quite generally that in a hexagonal lattice D is independent of direction in the basal plane, and that out of the basal plane it varies with 0, the angle between the c-axis and the direction of diffusion, according to the equation D(B) = D,,cos2B + D,sin2B. [I] The proof of Eq. 1 depends only upon the symmetry elements of the hexagonal lattice and upon the transformation properties of a second order tensor." Therefore, Eq. 1 holds for any mechanism of diffusion and any c/a ratio. Experimental Procedure The experimental procedure used with polycrystalline specimens can be briefly outlined as follows. Radioactive Mg" was produced by bombarding a NaCl crystal with 350 mev protons and was chemically separated from the target as MgO. The Mg" was then vapor deposited on a specially cleaned magnesium specimen by heating the MgO on a tantalum ribbon in a vacuum. During the diffusion treatment, oxidation and vapor loss of the radioactive material were minimized by annealing the samples in pairs with the active faces in contact, each pair being inside a magnesium container, which was in turn surrounded by an argon atmosphere in a sealed Pyrex tube. The distance-activity profiles were obtained by measuring the activity of thin sections cut parallel to the original interface with a lathe. The only technique which was peculiar to this work was the preparation and orientation of the single crystal specimens. The single crystals used in this work were grown by E. C. Burke of the Dow Chemical Co., using a modified Bridgman method, in which the furnace and specimen were stationary while the temperature gradient moved.' In growing these crystals the starting material was distilled magnesium, the crucibles were machined from Acheson electrode graphite, and the furnace atmosphere was tank argon. The crystals were grown from sublimed magnesium with the following analysis: 0.0002 pct Al, 0.0017 pct Fe, 0.0009 pct Mn, 0.0001 pct Ni, 0.0006 pct Pb, and less than 0.01 pct Ca, 0.0001 pct Cu, 0.001 pct Si, 0.001 pct Sn, and 0.02 pct Zn. The two crystals used were roughly lh in. diam and eight in. long. The c-axis made angles of about 7" and 78", respectively, with the specimen axes. If the values of D obtained by the use of these two crystals are taken equal to D,, and D,, respectively, the error introduced by this assumption is less than 1 pct. This can be shown by combining Eq. 1, the identity sin% + cos'8 = 1, and the experimental fact that DJDn in magnesium was always less than 1.25.

Jan 1, 1957

By F. E. Jaumot, R. L. Smith

Self-diffusion in zinc at temperatures below 200°C has been studied using both single crystal and polycrystal samples. Anomalous results were obtained for single crystal samples, the data indicating that in some cases grain boundary diffusion predominated. These anomalous results are presumed to be due to low angle lineage boundaries in the single crystals. When volume diffusion occurred in either single or polycrystal samples, the values for the diffusion coefficient were as much as several orders of magnitude larger than would be expected from high temperature data. ONSIDERABLE work has been done on self-^-*diffusion at temperatures in the neighborhood of two thirds of the melting temperature (in OK) and higher, but very little has been done at lower temperatures. This is particularly true of self-diffusion in single crystals. This paper reports work on self-diffusion in zinc at temperatures below 200 °C where both polycrystalline and single crystal samples have been used. The measurements were made using both the sectioning and absorption techniques. The experiments on diffusion at low temperatures were initiated primarily for three reasons: to obtain data from single crystal diffusion covering a wide range of temperatures, to obtain values of the activation energy for grain boundary diffusion, and to obtain, if possible, a lower limit to the temperatures at which the absorption technique may be used. It is possible to determine whether volume or grain boundary diffusion predominates at low temperatures by analyzing the manner in which the concentration of the diffusing atoms varies with the depth of penetration. The analysis is possible only for the sectioning technique. For volume diffusion and for the boundary conditions of the present experiment, the curve of the logarithm of the concentration, C, vs the square of the penetration depth, x, is a straight line with the slope proportional to — 1/D. If grain boundary diffusion predominates, Fisher' has shown that a curve of In C vs the first power of the penetration depth should be a straight line. This linear dependence of concentration on depth has been observed experimentally by several investigators. (See, for example, refs. 3 and 4.) Following Fisher's analysis, the grain boundary diffusion coefficient can be written as where 8 is the grain boundary width, D, is the volume diffusion coefficient at the temperature involved, t is the time of diffusion, C is the concentration of diffusing material, and x is the depth of penetration. A more general analysis employing the same model as Fisher's but with fewer assumptions has been given by Whipple.' In contrast to Fisher's analysis the more general analysis of Whipple does not always yield a straight line relation between In C and x. Recently Turnbull and Hoffman have discussed both analyses and have applied the Fisher-Whipple model to a more refined dislocation model of the grain boundary. They have also discussed the possibility of a large effect of grain boundary direction on diffusion. In the case of the absorption technique, for which results are also given, one simply gets a value for the diffusion coefficient with no indication of the predominating mechanism. Experimental Techniques Single crystals of 99.99+ pct Zn were grown using a modified Bridgman method. Polycrystal samples were prepared in three grain sizes (small, about 4 mm2; medium, about 9 mm'; and large, about 25 mmz) by quenching, air cooling, and furnace cooling. The grains of the polycrystalline samples tended to be columnar, with some preferred texture such that the c-axis was inclined at about 20" to 25" from the normal to the diffusion face, particularly in the medium and large grain size samples. The samples were cut from the rod, polished, and heavily etched, and faces cut accurately parallel using a jeweler's lathe. They were again etched to remove the lathe smear and annealed for 3 hr at 250" to 300°C. After annealing, they were etched, examined, and the orientation determined by Laue back reflection photographs. They were then electroplated with Zn. The plated surfaces were examined for uniformity; nonuniform coatings were removed by etching and the samples replated without additional preparation. For the diffusion anneals, the samples were placed in pairs, with active faces together, in evacuated Pyrex tubes. Constant temperature baths were used, and the variation in temperature did not exceed ±l°C, Diffusion runs were made at l00°,

Jan 1, 1957

By G. C. Kuczynski

Two particles in mutual contact form a system which is not in thermo-dynamical equilibrium, because its total surface free energy is not a minimum. If such a system is left for a certain period of time, the bonding of the two particles will take place in order to decrease the total surface area, even though the temperature is lower than the melting point. This phenomenon of bonding of two or more particles with the application of heat only and at temperatures below melting point of any component of the system will be called sintering, although the powder metallurgists use this term in a broader sense, including the presence of molten phase and pressure. It is the objective of this paper to study this process and the mechanisms involved in it. This problem is of utmost importance to powder metallurgy and powder ceramics, and its technological aspects have been studied for a good many years. However, the powder metallurgical operations are too complex and include too many superimposing mechanisms, and too many variables for a direct study. It was therefore advisable for the purposes of this study to reduce the variables to a minimum. In this work the radius of the interface formed during bonding in a simple system composed of a spherical particle and a large block of the same metal was studied as a function of time and temperature. It is believed that the mechanism involved in this simple process is fundamental to any sintering operations. Previous Work J. Frenkell was the first to make a serious attempt to develop a theory of sintering. He assumed that the process consists of a slow deformation of crystalline particles under the influence of surface tension which reduces to a viscous flow where the coefficient of viscosity n is related to the self-diffusion coefficient D by the following equation 1 _ D D6kT [1] where 6 is interatomic distance, k the Boltzman constant, and T the absolute temperature. This type of viscous flow of a crystalline substance is essentially different from the ordinary plastic flow. The latter is a specific propcrty of crystals and cannot take place in amorphous bodies. According to Frenkel this viscous type of flow is due to the diffusion of the holes or vacancies arising in the lattice. He was able to derive an equation relating the growth of the interface between two spherical crystalline particles or between a particle and a semi-infinite crystal (Fig 1) to time t at constant temperature. This relationship can be written as follows: x²— 3/2 a/nt [2] where x is the radius of the interface assumed to be circular, a the original radius of the sphere and a surface tension of the material. The other assump- x tions are that x is less than 0.3 and that during the period 1 the original radius, a, of the metallic particle did not change appreciably. A. J. Shaler and J. Wulff2 followed closely the ideas of Frenkel in their theory of sintering of a mass of metallic powder. Neither Frenkel nor Shaler has validated his theoretical speculations with conclusive experimental data. Two measurements reported by

Jan 1, 1950

By W. C. Hagel

Previous inuestigators have repovted unusually low H* and Do values for self-dzf@szon in certazn bcc metals, e.g., chromium nnd y -uvanium. It has been postulated that this is nn experimental crl -tetion for the existpnce of a four -atom ring meclzanzsm, mid there could be. zmpovtant theoretrcal Implicatlons. By utilizing a precise sectioning technique with Cr51 as the tracer, self-dzffi-lsion measurements in large grains of 99.99-pct Cr were extended from 1200° fo 1600"C. A least- squares analysis of the data yields that D 0.280 exp (-73,20U/RT) cm2 sec-'. These AH* and Do unlues are not anomalous; there is little reason to believe that n vacancy mechanism is not opevatiue. Apparent differences at lower temperatures may result from preferential diffusion along short-circuititing paths and/or sample contamination. WITH continued technological effort, chromium and chromium-base alloys should ultimately become useful high-temperature structural materials. Accurate measurements of self-diffusion coefficients in the pure metal are necessary for a quantitative understanding of sintering, grain growth, creep, and other related rate processes. However, two conflicting determinations have been reported.* Using an Since careful diffusion studies normally yield Do values ranging from 0.1 to 10 cm2 sec-l, the Paxton-Gondolf results require independent experimental corroboration before an undue amount of speculation arises to explain the apparent anomaly. As discussed by Nowick6 and clearly shown by Hoffman and Turn-bull7 for self-diffusion in silver, a low AH* and Do can arise from preferential diffusion along grain boundaries or other short-circuiting paths. The most reliable data come from high-temperature measurements where volume effects predominate. Following a precise sectioning technique developed for determining silver diffusion in the intermetallic compound AgMg8 and cation diffusion in the corundum oxide Cr2O3,9 the purpose of this study was to measure true volume diffusion in high-purity, large-grain samples at higher temperatures than considered previously. Another point of interest is the frequent proposal10-12 that chromium undergoes an allotropic transformation between 1375" and 1800°C where the diffusion data might then show a discontinuity. I EXPERIMENTAL 1) Sample Preparation. The highest purity (99.997 pet) Cr currently available is produced by reduction of chromium tri-iodide. Three pounds of the resulting crystal bar were shipped in a sealed container with a complete chemical analysis from the vendor.* In conformity with the procedure used for

Jan 1, 1962

By R. E. Hoffman, R. A. Ward

The self-diffusion coefficient in high purity nickel has been measured over the temperature range 870' to 1248°C. The results are described by the relation D = 1.27 exp[—-66,800/RT 1cm2ec-1. The measured activation energy correlates satisfactorily with absolute melting point, heat of fusion, and heat of sublimation. KNOWING the rates of self-diffusion is important in the understanding of many metallurgical reactions. However, in spite of the rather widespread interest in nickel, both commercially and in fundamental investigations, no measurement of the self-diffusion in solid nickel has previously been re- ported." In connection with a program of measuring rates of diffusion in some nickel alloys, self-diffusion in pure nickel has been investigated over a rather wide temperature range by combining a sectioning technique and a surface counting technique.

Jan 1, 1957

By L. Himmel, R. F. Mehl, C. E. Birchenall

The rates of self-diffusion of iron in artifically prepared wustites of various compositions have been determined using the decrease in surface activity technique. Similar measurements are reported for artificial magnetites of nearly stoichiometric composition and for natural hematite single crystals. These data, together with appropriate thermodynamic data derived from the present study or from the literature, are used to calculate the rates of oxidation of iron and its oxides, taking as a basis the theoretical rate equations developed by Wagner. The calculations are compared with experimental rate constant data for these same reactions and are shown to provide essential confirmation for the Wagner theory. For the most part, the results are also consistent with the previously proposed transport mechanisms in the oxides of iron. WHEN a metal is exposed to an oxidizing atmosphere at elevated temperatures, a superficial oxide layer is formed which then thickens according to some characteristic rate law. Provided that the oxide layer is dense and continuous and does not present any paths for gaseous diffusion, continued growth must inevitably involve the migration of the reactants—either the metal or oxygen or both—through the lattice of the solid oxide. This is true whether the reaction rate is controlled by the diffusion process itself or by a slow step in a reaction at one of the interfaces. If the overall rate is limited by diffusion, and if the concentrations or thermodynamic activities of the reactants at the boundaries of the oxide layer are independent of time, the familiar parabolic rate law is observed. Under these conditions, Wagner1 has shown that the rate constant may be expressed in terms of the mobilities of the reacting components and the appropriate concentration or activity gradients which are established across the growing oxide layer. In presenting the phenomenological basis for the theory, Wagner has emphasized the role played by lattice defects in diffusion processes in oxides. The essential validity of this theory has been confirmed by experiment for a number of simple systems including the growth of Cu2O on copper.'-' One of the objectives of the present study has been to extend the Wagner approach to the more complex process of the oxidation of iron and its oxides, and particularly to wustite, which is normally the major constituent of the oxide scales formed on iron at temperatures above approximately 570°C. For this purpose the rates of self-diffusion of iron in w?stite, magnetite, and hematite have been measured by tracer techniques and the necessary thermodynamic data have been obtained from equilibrium studies involving the oxides and their atmospheres. These data have subsequently been used to test the underlying assumptions of the Wagner theory as well as the detailed mechanism of the scaling of iron previously proposed by Davies, Simnad, and Birchenall.5 Lengthy treatments of diffusion and conduction phenomena in ionic crystals have been published." * The latest, by Jost,8 also summarizes much of the existing experimental data. In general, however, the oxides of iron have not been considered specifically and hence a brief review of the available

Jan 1, 1954

By C. E. Birchenall, R. H. Condit, M. J. Brabers

In the oxidation of pure iron above 700°C the overall rate is determined mainly by the rapid growth of wiistite, through which iron ions can diffuse rapidly.' Nickel added to the iron progressively decreases the stable range of composition of wustite.' When enough nickel is added to eliminate wiistite as a stable phase, the spinel is the fast growing phase. This investigation was undertaken to test the hypothesis that nickel substituting for iron in magnetite might decrease the rate of spinel growth by reducing the iron mobility. Nickel ferrite boules grown by the flame fusion process were purchased from the Linde Co. Chemical analysis gave an atomic ratio of iron to nickel of 2.88 and showed no other cations. They were cut into discs and ground to give flat, parallel faces. The experimental procedure employed was like that of Eisen and Birchenall in which the distribution of radioactivity diffused in from a vapor deposited surface layer was determined by counting the residual activity through a series of ground faces. The diffusivities were calculated in a manner consistent with the requirements discussed by Condit and BirchenallP The details will be given in connection with a more extensive spinel diffusion study now in progress. The results of the measurements are shown in the figure in comparison with earlier data on magnetite1 and zinc ferrite. The uncertainties arising from scatter in the activity vs distance relationship and uncertainties in the temperatures are shown by flags. Despite the scatter it is clear that substitution of a considerable part of the iron in magnetite by nickel, in this case about one third decreases the iron mobility substantially. sachs' determination of the distribution of iron and nickel in scales on iron-nickel alloys appears to show that nickel is less mobile than iron in the spinel layer. It is evident, therefore, that nickel plays several roles in reducing the oxidation rate of iron-nickel alloys. 1) It reduces progressively the stability range of wiistite. ' 2) It reduces progressively the stability range of the iron-nickel spinel phase in terms of the variation in cation to anion ratio.' 3) As shown in this investigation, it reduces the cation mobility in the spinel phase which is the faster growing phase in the absence of wiistite. The fe was obtained from the Oak Ridge National Laboratory. The research was supported by the Air Force Office of Scientific Research (ARDC) under contract number AF 18(600)-967.

Jan 1, 1961

By H. I. Aaronson, H. A. Domian

The self-diffusivity of Ag10 has been measured as a function of temperature and composition in AgMg. a CsCl-type intermetallic compound with a substitutional defect structure on both sides of the stoichiometric (50 at. pct Mg) composition. These measurements show that In D increases linearly, and both In Do and Q decrease linearly with deviation from stoichiometry. The slopes of these lines are significantly steeper in magnesium-rich alloys. Equations for the variation of Q with composition have been derived by application of the theory of random walk processes on the assumption that diffusion in compounds of this type takes place by the six-jump cycle mechanism of Huntington, Elcock, and McCombie. The favorable agreement obtained with experiment furnishes fresh support for the correctness of this assumption. A principal result of this treatment is that. although the concentration of vacancies is considerably higher in the silver sublattice than in the magnesium sublattice, the acfivation energies for movement of the magnesium sublattice vacancies are so much lower that these vacancies are responsible for effectively all diffusion of silver in this compound. A tendency for vacancies of both types to be kinetically bound to wrong atoms is also noted. THIS study was undertaken to examine the influence of substitutional defects upon self-diffusion in an intermetallic compound, AgMg, with a CsCl-type crystal structure. The CsCl structure is exception- ally simple. At the equiatomic or stoichiometric composition in a binary alloy, it consists of two interpenetrating simple cubic sublattices, each of which is exclusively populated by the atoms of one species. When atomic size and other factors are favorable, deviations from stoichiometry can be entirely accommodated by the substitution of atoms of the species present in excess of 50 at. pct on the sublattice of the other species on a one-for-one basis. Under this condition, the only vacancies present are those formed by thermal activation. The excess atoms thus incorporated into the sublattice of the minority species may be considered as substitutional defects in this sublattice. Several X-ray studies have shown that the defect structure of AgMg is entirely of the substitutional type on both sides of the stoichiometric composition.1"3 The thermodynamic investigation of Kachi indicates that, aside from a low level of thermal disorder and these constitutional defects, order is maintained to the solidus temperature. This compound is therefore a particularly useful vehicle for a study of the influence of substitutional defects upon diffusion kinetics. Other advantages of AgMg for this purpose include: the broad composition region, as much as approximately 10 at. pct on either side of the stoichiometric (50 at. pct Mg), in which the compound is stable; the comparatively low temperature range of the solidus (820°C and below),5 making diffusion anneals near this range experimentally convenient; the reasonably good machinability of the compound, permitting utilization of the standard sectioning method of radiotracer analysis; and the availability of a good tracer, A for one of the constituent species. While this investigation was in progress, Hagel and westbrooks reported data on the self-diffusion

Jan 1, 1964

By Appendix by A. S. Goldoni, R. E. Tate, E. M. Cramer

The diffision coefficient for self-diffision of plutonium in the temperature range 350" to 440°C has been measured by using puZ3 as the tracer isotope. Autoradiopaphic techniques were used to inzlestigate the possibility of grain boundary diffusion, hut only evidence for volume diffusion was found. The least-squares fit of the data gives the .following equation for the diffision coefficient: The computer least-squares technique for fitting the nonlinear equations is outlined. DETERMINATION of the self-diffusion coefficient of the fcc 6 phase of plutonium is in principle a straightforward experimental task. However, the chemical reactivity, the intense @ activity, and the toxicity of plutonium put limitations on the experimental techniques. The technique selected included roll bonding for preparation of the diffusion couples and pulse-height analysis of the @-particle activity to determine the distribution of the PU tracer in the diffusion couples. EXPERIMENTAL PROCEDURE Couple Preparation. Cylinders about 0.5 in. in diam were cast from two special stocks of plutonium, one of which had been enriched in puZ3', as shown in the isotopic analyses listed in Table I. For each roll-bonded composite sheet, a cylinder 0.437 in. in diam and 0.190 in. thick was turned from each kind of plutonium on a lathe in a 98 pct He atmosphere. The two freshly machined cylinders were positioned face to face in a tube of commercially pure aluminum which had been sealed at one end by welding and the assembly was evacuated on a vacuum manifold overnight. The elapsed time between machining the faces of the plutonium cylinders and evacuating the loaded tube was about 15 min. After overnight evacuation of the assembly the indicated vacuum was 1 X 10"5 torr or better. The aluminum tube was then warmed and pinched off with a cold-welding tool. The pinched-off weld was also fusion-welded as an additional precaution against leakage of air into the evacuated assembly. The assembly was immediately heated for 30 min in a 250°C furnace and reduced in thickness by being passed through a rolling mill with rolls heated to 200°C. The rolling schedule (four passes of 100 mils each with a 10-min reheat after two passes) reduced the thickness of the assembly to 100 mils. The rolled assembly was allowed to cool normally in air. The rolled assembly was sheared at the edges and the aluminum peeled from the composite plutonium sheet. The elliptical sheet was about 0.060 in. thick and usually three 0.383-in.-diam disks could be punched from its central portion. The sheet was heated on a hot plate to the ductile low 0 range (140°C as measured by temperature-indicating pellets) before each disk was quickly punched. The quality of the bond in the disks was evaluated by metallographic examination of the scrap sheet adjoining the hole left by the punch. Only well-bonded specimens without oxide in the interface (as indicated by metallography) were considered satisfactory for further use. More than half of the specimens so examined contained sufficient oxide in the interface to be rejected. Diffusion Anneal. Each disk to be diffusion-annealed was wrapped in 1-mil-thick tantalum foil and sealed within a Pyrex capsule evacuated to 1 x 10~5 torr or better. This capsule was then sealed within another Pyrex capsule at a similar pressure. The diffusion anneals were carried out at temperatures between 350" and 440°C in Marshall furnaces adjusted to have a temperature gradient of not more than *1/2"C over a 5-in. length. This gradient was then further smoothed by using a nickel tube as a liner in the furnace. The liner was divided into three longitudinal cavities by a septum of nickel sheet to which two calibrated Chromel-Alumel thermocouples were attached. One thermocouple was used for controlling the furnace temperature by means of a Brown Pyrovane controller equipped with a Capaciline anticipation circuit; the second thermocouple was monitored twice daily with a Leeds and Northrup K-2 precision potentiometer.

Jan 1, 1964

By D. L. Feucht, R. L. Longini

The semiconductor heterojunction is considered in terms of simple models which may lead to an understanding of move complex heterojunctions. Metallurgical and electrical properties of hetero-junctions aye discussed including the interface structure, energy -band diagram, and carrier transbovt across the interface. It is found that in a heterojunction all mechanisms such as injection, tunneling, and junction recombination found in simple junctions play modified voles. INTERFACES between materials (grain boundaries, the electrical junction between two differently doped materials in a single crystal, the oxide-metal interface, or metal-metal junctions) are of considerable importance in many situations. These various interfaces all have one very fundamental thing in common. Quantum mechanically speaking, the wave functions of the electrons in one material may penetrate the other material but, in general, only to the extent of angstroms. From an electrical point of view the conduction mechanism changes as a current passes through such junctions. In some cases the change is tremendous, in others almost negligible. The interface, then, is the locus of a change of conduction mechanisms. Some of these, particularly in semiconductors, are well-understood. The ordinary p-n junction in a single crystal can be the locus of an injection mechanism or a tunneling process, depending on conditions. The mechanisms are probably best understood in semiconductors because of the possible simplified view of particlelike conduction. The bands are either nearly filled or nearly empty and band overlap is seldom involved. The same fundamentals are probably important in other situations too but they are very difficult to look at naively. Although the simple look at the semiconductor case only gives us a relatively rough picture which must then be refined, the other systems, which involve a more complex situation, immediately are in many ways too difficult. There are too many initial choices of complex systems and therefore it is not possible to be even reasonably certain of any one model. Because of the relative simplicity of semiconductors, their good and controllable structure, and because of the ability to make many measurements on them not normally available to either metals or insulators! they are probably the best understood materials. It is therefore desirable to use them as a tool to further the understanding of interfaces in general. Semiconductor-heterojunction concepts were first proposed by kroemer1 in 1957. This was followed several years later by reports on the fabrication and experimental characteristics of heterojunction structures by Anderson2 and Diedrich and jotten.3 I) THE HETEROJUNCTION STRUCTURE To get down to hardware, when we refer to a semiconductor heterojunction we imply that there exists an intimate contact between different semiconductor materials. We could put two pieces of material together, complete with oxide layers, we could remove the oxides, or we could even melt the interface and hopefully get wetting and a good "bond" on solidifying. In fact we could by some means grow a crystal of one material using the other as a seed. Essentially we are interested only in the last two because they are the simplest to look at analytically. The degree of perfection of fit varies greatly and is reflected somewhat in the arc welder's joint strength. The lattice match of the two materials, their orientation, and so forth. is obviously necessary for a good bond but so is the continuity of any polar bonds which are involved such as in the III-V semiconductors. The mechanical misfit between two similar lattices can be described in terms of edge dislocations. The edge-type dislocations must be very close together for the usual misfit and there must be dislocations for each of several different Burger's vectors in order to produce a lattice match. The .'dangling bonds'' resulting will be involved in producing interface charge. Order of magnitude estimates of the charge density extrapolated from low densities of dislocations in homogeneous materials give 5 x 1013 cm-2 Ge-Si and 1 X 1012 cm-2 Ge-GaAs electronic charges. Edge dislocations also act as very active recombination centers between holes and electrons. One lattice "matching" difficulty usually exists even if two structures have essentially the same lattice constants as they will have different coefficients of therma1 expansion. Thus, on cooling from the usually high temperature of fabrication to room temperature, dislocations are produced, a good fit not existing at both temperatures. In brittle materials this shrinkage may even result in cracking. For the Ge-Si interface the mismatch is about 2 x 10 -6 per degree whereas it is less than 10"7 per degree between germanium and GaAs. The exact effect of the misfit is dependent on the thickness of the materials involved. For a very

Jan 1, 1965

By A. J. Shaler

The subject of the mechanism of sintering has received much attention in the past few years, particularly since the beginning of the series of AIME seminars in powder metallurgy of which this paper introduces the fourth. In the first of these, F. N. Rhines1 brought together and discussed the available experimental data on the sintering of pure metallic powder, and succeeded in bringing to a sharp focus the attention of workers in this field on the established observations which a satisfactory theory must explain. Several other authors3,5,6 have, in the last few years, studied the phenomena that occur when cold metallic powders, loose or in the form of compacts, are first brought to elevated temperatures. Some workers' in the field of friction have recently studied the adhesion of solid metal surfaces when they are brought into close contact. These researches have indicated that several separate mechanisms operate simultaneously, at least during the first part of the sintering process. Some of them have been called transient mechanisms4 because they are in general not absolutely necessary to sintering. Powders may be so prepared and so treated that these transient phenomena do not take place during subsequent sintering. This does not mean, of course, that their industrial and scientific importance is any less than that of the steady-state phenomena. The latter are changes that go on during sintering no matter how the powders are made or treated; they cannot be divorced from sintering. One way to analyze the process of sintering into its component parts is perhaps to distinguish between these transient and steady-state phenomena. Some of the transient phenomena have been studied in the past few years. Huttig3 has shown that, when the temperature of metallic powder is slowly raised, the following events generally occur in order: (1) physically adsorbed gases are desorbed; (2) there is an atomic rearrangement of the surface, a sort of two-dimensional "surface-reciystallization"; (3) there is a breakdown of chemically adsorbed surface compounds; (4) there is a recrystalliza-tion in the volume of the metal. All these changes are shown by Huttig and his coworkers to be completed fairly rapidly at lower temperatures than those generally used in sintering and are therefore not a part of the mechanism whereby the density of a mass of powder continues to change after long heating at an elevated temperature. But the first and third of these changes release gases in quantities which may or may not help to control the steady-state mechanisms, depending on when the voids become isolated from the outside of the compact. Among the phenomena studied by Steinberg and Wulff,8 there is the effect on sintering of residual stresses arising from the pressing operation. They found that the lateral surfaces of a green compact of iron are under a longitudinal residual tension-stress of the order of magnitude of half the yield-point for solid iron. If the outside surface is in tension, the core must be under longitudinal compression. When the compact is heated, the surface residual stress is thermally relieved first, and the compact therefore initially expands in the direction of its axis. This is a transient phenomenon, if for no other reason than the possibility of sintering unpressed powders, as demonstrated by Delisle,9 Libsch, Volterra and Wulff10 and others.1 The subject of recrystallization is dealt with further in a separate section, in view of its prominent place in sintering literature. It, too. is one of these transient phenomena. Among the steady-state parts there may be distinguished the attraction between particles and its consequences, the spheroidization of voids in the compacts, and the densification or swelling of the compact. There is considerable evidence4,7 showing that cold metallic surfaces, when brought to within a few interatomic distances of one another, are attracted to each other by forces of the order of many thousands of pounds per square inch. A calculation, discussed in greater detail in another section, shows that this force changes but slightly when the temperature of the surfaces approaches the melting point. Actual measurements of forces of adhesion of this magnitude have been made by Bradley12 on some nonmetals, but none has yet been made on cold or hot metals. This force is of sufficient magnitude to cause some plastic deformation in powder compacts, as will be shown below. A second force of steady-state nature is due to the surface tension, which probably has the same origin as the force of attraction between surfaces.164 A paper by Udin, Shaler, and Wulff1,3 gives the results of precise direct measurements of its value for solid copper. The demonstration of the tendency for the surface tension to shrink a pore was long ago given by Gibbs.17 He showed that its effect on a curved surface between two phases is equivalent to a pressure perpendicular to that

Jan 1, 1950

By George R. Cowan

A number of studies hare been reported of the effects produced in metals subjected to deformation by shock waves with maximum pressures ranging from tens to hundreds of kilobars. On the basis of the equations for the flow of mass, momentum, and energy through a stationary shock front, the macroscopic stress-strain curve for the resulting shock deformation can be calculated within narrow limits from the experimentally determined Hugoniol curve. In relatively weak shocks which are preceded by an elastic wave, the stress rises above the clastic limit only as plastic deformation proceeds cold thus the shock has a long toe. In strong shocks that override the elastic wave a high stress is applied without prior plastic deformation. A more important effect of increasing the shock pressure is the generation of shear stresses, called supercrilical shear stresses, that exceed the strength of the perfect lattice. A change in the mechanism of deformation is expected to result from the onset of supercritical shear. The shock disordering of ordered Cu3Au in strong shocks appears to be an example of such a change. It is suggested that the formation of fine twins in copper and nickel and the formation of structures which enable visible twins to be formed in the rarefaction ware, observed in copper and presumably in disordered Cu3 Au, are related to the occurrence of supercritical shear in shock dcformation. In recent years several studies1,2 have been made of the changes in structural and mechanical properties of metals produced by the passage through the metals of strong shock-compression waves ranging from about 50 to 800 kbar pressure. Recent work involving dynamic measurements of the shock compression "Hugoniot" curves 3-8 of many metals has developed techniques and provided data required to obtain the shock pressure and the (transient! plastic deformation produced in the shock-conlpression experirnents.9 Shock deformation has been found to be much more effective than slow deformation in changing the mechanical properties of metals, when the two are compared on the basis of equal plasti strain, Holtzman and Cowan9 made quantitative estimates of the shearing stress occurring in a shock front in a metal by assuming that the shearing stress is similar to that occurring in a shock front in a viscous, heat-conducting fluid, with the addition of a yield stress. Taylor's solution9 for a weak shock was used to estimate pairs of values of shearing stress and thickness of the shock front obtained by assumed choices of the ratio of effective kinetic viscosity to thermal diffusivity. It was noted from these values that. unless the shock front is extremely thin. heat conduction has slight effect, and the shearing stress is nearly independent of the mechanism of deformation. This mechanism does, however, determine the thickness of the shock front and the rate of strain. Furthermore, since the maximum possible shearing stress occurring in shocks of moderate strength does not greatly exceed the shear stress occurring in conventional slow deformation, the mechanism of deformation is not expected to be qualitatively different. The greater effectiveness of shock deformation in changing the mechanical properties of metals can be attributed partly to the fact that dislocations, when driven by near-conventional stresses, cannot keep up with the shock front, thus necessitating a higher dislocation density than required for an equivalent slow strain. The fast uni-axial strain occurring in the thin shock front would also be expected to cause a larger number of dislocation intersections to occur. In the upper range of shock pressures that have been studied the estimated values of the shearing stress exceeded the estimated shear strength of a perfect crystal. Under these circumstances it is reasonable to expect that the mechanism of deformation might be considerably different from that involved in slow deformation. Except for the observation by smith1 of twins in shocked copper, the effects of shock waves on metals did not show any obvious or large changes in properties that would indicate the onset of a change in the mechanism of deformation. The recent investigation of the effect of shock waves on ordered and disordered specimens of Cu3Au by Beardmore, Holtzman, and ever" showed a spectacular decrease in the amount of long-range order retained by initially ordered Cu3Au when the shock pressure was raised from 290 to 370 kbar. Since Dr. Holtzman and I suspected that this behavior probably was due to the onset of a shearing stress in the shock front in Cu3Au which exceeded the limiting shear strength of the perfect crystal. it was considered appropriate to examine directly the shock-front equations for a solid. and to obtain a sound estimate of the shearing stress occurring in the front using equation of state data obtained from shock studies. In this paper an estimate is made of the

Jan 1, 1965

By P. C. Johnson, B. A. Stein

This paper describes a study of the effects of combined heat treatment and explosive loading on the mechanical properties of high-strength steels. nis program investigated two distinct areas: 1) the effect of shock waves, without gross irreversible defmmution, on a 3-Cr steel at various stages of heat treatment; and 2) the effect of rapid deformation (explosive forming) on H-11 and D6-AC steels in the metastable austenitic state. The mechanical properties of these steels were improved, in some cases markedly, as a result of these treatments. ,AUSFORMWG, which requires the plastic deformation of metastable austenite, is a process which can appreciably improve the properties of selected alloy stee1s.l,2 The Ausform process significantly increases the strength of these steels without decreasing their ductility. The properties at high temperatures are also improved through a change in the response of the steels to tempering. Although the mechanism by which ausforming alters the properties of these steels is not fully understood, it appears that the dislocation arrays produced by deformation of the metastable austenite influence the structure of the martensite on subsequent transformation. This, in turn, affects the strength, ductility, and tempering response of the martensite. This research used chemical explosives to deform steels at various stages in their heat treatment in order to improve the properties of these steels. The explosive energy is used in two ways; 1) high-pressure shock waves are propagated through the steel to produce extensive microscopic shear strain without causing a large irreversible change in shape, and 2) explosive energy is used to cause extensive macroscopic plastic strain in the metastable austenitic state (explosive forming). I) AUSFORMING WITH INTENSE SHOCK WAVES The steel used in this phase of the research was an alloy having a nominal composition 0.43 pct C, 3.0 pct Cr, 1.5 pct Ni, and 1.5 pct Si. The steel was subjected to intense shock waves in three conditions: 1) in the metastable austenitic state, 2) in the tempered mar tens itic state, and 3) in the tempered martensitic state after ausforming by conventional techniques. The specimens were in the form of disks 2.75 in. in diam and 5/16 in. thick. These were incorporated into a specimen assembly consisting of two disks pressed into a 5 by 5 by 1 in. block of stainless steel, Fig. 1. Spalling (or scabbing) is confined to the front disk. The specimen is protected from oxidation and decarburization by the surrounding metal. The temperature of the assembly is monitored by a thermocouple inserted into one side of the stainless steel block. The assembly is positioned over an oil reservoir which serves both as a means of catching the disks and as quenching medium for the disks shocked under ausforming conditions. Plane shock waves are introduced into the assembly by a metal driver plate impacting the top surface of the block. The driver plate is accelerated by a chemical explosive sheet supplied by E. I. du Pont de Nemours & Co. All the specimens were subjected to plane shock waves having a peak pressure of approximately 430 kbar. The pressure is that quoted by G. E. Dieter for the plane wave generator used in this work.' The driver plate used was 1/4 in. thick, so that the initial pulse was essentially a l/2-in.-wide square wave. The attenuation of the peak pressure during the subsequent 1/4 in. is estimated to be less than 5 pct. The shock front induces a temperature rise, a portion of which is irreversible. Rough estimates (+25 pct) of this temperature rise have been made for iron shocked at room temperature.4 For a 500-kbar shock wave, the temperature rise in the shock front is about 700°F, and is held for a time of the order of microseconds. The irreversible temperature rise, which remains after the shock wave passes, is about 450°F.4 The disks are quenched to room temperature within a few seconds of the shock treatment. It should be emphasized that the temperature rises given above are estimates for pure iron at room temperature, and are not necessarily true for the tests made in this work. The disks shocked at temperatures in the metastable austenitic range were austenitized in the stainless steel assembly in a furnace protected from the firing area. The assembly was removed from the furnace and placed over the recovery reservoir. The plane wave generator was then positioned and

Jan 1, 1963

By R. G. McQueen, E. G. Zukas

THE production of isotropic fine-grained ingot iron would be most useful since physical measurements associated with the elastic properties of iron are influenced by the size and orientation of the individual grains. This can be accomplished at present for small samples by established metallurgical procedures, but for large samples (in excess of 2 in. diam by 1 in. thick) it is virtually impossible to produce reasonably small uniform grains with random orientation. Such pieces can, however, be produced by impulsive loading followed by a suitable recrystallization treatment. The shock loading system employed is diagrammed in Fig. l. Here the 3/8-in. iron plate is accelerated by the plane-wave initiated high explosive charge through a 1 5/8-in. air space. Collision of this plate and the specimen of interest generates a shock wave in excess of 300 kbars which passes through the specimen. For this type of work it is not necessary to use machined parts: for example, the ingot iron pieces are saw cut from the billet so that they can be inserted in short sections of iron pipe. The recovered specimens are less distorted, however, if the air gap between the iron sample and pipe is filled with Woods metal. The dimensional changes resulting from this type of loading technique are minor, usually less than a 10 pct reduction in thickness. Compressive yield

Jan 1, 1962

By M. C. Smith, W. V. Green, D. M. Olsen

The creep-rupture behavior of commercial powder-metallurgy molybdenum rod is reported in the temperature range 1600" to 250O°C, at stresses up to 9000 psi and times up to 1 month. The effects of temperature, stress, and grain growth are discussed. Rupture time is fitted to the Larson-Miller parameter and compared to lower-temperature and higher-stress results reported by pugh.1 BECAUSE of its high melting point, molybdenum should retain useful strength to relatively high temperatures. Combined with its ready availability in the United States, this makes it attractive for many applications in missiles, rockets, and so forth—wherever its susceptibility to oxidation can be tolerated or overcome. The mechanical properties of molybdenum rod in the temperature range —200" to 1540°C have been reported by pugh,' Bechtold,' Parke,3 and Carriker and Guard.4 Madden and chen5 have measured the tensile properties of molybdenum single crystals in vacuum up to about 2500°C. As one further step in evaluating its mechanical usefulness, the constant-load creep-rupture properties of commercial powder-metallurgy molybdenum rod have been investigated in the range 1600" to 2500°C. MATERIAL TESTED Creep specimens were machined from 1/2-in. round commercial molybdenum rod, manufactured from powder by pressing, sintering, and swaging. Spectrochemical analysis of the rod showed "traces" (less than 0.01 pct) of silicon, aluminum, chromium, iron, and zirconium, and "faint traces" (less than 0.001 pct) of manganese, magnesium, cobalt, and nickel. Carbon content was 130 to 200 ppm, nitrogen was 110 to 180 ppm, and oxygen 30 to 35 ppm. A typical microstructure of the as-received rod is shown in Fig. 1. Room temperature tensile properties for five specimens strained at about 0.015 in. per in. per min are shown in Table I. CREEP SPECIMENS USED The specimens used for creep-rupture testing are illustrated in Fig. 2. The 1/4-in.-diam gage section was 3/4 in. long, and terminated at shoulders 5 mils high. These shoulders served as fiducial marks for optical strain measurements. Surface finish on the gage section was 16pin. r.m.s. One specimen, for a "long-time" test described below, was modified by dividing the 3/4-in. gage length into three 1/4-in. long sections with individual diameters of 0.250, 0.230, and 0.210 in., each terminating in a pair of fiducial shoulders. TESTING PROCEDURE The constant-load creep-testing machine used has been described by Smith, Olson, and Brown.6 In it the specimen is held vertically on the axis of a cylindrical tantalum or tungsten heater tube by threaded molybdenum or tungsten grips. Both specimen and grips are heated by radiation from the heater-tube, which is heated by its own electrical resistance. The bottom specimen grip is held at its lower end by a clevis pin. The testing load is applied to the specimen through the upper grip by means of hanging weights, a constant force-multiplication lever system, and a pull rod sealed to the chamber lid by a bellows. The incandescent specimen is viewed by an external optical system through slots in the heater-tube and radiation shielding, and an enlarged image of it is projected on a ground-glass screen. Gage-length measurements are made on this image with a pair of cathetometers. Thorium oxide coatings were applied to the threaded ends of most specimens, to prevent diffusion-welding of specimens to grips during testing. Without such a coating welding usually occurred, and grips were often broken by subsequent efforts to remove the tested specimens.

Jan 1, 1960

By W. V. Green

The creep-rupture behavior of commercial powder-metallurgy tungsten rod is reported for temperatures of 2250°, 2500°, 2700°, and 2800°C, stresses up to 7000 psi, and times up to 4 hr. The temperature dependence and the stress dependence of creep rates are evaluated. Rupture time is fitted to the Larson-Miller parameter and compared to lower-temperature and higher stress results reported by pugh.4 THE tensile strength of single-crystal wire1 and of polycrystalline wire2 have been measured by Goucher. More recently Bechtold3 and pugh4 have studied the mechanical properties of tungsten rod between room temperature and 1200°C. Since tungsten has the highest melting point of all metals, it should retain useful strength to very high temperatures, and should find many applications in missiles, rockets, and so forth. Therefore, the mechanical usefulness of polycrystalline tungsten rod was investigated in the 2250" to 2800°C temperature range by short-time creep-rupture tests. MATERIALS TESTED Creep specimens were machined from 1/2-in. round commercial tungsten rod which was manufactured from powder by cold pressing, sintering, and hot swaging. Purity reported by the vendor was 99.95 pct W. Spectrochemical analyses showed "traces" (less than 0.01 pct) of silicon, iron, and titanium, and "faint traces" (less than 0.001 pct) of calcium and manganese. Carbon content was 30 ppm and nitrogen content was 70 to 110 ppm. No oxygen analysis was obtained. Room-temperature stress-strain tests on the as-received tungsten gave badly scattered results. Threaded end specimens broke at the threads. When these specimens were retested using shoulder grips, the specimens broke at the shoulders. No fractures occurred in the gage lengths. The fracture stresses were: 127,000; 137,000; and 154,000 psi for three specimens which fractured at the shoulders. The microstructure of the as-received tungsten rod is shown in Fig. 1. SPECIMENS USED Fig. 2 shows the two types of creep specimens tested. The threaded-end type specimen, which was used in most tests, had a 3/4-in. gage length and 1/4-in. gage diam. The cone-end specimen, which was used primarily to investigate the effects of a smaller gage diameter and the practicability of the modified grips and specimen, had a 3/4-in. gage length and a 1/8-in. gage diam. In both cases, the gage length terminated at 0.005-in. high shoulders which served as fiducial marks for optical strain measurements. Surface finish on the gage length was 16 µ-in. rms. Creep rates and rupture times were not significantly different for the two types of specimens and were not affected by electropolishing the specimens before testing. TESTING PROCEDURE The constant-load creep-testing machine used has been described by Smith, Olson, and Brown.5 In it the specimen is held vertically by grips of similar material and on the axis of a cylindrical tungsten or tantalum heater-tube. The specimen is loaded by means of the specimen grips, a pull rod (which is sealed to the chamber lid by a vacuum-tight bellows), a mechanical lever system, and hanging dead weights. Both specimen and grips are heated by radiation from the heater-tube, which is heated by its own electrical resistance. An optical system views the incandescent specimen through slits in the radiation shielding and heater-tube. The optical system projects an enlarged image of the specimen gage length on a ground-glass screen. Periodic gage-length measurements are made on this image with two cathetometers. Thorium oxide coatings on the specimen threads or conical end surfaces completely prevented diffusion-welding of specimens to grips, and were used

Jan 1, 1960