Search Documents

By Harry W. Antes

The density changes that occurred on annealing cold-worked poly crystalline molybdenum, over the temperature range of 870" to 1630 SC, were determined. Increases in density were observed for recovery and the beginning of recrystallization. An initial decrease in density was observed during re-crystallization. A second decrease in density was observed after recrystallization was completed, as the microstructure changed from columnar grains to equiaxed gvains Both decreases in density were associated with an increase in gain boundary area to volume ratio. The second decrease in density was observed in the annealing range that immediately precedes secondary recrystallization as reported in the literature VARIOUS techniques have been used to identify the recovery, recrystallization, and grain growth processes that occur when cold-worked metals are annealed. As early as 1928 work was conducted that indicated measurable density changes occur when cold-worked single crystals of brass are annealed.' More recently, work by Murphy exhibited a corre- lation of density with microstructural changes observed on annealing cold-worked polycrystalline a brass.2 Other investigators have performed similar work on a brass and copper.324 In reviewing the literature, it was apparent that density work had been limited to fcc materials. Therefore, it was the purpose of this investigation to determine the density changes that accompany annealing the cold-worked bcc material, molybdenum. Two degrees of cold work, 30 and 90 pct reduction of cross-sectional area by rolling, were selected for this study. EXPERIMENTAL PROCEDURE High-purity vacuum arc-cast molybdenum was used in this study, the principal impurity being carbon in the amount of 80 ppm. The final rolling reductions were made at 1200°C in grooved rolls to provide 5/8-in.-diam rod. Density specimens 0.500 in. diam by 1.5 in. long were machined from the bar stock. The specimens were ground to the final dimensions to provide a smooth surface. Density measurements were made using a hydrostatic technique similar to that used by ~urphy.' This type of equipment permitted weighing in liquid immediately after the air weighing. During each weighing the temperature of the air and liquid was controlled to within 0.0l°C. This was accomplished by sealing the analytical balance in an air-tight brass chamber and surrounding it by an insulated wooden case. Preheated air was circulated in the air space between the brass chamber and wooden case by means of a blower. The temperature of the

Jan 1, 1964

By R. A. Vandermeer

It is usually assumed that the rate-determining step in the migration of a grain boundary involves the thermally activated transfer of single atoms across the interface. Chemical reaction rate theory then gives a migration rate which is proportional to the driving force when this is small compared to kT.1 In their recrystallization studies on aluminum, Gordon and vandermeer2 obtained data which was capable of providing the first experimental test of this proportionality. They correlated stored energy (driving force) release measurements determined calorimetrically with fraction recrystal-lized kinetic (growth rate) data acquired metallo-graphically at a temperature where a significant amount of recovery takes place concurrently with recrystallization. Within experimental error, the results of Gordon and Vandermeer confirmed experimentally, at least over a limited range, the linear dependence of boundary migration (growth) rate on driving force in accordance with theory. In obtaining these results, however, an incorrect, implicit assumption was made in relating the average instantaneous growth rate of the recrystallized grains to the measured fraction recrystallized kinetic data. The purpose of this present note is to point out and correct this assumption. An alternate approach, whereby a more proper average growth rate can be calculated from the recrystallization kinetic data, is presented. The earlier data, reevaluated in terms of this new approach, show the same general trend as before so that the original conclusion of Gordon and vandermeer2 is still valid. As was shown in a detailed study3 of the geometrical features of recrystallization in aluminum, the colonies of recrystallized grains can be regarded as uniform cylinders embedded in a three-dimensional matrix, the number of such colonies being constant. Thus during the early stages of recrystallization the volume fraction recrystallized, Xv, can be written as Xv=ynvlr2 [l] where y is a shape factor and i and r are defined as the average length and radius of a recrystallized colony and are spatial averages over the specimen. -nv, is the number of such colonies in a unit of volume. The erroneous assumption made in the earlier paper2 was that r in Eq. [I] could be replaced by

Jan 1, 1965

By H. P. Stuwe

It is investigated whether a model of sphere packing permits the computation of the lattice parameters and their variation with concentration in various a phases; it does, except in phases containing silicon. Several observations indicate that a particular role is played by the "E-atoms" in the lattice. THE phase is formed by many alloys of the transition elements.'-' Its structure has been described by Bergman and Shoemaker,5,8 Dickins, Douglas, and Taylor,7 and Kasper, Decker, and elanger.' There are five kinds of crystallographically equivalent positions for the 30 atoms in the unit cell which have been designated by these authors I, 11, 111, IV, and V or, in the same sequence, A, B, C,D, and E, as shown in Fig, 1. For the purposes of the present paper two elements of the lattice will be discussed separately: The lattice planes perpendicular to the c-axis which are made up by the atoms A, B, C, and D and which determine the a-parameter; and the close-packed "vertical rows" of E-atoms which determine the c-parameter. asper,9 and Frank and kasper10 described the a phase and other complex structures as sphere packings. In these papers particular attention is paid to the coordination polyhedra. Lattice positions with an equal number of nearest neighbors are considered equivalent regardless of their crystallo-graphic description. This seems to work very well for the explanation of ordering phenomena in the a phase as far as information on this is available." If the description of the phase as a sphere packing is valid it should be possible to draw two further conclusions: 1) It should be possible to calculate the lattice parameters from the atomic radii of the components, and 2) It should be possible to predict the variation of the lattice parameters with concentration within one phase field. Both points are discussed in this paper. PROCEDURE Measurements of lattice constants were done with a symmetrical back-reflection X-ray camera. With Cr-radiation, about a dozen a1 lines could be observed with most samples. From the (550/710)- and 720-lines the a-value was computed. With this value the c-parameter was calculated from the (333)- and (413)-lines. Finally, the position of all the other lines was computed from the lattice parameters thus obtained. In this way the validity of the indexing could be checked and, at the same time, this proce- dure gave an estimate of the accuracy of the lattice parameters. A correction was made for film shrinkage. The atomic radii used in the computations are the Goldschmidt radii for coordination number 12. Actually, some of the atoms have a coordination number of 14 or 15, but the error thereby introduced is small. * For the computation of lattice constants from the atomic radii an "average atomic radius" of all components was used, i.e., complete disorder was assumed. Although this seems to be true for some systems like OS-Cr,4 it is not true in others.11,13,14 The ordering model, however, which has been suggested by Kasper on the basis of extensive research lets both kinds of atoms contribute to both the ''vertical rows" and the lattice planes perpendicular to them, so that even with ordering of this kind the assumption of complete disorder cannot introduce a very serious error in calculating lattice parameters. RESULTS Bergman and shoemaker6 gave a table of the interatomic distances in the Fe-Cr phase. If we disre-

Jan 1, 1960

By T. P. Papazoglou, N. A. D. Parlee, W. C. Phelps

PRACTICAL designs for good "home made" molybdenum furnaces are hard to find in the literature. The one described briefly below left something to be desired but was good enough to operate as a rather long (30 in.) two-zone furnace for periods of over 2 months at temperature (1400° to 1600°C) without shutdown. The principal problem in our application was to establish a temperature profile with two distinct constant-temperature zones and no dip between the zones. This and other problems mentioned below would not arise, however, if both zones were operated at the same temperature and if a shorter furnace were acceptable. Since molybdenum windings oxidize very rapidly when heated in air, impervious refractory tubes were used for both the furnace core and the outer jacket tube shown in the accompanying figures. A protective atmosphere of forming gas (10 pct H2, 90 pct N2) was continuously passed through the gas-tight annular volume between the core and outer jacket. The water-cooled copper ends shown in Figs. 1 to 3 sealed the ends of the tubes. Annealed molybdenum wire (40 mil) was wound on the recrys-tallized alumina core (35.5 mm OD by 28.5 mm ID by 30 in.) at a spacing of 0.36 in. The spacing was reduced to 0.29 in. close to the ends to partially compensate for end heat losses. Fig. 2 shows two molybdenum-ground lead taps off the center of the winding to produce the two independect temperature zones. The ground lead was insulated with 1/4-in. alumina tubing and connected to the grounded copper end by passing the wires through the gas port tube and crimping each wire into notches cut at the mouth. To prevent sagging of the core at high temperatures, refractory "troughs" were cut from alumina and mullite tubing to cradle the core. The support "troughs" which were 6 in. long and located about 5 in. from each end of the annular volume also served as radiation shields. In view of the different expansion coefficients and operating temperatures of the core and outer jacket (3.5 in. OD by 3 in. ID by 30 in.), the ends of the tubes were smoothed and squared to produce good sealing surfaces, and the core was ground 1/32 in. shorter than the outer tube. The power terminals were passed through their respective conductor ports which were internally lined with alumina tubing and sealed with Armstrong adhesive A-6 leaving about 1 in. of protruding lead wire for external connections. (Adhesive A-6 is a two-component system consisting of an epoxy-type resin with a mineral fibrous filler and an amine catalyst.) Figs. 1 and 3 show the entire assembly of concentric refractory tubes, copper ends, and sealing o rings, held together with two brass flanges and 3/8-in. bolts with heavy springs for dimensional flexibility. The furnace shell (19 by 19 by 30 in.) consisted of a steel frame with sheets of transite forming a box. The copper ends protruded through two 3.75-in. circular holes cut at the center of each transite square end. Thermal insulation next to the transite exterior was effected by K-23 B&W bricks alld in a central volume of approximately 9 by 9 by 30 in. a row of K-30 bricks was lined up to support the hot assembly. The rest of the volume around the outer

Jan 1, 1965

By M. E. Shank, J. Wulff

At the present time, the designer of dies for metal powder pressing is handicapped by relative ignorance of stress distribution and frictional effects at the interior surface of the die. Unckell was the first to develop a method for the study of wall friction. He used three Brinell balls on which the die rested during pressing. The total frictional wall force was determined by the size of impression these balls left on a soft metal plate. Since the method does not give radial pressures, or distribution of such pressures, coefficients of friction could not be determined. Although Unckel measured density distribution, he was not able to determine radial or shear stresses. Shaler2 has proposed theoretical expressions for the stress and density distribution within cylindrical compacts during pressing, in accordance with the experimental results of Kamm, Steinberg, and Wulff.3 By application of Siebel's method,4 Kamm et a13 plotted stress trajectories for two compacts. From the stress trajectories they calculated coefficients of friction from point to point along the die wall. As pointed out by Shaler in the discussion of Ref. 3, these values are based on progressive point-to-point calculations on finite size grid squares across the compact. In the region of the die wall such calculated values may therefore have considerable cumulative error. The purpose of the present paper is to develop an experimental method by which the nonhydrostatic pressures and shears acting on the interior wall of a cylindrical die can be measured. Such measurements can then he correlated with existing data to aid in the explanation of the pressing process. The method used is based on the elastic: properties of the thick-walled tube used as the die. The principle of super-position of force systems on an elastic body is assumed to hold. Electric strain gauges were mounted in adjacent positions on the exterior die wall in order to get an exact measurement of the variation of tangential strain over the length of the die during pressing. While in this paper, measurements in terms of only tangential strains are considered, it is well to note that similar calculations may be set up for axial strains. The latter are not preferred, since they tend to be smaller than the tangential strains and therefore permit less sensitive measurements. Discussion in this work is restricted to compacts pressed from both ends, since the elastic deformation of the die is then more amenable to analysis. Before choosing the electric strain gauge method, a more direct line of attack was considered and discarded. The discarded idea was the insertion of a pressure gauge through a hole in the die wall.* The gauge would have been in the form of a small piston. If pressure were exerted against such a gauge, it would move outward along a radius of the die. One disadvantage of the scheme is its inability to measure shears along the die wall. Another more serious disadvantage is the disturbance caused by the device itself. It would serve to change the forces it was designed to measure. No matter how small the movement of the gauge, when pressure is applied a discontinuity would exist in the wall surface at that point. Due to the stress concentration caused by the hole, abnormal deflections of the die wall would occur around the gauge. During pressing, powder would be forced into the resulting depression. The depression would then become larger with increasing compacting pressure. Powder, not being a fluid, is capable of supporting shear. The ease with which it would flow into the die wall depression to further move the piston is an indication, not of the radial pressure at that point, but of the state of shear retarding the movement. Thus the "pressure" gauge is really a criterion of flowability, and of the capability of the powder to support shear. For these reasons, it was decided that the electric strain method, herein employed, was more reliable, if more indirect. The gauges and lead wires, mounted on the external die wall do not in any way affect the behavior of the metal powder or the die during pressing. Theory of the Method THE EFFECT OF RADIAL PRESSURE ON THE DIE WALL Effect of a Single Small Band of Hydrostatic Pressure Consider a die which is a thick-walled cylinder of outer radius R. and inner radius Ri. If over a small finite length L there is a normal pressure P, a tangential strain distribution at the outer wall results. This is shown schematically in Fig 1. The exact shape of the curve may he predicted by an extension of the theory of a semi-infinite beam on an elastic foundation.6 This

Jan 1, 1950

By M. E. Shank, J. Wulff

In view of the current interest in magnetic materials having rectangular hysteresis loops, as for example those obtained with the grain oriented 50 nickel 50 iron alloys,t we wish to call attention again to the results obtainable with the perminvar (Co-Ni-Fe) alloys heat treated in a magnetic field. Data taken from direct current measurements made prior to and during World War II give the typical values shown below for two of the perrninvar alloys. Fig 1 and 2 show- the hysteresis loops for these samples. The first sample above consisted of small rings punched from 0.014 in. sheet stock. These rings were heat treated at 1000°C for one hour in a hydrogen atmosphere and then cooled with the furnace to 750°C at which point they were subjected to a magnetic field of 15 oersteds maintained during cooling to room telmperature. The molybdenum perminvar sample consisted of a spirally wound core of 0.001 in. tape. The heat treatment was the same except that box annealing methods were used and no hydrogen atmosphere was employed. Even better properties might be expected using hydrogen. The heat treating temperatures and cooling rates are not critical. Rectangular hysteresis loops produced in other perminvar alloys by heat treatment in a magnetic field were described earlier.',? Properties similar to those described above are realized in perminvars manufactured by conventional methods. Drastic cold working which in practice limits the final thickness and is gen- erally expensive may thus be avoided. This information may be of interest to those concerned with magnetic alloys and the development of contact rectifiers, magnetic amplifiers and so on.

Jan 1, 1950

By R. Steinitz, L. Seigle, R. Resnick

THE rates of growth of the carbide phases MC and M2C in the Ta-C and Cb-C systems have been measured at various temperatures and the results used to estimate the rate of carbon diffusion within the inter metallic phases. Sheets of high-purity tantalum (50 ppm Cb, <25 ppm Ti, 10 ppm Fe, 5 ppm Cr, <50 ppm Mo, W, and all other metals, 15-75 ppm O2, 10-30 ppm N2, and 10-30 ppm C) approximately 1/4 by 1/2 by 0.020 in. were heated to temperatures between 1800" and 2700°C in a carbon resistor furnace under an atmosphere of argon plus sufficient methane to maintain an excess of carbon at the sample surface. The thicknesses of the carbide layers, illustrated in Fig. 1, were measured with a filar micrometer and plotted logarithmically as a function of time. Fig. 2 is a typical plot for the TaC phase. The points may be represented within experimental error by lines with slope equal to 1/2; therefore the growth of the layers may be described by the usual expression X = kt1/2, where X is the layer thickness, t is the time, and k is a temperature-dependent constant. From these data and compositions at the phase boundaries, it is possible to estimate values for the diffusion coefficients of carbon in each phase, assuming that layer growth occurs by carbon diffusion alone, and that the dif-fusivity is not a function of composition within each

Jan 1, 1965

By Dale A. Vaughan, Oliver M. Stewart, Charles M. Schwartz

A. U. Seybolt (General Electric Research Laboratory)—The authors should be commended for adding some important information to our knowledge of the solubility of interstitial elements in metals. It is becoming increasingly evident that the effect of even traces of such elements have very far-reaching effects upon the mechanical properties of the body centered cubic metals. Those who have worked in this area know that the accurate determination of the small solid solubility limits in systems of the type reported by the authors is a quite difficult task, and it is therefore not surprising that frequently the results of different workers are not in agreement. It is instructive, and usually helpful, to plot the solubility results on log weight or atomic percent -1/T coordinates to find out if a straight line is obtained. A straight line is expected because in systems displaying solubilities of the order of 1 to 3 at. pet or less, Henry&apos;s law is usually obeyed—or at least well enough obeyed so that the deviation from linearity is not very appreciable. If Henry&apos;s law is obeyed, one canthen use the Van&apos;t Hoff Equation in the form In N = ?H/RT + C, where N is mole fraction, at. pet, or wt pet for small values, and AH is the partial molal heat of solution of the solute. R and T have the usual significance, and C is an integration constant. If one plots the reported nitrogen solubility values as indicated above, the three points fall reasonably well on a straight line. The oxygen values for the two upper temperatures fall very closely to the nitrogen values as shown in the authors&apos; Fig. 15. However, the value at 500°C departs widely from the straight line established by the data at 1500" and 1000°C. It is, of course, true that one cannot place too much emphasis on the significance of a line established by only three points, but in the absence of reasons for anticipating deviations, data exhibiting wide departures from linearity should at least be examined closely. Fig. 16 shows the log at. pct -1/T plots for the authors Ta-O and Ta-Ndata including a solid circle point at 500°C and 1.8 at. pet for Ta-O, which is simply extrapolated from the two higher temperature points. In addition, the data of R. P. Elliott9 for Nb-O are shown. These points were picked off his curve and are not very exact, but as can be seen they line up well on a straight line. It is interesting, and probably significant, that the slope of Elliott&apos;s results is not far from those of Vaughn, et al. This is probably to be expected because one would anticipate that the partial molal heats of solution of oxyten in these two very similar metals should be not too far apart. AH for Ta-O is about -1900 cal per mol, while for Nb-O it is near -2300 cal per mol. Hence, this lends some support to the thesis that the point at 500°C for Ta-O is much too high. The data of Gebhardt and Preisedanz10 are also plotted, and it is seen that their data while lying on a linear plot, have an appreciably steeper slope. The possible reasons for this will not be discussed here except to point out that their pressure-composition data show anomalies which suggest that they may have been dealing with a different equilibrium from that being discussed. There is another consideration which would also suggest that the solubility at 500°C is lower than shown. The solubility values were obtained by the classic method of first establishing a lattice parameter-composition curve. This the authors did, and there is probably little doubt that it is quite accurate. Such a plot is generally almost error-free because it has a self-correcting feature in that any deviation from linearity makes a data point immediately suspect, and subject to confirmation. Unfortunately, this is not true with respect to the actual solubility values. These are obtained ordinarily by taking an alloy containing more solute than is soluble at some temperature and then thermally

Jan 1, 1962

By A. S. Yue

It was deemed desirable to obtain an understanding of the vacuum desulfurization process. McKechnie1 has reported that the sulfur content of nickel- and cobalt-base alloys is reduced in vacuo. Keverian and Taylor2 have observed that vacuum melting causes desulfurization of iron-carbon-silicon alloys. Garnyk and samarin3 have desulfurized transformer steel by vacuum treatment. Experiments were conducted in order to investigate the desulfurization of liquid iron under reduced pressures, and to establish the effect of some alloying elements, and various crucible materials. A vacuum-induction furnace of 50-lb capacity was used. The charge was Armco iron. Silicon was added as 90 pct ferrosilicon, carbon as electrode graphite, and aluminum as high-purity aluminum metal. Magnesia and silica crucibles were used, their inside diameters were 5 1/2 and 5 3/8 in., respectively. The temperature was measured with an optical pyrometer and it was held at 1600 1 15°C. Samples were withdrawn with quartz tubes of 6 mm ID, without disturbing the furnace atmosphere. Pressures were measured with an alphatron gage. The experimental results are shown in Fig. 1. They indicate that: 1) Sulfur can be removed from liquid iron alloys by vacuum treatment; 2) The desulfurization is enhanced by the presence of silicon, carbon, and aluminum, all these elements increase the activity of sulfur dissolved in liquid iron;4 3) The pronounced effect of silicon indicates that probably a volatile silicon sulfide is formed, Alcock and Richardson5 have observed a similar phenomenon; 4) The same rate of desulfurization was obtained when the metal was contained in either magnesia or silica crucibles. Dr. J. Keverian has contributed many discussions and recommendations. M. S. Sutliff has helped in conducting the heats. The permission of General Electric Co. for this publication is gratefully acknowledged.

Jan 1, 1960

By H. C. Gatos, A. D. Kurtz

WITH the growing interest in the mechanism of self-diffusion of metals, the study of accurate and convenient methods for determining self-diffu-sion coefficients appears highly desirable. It was with this objective in mind that the present investigation was undertaken. Gatos and Azzam1 employed an autoradiographic technique for measuring self-diffusion coefficients of gold. This method involved sectioning of the specimen through the diffusion zone and recording the radioactivity directly on a photographic film. Because of the very short range of the emitted ß rays in gold, the activity recorded on the film was essentially the true surface activity. With proper choice of the sectioning angle, sufficient resolution could be obtained and the entire concentration-distance curve recorded in one measurement. For the boundary conditions of the experiment, where an infinitesimally thin layer of radioactive material diffuses in positive and negative directions into the end faces of a rod of infinite length, the solution of the diffusion equation is C/Cn = 1/v4pDt exp (-x2/4Dt) where C is the concentration of diffusing element (photographic density in this case), C,, is the constant (depending upon amount of radioactive material), x is the diffusion distance, D is the diffusion coefficient, and t is the time. Thus, by plotting the logarithm of the concentration vs the square of the diffusion distance, a straight line results and the slope contains the diffusion coefficient. In this manner, the self-diffusion coefficient of gold can be obtained as a function of temperature. In the present investigation the results reported by Gatos and Azzam1 have been verified, and the autoradiographic technique has been further developed and applied for the determination of the self-diffusion coefficient of gold at a number of temperatures. Furthermore, the energy of activation for the self-diffusion of gold has been conveniently determined. . Experimental Techniques Preparation of Specimens: The inert gold of high purity was received in the form of a rod from which cylinders were cut and machined to a diameter of 0.500 in. The specimens were annealed to a suitably large grain size and the faces were surface ground prior to the deposition of the radioactive layer. The radioactive isotope Au198 was chosen. It was produced in the Brookhaven pile by means of the reaction Au197 + n ? Au108. It decays by ß emission (0.96 mev) to Hg108 with the subsequent emission of a y ray (0.41 mev). 70Au 108 ? 80Hg 108 + -1e°. The half life of the Au108 is 2.7 days so that a strict time schedule had to be maintained in order to secure sufficient activity until the end of the experiments. For this reason, initial activities as high as 10,000 millicuries per gram were used. The gold arrived in the form of foil and was evaporated onto one face of each gold specimen cylinder to a thickness of about 100A. A sandwich-type specimen was formed by welding two such cylinders together. Evaporation of Gold: The gold was evaporated under vacuum from heated tantalum strips which were bent in such a way as to limit the solid angle through which the gold was allowed to vaporize, thus insuring a more efficient utilization of the gold. The specimens rested on flat brass rings which had an inner diameter of 0.475 in. The entire specimen-holding assembly could be manipulated from outside the vacuum system by means of a magnet which attracted a slug of soft iron attached to the assembly. By evaporating inert gold on glass slides under conditions identical to those employed for the radioactive gold, it was found that the thickness of the films was about 100A. Welding: The welding was performed by hot pressing in a stainless steel cylinder. The inside of the cylinder was threaded and fitted for two plugs. The specimens to be welded were placed in the middle of the cylinder and two pressing disks, one at each end, were inserted to avoid shearing stresses as the plugs were tightened. Mica disks were placed between the pressing disks and the specimens to prevent them from welding. The plugs were then tightened with a hand wrench and the entire unit was placed in an argon stream for about an hour to remove the oxygen. The unit was then inserted in the center of an argon atmosphere furnace maintained at about 700°C and left there for about an hour. Because of the difference in the temperature coefficient of expansion of the two metals, as the temperature rose. the pressure on the specimen-rollple increased and a weld resulted Welding was generally satisfactory under the conditions described.

Jan 1, 1955

By H. F. Webster, C. G. Dunn

Rolling md annealing procedures are described for developing the (110) preferred orientation in tantalum for use as a thermionic-emission materinl where electrodes of a uniform high work function are needed. The development of a (110) [001] annealing texture is also reported. A preferential growth process due to low (110) gas-metal surface energy is considered in explanation of the observed growth of (110) grains. ThE growth of (110)-oriented grains in thin strips of rolled zone-refined tantalum, previously discussed briefly,&apos; is reported together with more recent information on the formation of a (110)[001.] annealing texture, i.e., one where the [001] direction of each grain lies close to the rolling direction. The development of tantalum sheet with a (110) preferred orientation (position of [001 ] directions unspecified) is of importance as a thermionic-emission material in thermionic-energy converters. Since therm ionic-emission properties of cesium-coated crystals vary over a wide range depending on (hkl) a2-7 a single (hkl) preferred orientation is more useful than either several preferred orientations or none. Furthermore, the (110) preferred orientation yields the highest thermionic-emission density for a cesium coverage of less than a monolayer.5-7 A consideration of the stability of the grain structure needed at high operating temperatures suggests that the preferred orientation itself should be produced by annealing processes. Information on annealing textures in tantalum, however, is rather limited. Pugh and Hibbard 8 obtained (111)[112] and (lll)[112] components in a 1400°C recrystallization texture in 95 pct cold-rolled foil; these components were enhanced on annealing at 2500°C. Muller9 rolled 99.97 Ta to 90 pct reduction in thickness in the final stage and noted only a slight sharpening of the rolling texture, with some intensification of the (111)[112] component upon annealing at 1200°C. The experimental procedure followed in the present work stemmed from the idea of using possible differences in (hkl) surface energies to provide a small driving force for growth of grains having the lowest (hkl) surface energy.l0* This would mean using high-purity tantalum processed into thin sheet form and annealed at high temperatures either in a noncontaminating atmosphere or in one producing additional sample purification. EXPERIMENTAL Zone-Refined Tantalum. National Research Corp. tantalum in the form of 1/8-in.-diam rod and of 99.98 purity (53 ppm 0, 15 ppm N, and 8 ppm C) was zone-melted four times. The traversing speed was 4 mm per min. Such treatment increased the resistance ratio, R293k/R20K , where R293K is the resistance of the specimen at 20°C and R20K the re-resistance at liquid-hydrogen temperature, from a value of 25 for the initial rod to 175 for the zone-refined rod (the increase in the resistance ratio provides a measure of purification11,12). Part of a zone-refined rod was rolled unidirec-tionally to a strip 0.003 in. thick and 0.28 in. wide. Samples were given anneals in the range 1300" to 2100°C using ac conduction heating in an oil-free vacuum system. Recrystallization to small grains appeared to be complete at 1300°C. Large grains were formed at higher temperatures, but these were not entirely strain-free, some grains showing asterism in Laue X-ray patterns and some displaying a range in orientation. Part of the difficulty was caused by thermal expansion of the tantalum strip as it was held between fixed supports. However, in a different arrangement with the tantalum freely suspended in a tantalum can, high-frequency induction heating in vacuo at about l0-6 Torr produced

Jan 1, 1964

By Matti J. Saarivirta

Two new precipitation hardening copper-base alloys, Cu-1.5pct Ti-2.5 pct Sn and Cu-1.5 pct Ti-2.5 pct Sn-0.4 pct Cr were developed. High strength and medium conductivity are obtained by solution annealing and subsequent heat treatment. Combination of solution annealing, cold working, and heat treatment increases the strength further. Good elevated temperature strength and ductility makes these alloys superior to copper-beryllium-cobalt alloys. A considerable amount of research work is being done throughout the world to develop new and improved copper-base alloys. In many cases, the object is to develop alloys having a combination of high electrical and thermal conductivities, and high strength. The problem is complicated by the fact that any alloying element added to increase strength, invariably decreases conductivity. Among the few commercial precipitation hardening type copper-base alloys, the Cu-Be-Co alloys are best known. These alloys are used in many applications that require good spring characteristics cornbined with high strength and moderately high electrical conductivity. They can be formed readily after solution annealing, then heat treated to obtain high strength and conductivity. Because of the relatively high cost of the Cu-Be-Co alloys, considerable research has been aimed at developing new lower cost alloys having similar properties. As far as is known today, the binary Cu-Ti alloy is the only one whose properties are

Jan 1, 1962

By R. W. Fountain, J. F. Libsch

ONSIDERABLE time and effort have been ex- pended recently in research designed to provide a better understanding of the solid state transformations leading to the permanent magnet qualities of many commercial alloys. The knowledge derived from these investigations has resulted in the development of new magnetic materials as well as improvements in some of the older materials. The permanent magnet qualities of the newer alloys having high residual inductions and high coercive force values, have been attributed to the precipitation of a second phase or an order-disorder transformation in a solid solution. The ternary Co-Fe-V alloys provide an interesting group of magnetic materials having a wide range of magnetic properties. The low vanadium alloys&apos; possess soft magnetic properties similar to the binary Co-Fe alloys, while at higher vanadium contents (about 10 pct) interesting permanent magnet properties are obtained.2,3 Previous work by Nesbitt&apos; on the ternary Co-Fe-V permanent magnet materials, resulted in the conclusion that the precipitation of a second phase, ?, was responsible for the permanent magnet qualities of these alloys. However, unlike the conventional precipitation hardening alloys, the ? phase, which is stable at high temperatures, is precipitated in the low temperature a phase upon aging. Recent work by Geisler and Martin"." has established that the order-disorder reaction inherent in the binary Co-Fe alloys is also present in the ternary Co-Fe-V alloys. On the basis of their investigation, it was proposed that ordering of the a phase is also a possible explanation of the mechanical and magnetic hardening in these alloys. Thus, it appears that the Co-Fe-V alloys are rather unique in that two solid state transformations are taking place which may account for the properties of these alloys. In view of these facts, the present investigation was undertaken to study the mechanism of mechanical and magnetic hardening in the 10 pct V-Co-Fe alloy with particular reference to the role of the ? phase; and to correlate the results of this study with other magnetic properties. In addition, the influence of increasing vanadium contents on the transformation of Co-Fe alloys was also undertaken to supplement the main objective of the investigation. Experimental Procedure The Co-Fe-V alloys used for study consisted of: 1—a commercial lot of Vicalloy I, a 10 pct V alloy, and 2—alloys prepared by powder metallurgy and containing 52 pct Co and 0 to 14 pct V, balance iron. The commercial alloy was received in the cast and forged condition and was used primarily for the detailed study of hardness, electrical resistivity, and magnetic properties of the 10 pct V alloy. The powder metallurgy alloys were prepared from electrolytic iron, commercial cobalt, and ferro-vanadium powders. The processing cycle was as follows: 1—Elemental powders were weighed and mechanically mixed for 24 hr. 2—Mixed powders were pressed at 60,000 psi into the form of bars 5/8 x 5/8 x 5 in. 3—Bars were sintered in an atmosphere of purified dry hydrogen for 24 hr at temperatures ranging from 1380" to 1340°C, depending upon the vanadium content. The as-sintered bars were cut in half; and one half was machined to 7/16 in. diam for thermal analysis. The remainder of the bar was hot forged to approximately 0.050 in. for X-ray diffraction analysis. Additional details of sample preparation are presented subsequently according to the type of test performed. Thermal Analysis Measurements One of the simplest and most widely used tools for determining phase relations as they change with temperature and composition is to study the rate of change of temperature of a material as heat is supplied or extracted at a constant rate. The thermal analysis method used in this investigation is the inverse-rate method described by Smith.&apos;

Jan 1, 1954

By Frances H. Clark

IN wartime, the fabrication and use of metals assumes increased importance, for a modern war of sizable proportions cannot be undertaken with- out a vast supply of this material. Light alloys of aluminum and magnesium, which were comparatively unknown in the last war, will play an important role in this one. Due to research on a vast scale in the interim of years, industry is today well equipped to fabricate metals on an enormous scale. Research for the past year has been most productive and a comprehensive survey in the space of this article would be impossible. It is hoped that the stressing of a few items here and there out of a great quantity of able work will indicate in a small way the advances made within recent times. Specific references to the literature will be omitted at the Editor&apos;s re- quest but some authors of papers that I have found of special interest are mentioned.

Jan 1, 1940

By W. C. Leslie, R. M. Fisher, K. G. Carroll

A nitride, believed to be Si3N, has been separated from three nitrided silicon steels. Germanium nitride, Ge3N4, has been prepared from pure germanium. Comparison of the diffraction patterns indicates that the two nitrides are isomorphous; on orthorhombic structure is suggested in place of the rhombohedral structure previously reported for Ge3N4. THE possibility that a nitride of silicon may, under appropriate conditions, precipitate in silicon steels or in steels killed with silicon makes it desirable to have some positive means of identifying such a compound. One such means is the X-ray or electron diffraction pattern of the nitride. A review of the meager data in the literature indicates that the nitride most likely to form is Si3N4, a conclusion supported by the results of a study of nitrided silicon steels to be published shortly by L. S. Darken and R. P. Smith, of this Laboratory. Unfortunately, there is available no diffraction pattern for this nitride. Data have been reported, however, for Ge3N4 which, judging from the similarity between germanium and silicon, might be expected to be isomorphous with Si3N4. An effort was made, therefore, to form such a silicon nitride, to determine its composition and diffraction pattern and, if possible, its structure. To this end a series of three silicon steels was nitrided under controlled conditions with the resultant formation of nitride particles which yielded an electron diffraction pattern in situ. The particles were then extracted from the steel and an attempt was made to determine their chemical composition. X-ray and electron diffraction patterns were also obtained from the extracted particles, which indicate that the nitride is isomorphous with Ge3N4, although a complete determination of the structure has not been possible. These results show that a silicon nitride with a well-defined diffraction pattern can form in silicon steels, and they suggest that this nitride is Si3N4. Materials and Procedures The sillicon steels investigated were In the form of thin sheet or strip and had the composition shown in Table I. The 0.58 and 1.21 pct Si steels were nitrided by holding them at 1110°F in an H2-NH3 atmosphere containing 3 pct ammonia for 48 hr. The nitride particle size was increased by subsequent heating at 1500°F for 13 1/2 hr in helium. The resulting microstructure is shown in Fig. 1. The steel containing 3.20 pct Si was nitrided at 1200°F for 16 1/2 hr after which it was held in helium at 1500°F for 4 hr. Its structure as seen under the electron microscope is illustrated by Fig. 2. As would be expected from the higher silicon content and the shorter holding time at 1500 °F, the nitride particles are smaller and more numerous than those in the 1.21 pct Si steel. The ammonia-hydrogen treatment reduced the carbon content of the steels to a very low level, so no interference was encountered from carbon or carbides. In the case of the 3.2 pct Si steel, the carbon was reduced to 0.003 pct before nitriding by heating in dry hydrogen. Attempts to obtain an X-ray diffraction pattern from polished and etched surfaces of the 1.21 and the 3.20 pct Si steels were unsuccessful. However, an electron diffraction pattern was obtained from the surface of the steels. The interplanar spacings obtained from these patterns arc shown in Table 11, col. 5. The nitride particles were then extracted from all three steels by dissolving the ferrite matrix in bromine-methyl acetate, the solution used in the Beeghly method for the extraction of aluminum nitride from steel. X-ray diffraction patterns of these residues, obtained by means of a spectrometer and by a 57 mm Debye-Scherrer powder camera using filtered cobalt or chromium radiation, are given in Table II along with the pattern obtained by

Jan 1, 1953

By Ulf S. Landergren

Diffusion coefficients and marker movements have been determined in brass using welded couples. Three different concentration ranges were employed at 750°C, while a fourth concentration range was measured at 500°, 600°, 700°, and 800°C. Marker displacements toward and porosity development in the high zinc side of the couple were observed in all cases. The results were interpreted as favoring a vacancy diffusion mechanism. IN the large amount of diffusion literature which has accumulated during the past half century, very few experimental data have been presented on body-centered-cubic metallic phases. The impressive combination of experimental and theoretical studies which has given the vacancy mechanism a fairly secure position as the preferred mechanism for most face-centered-cubic metals has no counterpart for body-centered-cubic phases, although the theoretical picture seems to be in a better state than the experimental work. The attempts to select diffusion mechanisms by the theoretical calculation of the activation energy for the various conceivable unit diffusion processes and the energy of formation of the type of lattice defect required have been based on models of two kinds. The first kind utilizes potential functions fitted for certain properties of pure crystalline copper; the second kind is fitted for sodium. The latter is an example of an open metal in which the metallic ion is small compared with interatomic distance,&apos; while the former is characteristic of the larger class of metals in which the ions have diameters about as large as the interatomic distance. brass should resemble copper in this fundamental property. It should be evident that results on the mechanism of diffusion obtained for one of these classes need not necessarily apply to the other. Huntington and Seitz, using a model of the copper type, showed that the activation energies to be expected for interstitial migration or a two-atom direct interchange were much higher than that for vacancy diffusion. Zener pointed out that a four-atom ring rotation would involve an activation energy considerably lower than the two unlikely mechanisms although still higher than the vacancy mechanism in the face-centered-cubic structure. Furthermore, he argued, the four-atom rotation would be relatively easier in a body-centered-cubic lattice and might be competitive with the vacancy mechanism. Paneth showed that a body-centered-cubic crystal-like sodium could form interstitial defects of special type, called a crowdion, by crowding an extra atom into < 111 > directions where the defects would affect a line of about eight atoms. The defect was constrained to move along the defining line. Unlike the face-centered-cubic case, therefore, the theoretical calculations for the body-centered-cubic mechanism do not provide a very clear-cut answer, and the absence of adequate experimental studies is the more serious. This investigation was undertaken for the purpose of obtaining useful information on diffusion in body-centered-cubic phases. brass was chosen for several reasons: 1—the phase field is sufficiently wide at high temperatures to permit the use of diffusion couples with adequate concentration ranges for satisfactory chemical analysis, 2-—thermodynamic activity data are available for the calculation of mobilities from diffusion coefficients, 3—the phase is as close to the theoretical model of the copper -type on which the calculations have been done as any body-centered-cubic metallic phase is likely to be. Measurements of the movements (if found) of inert markers during the diffusion process would indicate that a vacancy or Or mechanism played a major role in diffusion in brass. If no marker movement should be found, a ring mechanism would be indicated but not assured. Experimental Procedure The alloys used in these experiments, listed in Table I with analyses, were supplied by the Naval Research Laboratory. They were from ingots of 3x3 in. cross-section, heated to 760°C, reduced under a

Jan 1, 1957

By P. E. Busby, C. Wells, M. E. Warga

Fundamental data on the rate of diffusion of boron in austenite and solubility of boron in the a and y phases of iron and steel have been obtained from deboronizing experiments and provide partial explanations for some of the phenomena observed in boron steels. The rate of diffusion of boron is about the same as carbon in austenite. The solubility of boron in austenite at normal heat-treating temperatures is less than 0.001 pct. A partial tentative Fe-B phase diagram in the important low boron concentration ranges and an equation representing the diffusion of boron in austenite are presented. A LTHOUGH a search of the literature revealed ALTHOUGHthat boron diffusion had not been studied quantitatively and systematically prior to 1948, a few qualitative observations which were made by following the diffusion of boron into iron packed in ferro-boron1-3 suggest that boron obeys normal diffusion laws and that the rate of diffusion increases with increasing temperature. The claim of Cornelius and Bollenrath1 that boron does not appear to influence the rate of carbon diffusion has recently been substantiated by Wells, Batz, and Mehl.4 Calculations based on data from the paper by Campbell and Fayv indicated that the diffusion coefficient (D) for boron in iron at 900°C is approximately 3x10 sq cm per sec; a value of 2x10-7 sq cm per sec at 1038°C has been reported by Digges et al in connection with decarburizing experiments on a commercial boron steel containing 0.43 pct C. During the period 1948 to 1950 several diffusivity constant (D) values for the diffusion of boron in the y phase of iron and steel and a number of solubility values for boron in both a and y phases were reported. It was concluded tentatively as a result of Metals Research Laboratory studies that D values for boron in y and a phases are about the same as for carbon in the comparable phasesa and that carbon up to 0.4 pct did not affect the rate of diffusion of boron in y iron above 1000°C within the limits of experimental error. Whether saturation of the y or a phases with carbon would significantly affect rates of diffusion of boron through them was then and still remains in doubt. The best estimate of Q (activation energy) was reported to be about 25,000 cal, somewhat lower than that for carbon in y iron. The solubility of boron in y iron at 1000°C was thought to be higher than 0.004 pct B but not as high as a more recent analysis of available data shows it to be. The solubility of boron in a iron at 700°C was reported to be 0.0004 pct B, but it would not have surprised the authors if the true solubility value is actually lower than this. Breaks in diffusion curves which were not understood when first obtained prior to 1950 have now been recognized as indicating solubility limits, and these are included in the present paper. Experimental Procedure Two methods were employed in an effort to determine diffusion coefficients (D) for boron in austenite. Early experiments involved the use of welded couples prepared in accordance with the procedure of Wells and Mehl,&apos; but when the results of these experiments proved to be unsatisfactory for calculating D values, studies were continued by means of deboronizing experiments. In both cases, boron analyses following the diffusion anneal were carried out spectrographically and all D values were computed using the Grube solution of Fick&apos;s law. The precision of the spectrographic method used proved to be about equal to that reported by Corliss and Scribner" —average deviation from the mean about 5 pct of the amount present when the boron content is 0.003 pct. Concentration-penetration curves obtained from spectrographic analyses of welded couples generally indicated that practically no boron was transported across the weld interface during the diffusion anneal. Furthermore the concentration-penetration

Jan 1, 1954

By R. F. Mehl, W. Batz, C. Wells

Diffusion coefficient values for carbon in austenite covering a wide range of temperature and composition have been determined employing statistical methods. In addition, the relation between concentration and each of the following, D (diffusion coefficient), Q (activation heat of diffusion), and A (the constant in the diffusion equation), has been obtained. A study of the rates of diffusion of austenite was published in Metals Technology in 1940.&apos; The present investigation is an extension of the earlier work, undertaken (1) to obtain values of the coefficient of diffusion, D, over a much wider range of carbon concentration, and (2) to provide data in all ranges of concentration and temperature in such abundance that statistical methods could be employed to evaluate the accuracy of the data with unusual precision. Composition of Materials: Composition of materials used in this research program are listed in table I. These materials, all forged to about 1 1/4 in. rounds, consist of a high-purity iron, Armco iron, a large number of laboratory-made plain carbon steels containing amounts of impurities normally expected in high-quality commercial steels, and three silicon steels. Since it was known at the time these steels were being made that impurities in the amounts present were unlikely to affect carbon diffusion rates&apos; significantly, the effort made to obtain high-purity steels was not as persistent as it otherwise would have been. Procedure: In general, the procedure followed by Wells and Mehl and described&apos; in detail in an earlier publication&apos; is the one used by the present authors. However, certain modifications have been made which it is believed allow diffusion data to be interpreted more objectively and correctly. These are described completely under appropriate subheadings which follow. Experimental Procedure: Experimental procedure includes (1) the preparation of specimens by welding steels of different carbon contents, (2) the heating of these for certain times at selected temperatures in order to diffuse carbon along the specimens across the welded "interface," and (3) the determination of the carbon distribution across the diffusion zone. Preparation of Specimens: Prior to welding steel of one carbon content to iron or steel of another carbon content, surfaces to be welded are machined perpendicular to the longitudinal axis of cylinders which are about 3/4 in. in diam and 1 1/2 in. long. The prepared, flat, parallel surfaces are brought together and butt-welded electrically. Evidence of a good weld is given in fig. 1. Welding temperature

Jan 1, 1951

By D. Y. F. Lai, R. J. Borg

Tracer diffusion of Fe59 has been measured in the a-stabilized Fe-1.8 at. pet V alloy from 700° to 1500°C. The activation energies are obtained in both the presence and absence of magnetic order. Furthermore, it is established that diffusion in the alloy is identical to that in pure iron and consequently the values of Do and Q accurately represent the temperature dependence for self-diffusion. The purpose of this investigation is to obtain an accurate estimate of the temperature dependence for self-diffusion in bee iron in both the presence and absence of magnetic order, and, in so doing, to establish the temperature range of the magnetic effect.&apos;" As the temperature interval suitable for diffusion measurements is severely limited in both bee phases of pure iron because of the intervening fee ? phase, the experiments were performed on an a-stabilized alloy containing 1.8 at. pet V. This alloy is bee over the entire range from room temperature to the melting point. Although there have been several independent investigations of self-diffusion of iron in a, iron,1, 3-6 there still exists considerable disagreement regarding the values of Do and Q for the paramagnetic region. The two systematic studies of diffusion in 6 iron6, 7 previously reported are also only in fair agreement; but in view of the extremely small temperature range available for diffusion studies, i.e., 1390o to 1535oC, this is not surprising. It is comparatively easy to obtain accurate values of Do and Q for the a-stabilized alloy inasmuch as measurements can be made over the entire temperature range -700o to 1500°C. However, in order to assume that these same values apply to pure iron requires careful comparison of the data in the a, and 6 regions in both the alloy and pure iron. We have made several measurements in the appropriate temperature ranges and are unable to establish any systematic difference between the diffusion coefficients of iron in pure iron and in the alloy. We therefore conclude that the values obtained for the alloy are truly applicable to pure iron; the complete evidence favoring this conclusion will be discussed later in this paper. EXPERIMENTAL The experimental methods will be given here only in barest detail since they have been thoroughly de- scribed elsewhere.l, 7 The alloy was prepared by induction melting and chill casting under argon. Diffusion samples were machined from the ingot and annealed in hydrogen for several days at 900°C to give an average grain diameter of 1 to 2 mm. The penetration profiles of the tracer were established by a sectioning technique, the residual activity being counted after the removal of each section. The tracer used is Fe59 which emits two high-energy ? rays of 1.098 and 1.289 Mev, respectively; these were detected by a ? scintillation counter equipped with a pulse-height analyzer. For the measurements in the temperature range -700o to 1130°C the samples were vapor-plated with Fe59, encapsulated in quartz under vacuo, and annealed in resistance-heated furnaces which are controlled to ±1°C. The specimens diffused at higher temperatures are prepared as edge-welded couples, the two halves being separated by a thin washer of the alloy to prevent sintering. The diffusion anneal is then carried out by inductive heating under a dynamic vacuum. The temperature is monitored pyrometrically. RESULTS The diffusion coefficients are obtained from the penetration profiles in the usual way using the error-function complement relationship. The results over the entire temperature range are shown in Fig. 1. In the linear region, 900o < t > 1500°C the least mean squares (lms) values of the diffusion coefficients are given by D = 1.39 exp[-(56.5 ± 1) x 103/Rt] cm2/sec [l] The average departure of the measured diffusion coefficients from the values given by Eq. [1]In order to determine whether or not the slope is truly constant over the entire range from 900" to 1500°C, the data are arbitrarily divided into two groups, the first containing values between -900" and 1133°C and the second between -1133o and 1500°C. The lms values for the two groups are given by Eqs. [2] and [3]: D = 0.519 exp[-55.7 x 103 /RT](900° to 1133°C) cm2/sec [2] D = 1.45 exp[-56.7x103/RT] (1133° to 1500=C) cm2/sec [3] Thus, there is no significant difference between the high- and low-temperature segments of the linear region. This not only assures us of the consistency of the values obtained by induction heating as compared to those obtained from the resistance-heated

Jan 1, 1965

By Leonard R. Weisberg

The general properties of diffusion in GaAs are reviewed. A total of .fourteen atoms have been studied to date, and activation energies for eleven reported are (in ev): Ga (5.6), As (lo), Zn (2.49), Cd (2.43), Sn (2.5). Mn (2.75). S (4.0). Se (4.2). Ag (0.33), Cu (0.52). and Li (1.0). The dijfusion of the first eight atoms, as measured by Goldstein using radiotracer techniques, established the principle of sub lattice diffusion for both host and impurity atoms, since atoms substituting for gallium have lower activation energies than those substituting for arsenic. The diffusion constant of interstitial copper has been determined for the first time by Hall and Racette using heavily doped p-type samples in which interstitial copper predominates. The anomalous behavior of zinc, which has an abrupt diffusion front and a strong dependence on zinc concentration, has recently been quantitatively explained in terms of an interstitial-substi-tutional equilibrium-diffusion mechanism. Lithium and silver diffuse mainly interstitially, while the diffusion of phosphorus is complicated by the continual formation ofGap. Junction-migration measurements indicate diiferent results than radiotracer techniques, and this is one problem that still remains, together with discrepancies in cadmium-diffusion results, and an unexplained dependence of impurity diffusion on arsenic pressure. BESIDES the usual insights into the behavior of atoms in solids, studies of diffusion in semiconductors have additional importance for device applications. In fact, the amount of diffusion studies performed on a semiconductor might serve as a simple barometer of its technological importance. Thus, the information accumulated for GaAs is not yet quite comparable to that for germanium or silicon, but considerable knowledge is available. The diffusion of at least fourteen atoms has been investigated for GaAs, and the diffusion constants have been determined for eleven of these. Interesting results were found for GaAs that elucidated problems not previously solved for germanium or silicon. For example, the interstitial-diffusion constant for the very fast diffusant, copper, was first measured in GaAs. Also, solutions for interstitial-substitu-tional equilibrium diffusion in extrinsic material were provided first for GaAs, although they are ap- plicable to germanium, silicon, and other semiconductors. Studies in GaAs firmly established the concept of sublattice diffusion, which should have application in many different compound systems. The purpose of this paper is to review briefly the general state of knowledge concerning diffusion in GaAs. First some general aspects of diffusion will be covered, and next attention will be given to the results mentioned above. Diffusion in GaAs has been measured both by radiotracer and junction-penetration techniques, and some discussion will be given of differences in the two sets of results. The comprehensive work of oldsteinl-&apos; has served as the primary reference for the diffusion of well-behaved substitutional atoms in GaAs. Since a review has recently been presented of many of these reults, details of the diffusion data will not be repeated. Neither will any discussion be given of the experimental techniques of diffusion measurements, except to note here, in passing, the simplicity and effectiveness of the precision lapping device employed by Goldstein.&apos; I) EXPERIMENTAL RESULTS AND DISCUSSION A) Summary of Experimental Results. Diffusion constants D = Do exp(E/kT) have been determined for eleven atoms in GaAs: a,&apos; AS,&apos; n,&apos;" Cd,&apos;" n,&apos; n,8 s, e,&apos; Ag,O CU," and i." These results are summarized in Table I. In addition, diffusion was investigated for phosphorus,4&apos;12 germanium,I3 and ilicon,&apos; but Do and E were not determined. Radiotracer techniques were used for most of the studies except for lithium, where a combination of chemical and electrical techniques was employed, and germanium and silicon, where junction-migration techniques were applied. The diffusion of zinc, manganese, sulfur, and tin was also measured using junction migration.13&apos;14 Goldstein demon-

Jan 1, 1964