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By F. V. Lenel

Resistance sintering under pressure is a method of hot pressing in which a powder compact is subjected to pressure and simultaneously heated by passing a low voltage high amperage current through it. Equipment for this process is described. Its basic characteristics such as resistance requirements for powders and compacts, temperature distribution in compacts, and gas reactions during resistance sintering are discussed. Examples of the sintering process in compacts made of a single metal or an alloy powder and in compacts made of mixtures of powders are presented. Potential commercial applications of the process are evaluated. THE usual sequence of operations in commercial powder metallurgy is to compact metal powders in a die at room temperature and sinter the compact subsequently without applying pressure while the compact is in the sintering furnaces. In hot pressing, on the other hand, the compacting and the sintering are combined. The loose powder, or in many cases a cold formed compact, is inserted into the die which is held at the hot pressing temperature, the compact is left in the die until it attains its temperature, and then pressure is applied and maintained for a given length of time. The die may be heated by surrounding it with a suitable furnace, by high frequency induction heating, or by passing current through the die. In hot pressing, compacts of high density and good mechanical properties can be produced in a relatively short time. One of the principal difficulties in hot pressing is the lack of suitable die materials which will have adequate strength at the hot pressing temperature. This difficulty can be overcome at least partially by heating only the material to be hot pressed without heating the die directly. This can be done by passing a low voltage high amperage current through the material and simultaneously subjecting it to pressure. Either loose powders or compacts can be hot pressed by this method in which the desired temperature is produced by the power dissipated in the metal powder. This method of hot pressing has been termed "electrical resistance sintering under pressure." The most significant differences between this operation and conventional hot pressing are: 1—The sintering times are very short, usually a fraction of a second and at most a few seconds. 2—The powder and die are initially cold. 3—Heat is generated within the powder itself and not conducted in from the die. 4— The pressure used is high. 5—Cooling following sintering is rapid, amounting to a quench. Resistance sintering of metal powders under pressure has been suggested repeatedly. In 1933, G. F. Taylor' proposed an apparatus which consisted of an insulating tube made of glass, or a ceramic filled with the powder to be pressed, and plungers above and below the powder. The powder was to be heated by passing an electric current through it and pressure was then applied. The apparatus was intended principally for hot pressing cemented carbides. Although the principle of resistance sintering under pressure is clearly shown in this patent, few details are given. A sintering period of a second or a fraction of a second, which is terminated by the operation of an inertia switch, is mentioned but no values for current density are mentioned. Low pressures, such as atmospheric pressure or a somewhat higher pressure exerted through a lever, are suggested. W. D. Jones' discussed electrical resistance sintering under pressure and proposed using resistance welding apparatus for this purpose. In a patent issued in 1944, G. D. Cremera described a method of electrical resistance sintering under pressure using resistance welding apparatus which was to be applied mostly to nonferrous metals such as copper, brass, bronze, and aluminum. Current densities of 400,000 amp per sq in., sintering times of 1 and 2 cycles of 60 cycle current, and pressures of 5 to 10 tsi are proposed. Cremer suggested using an

Jan 1, 1956

By L. F. Mondolfo

An aluminum-copper 4 pct Cu alloy aged at room temperature for times increasing up to 78,000 hr was annealed at 170°C and the hardness and electrolytic potential determined during retrogression and subsequent aging. It was found that there is a change of behavior with increasing time of aging at room temperature which indicates that, given sufficient time, retrogression disappears and the room-temperature aging tends to progress directly into the high-temperature aging. WHEN an age-hardenable alloy is aged at low temperature after proper quench, changes of properties and structure take place. If this material is then heated to a temperature higher than the previous one, but still well below the solution-treatment temperature, the properties and structure changes produced by the low-temperature aging disappear and the material apparently reverts to the as-quenched condition, ready to undergo aging from the start. This phenomenon is termed reversion or retrogression. First discovered by Cayler3l it has been extensively investigated, as shown by the number of publications listed in the bibliography. From all the information available the following facts emerge: 1) All aeg hardenable alloys can be retrogressed.9 13, 19) 24, 33, 41, 42, 44, 47, 53, 54, 61, 63, 64, 66, 73, 78 2) All the properties changes that take place during aging at low temperature can be retrogressed to a smaller or larger extent.4,5,7,12,19,32,49,50,57,58,60,67,75,76 67, 75, 76 3) Retrogression requires that the temperature be well above the preliminary aging temperature. If the difference between the two temperatures is small, Little or no retrogression takes place.7,20,32,33,41,49 57. 65 4) The larger the difference between the preliminary aging and the retrogression temperature, the faster and more complete is the retrogression.20, 33, 41, 48, 65, 67 5) Retrogression can be produced several times in the same alloy.23, 35,41,57,59 6) The amount of retrogression that can be obtained depends on the aging temperature. Alloys aged at the lower temperatures can be retrogressed the most. The higher the preliminary aging temperature the less retrogression can be produced.20,25,33,37,44,49,54,58 7) Appreciable retrogression after aging at elevated temperatures is possible only if the preliminary aging has lasted a short time. After a certain time of aging at high temerature retrogression does not take place any more,:5,6,9,10,11,21,40,58 8) During retrogression the Guinier-Preston zones redissolve and disappear. The other precipitate

Jan 1, 1960

By E. P. Abrahamson II

The effect of transition elements which form binary solid solution upon the recrystallization temperature of zirconium has been investigated. All additions raised the recrystallization temperature. A correlation is obtained between the logarithm of the rate of change of recrystallization temperature with atomic percent solute and the free atom ground state electron configuration of the solute element. ThE work of Abrahamson, et al., on dilute binary solid-solution alloys indicated a correlation between the free-atom ground state electron configuration of the solute and either the brittle-ductile transition or recrystallization temperature. These studies were carried out on bcc base materials. The implication is that the outer s and d electrons of the solute are the prime determinant of the absolute rate of change of recrystallization or transition temperature. Furthermore, the limit of linearity has been shown to be a function of solute electron configuration for recrystallization in iron and vanadium. To date no Complete systematic recrystallization study of dilute binary zirconium base alloys has been made. It is the purpose of this study to note whether the change in solvent structure from bcc to hcp will influence the correlation. It was also desired to learn more of the role of the electron configuration of the solvent on recrystallization temperature. PROCEDURE All alloys were made using 99.87 pct Zr with 0.01 Cr, 0.04 Fe, 0.006 Hf, 0.003 Mg, 0.003 Mn, 0.003 N, and 0.080 0 (132 BHN). The solute elements were 99.9 pct pure. According to the published binary phase diagrams6 and metallographic examinations at X750, all alloys used were solid solutions. The alloys were arc melted and remelted six times in the form of cubic 200-g buttons under an argon atmosphere. They were then hot pressed at 950°C to 0.450 in., upset pressed to 0.350 in., and annealed at 800°C for 1 hr. The specimens were then Blanchard ground to 0.250 in., removing 0.050 in. from each side. The grain size of the material at this stage was found to be 8000 100 grains per sq mm. The specimens were then cold rolled to 0.130 in. and cold pressed to 0.125 in., yielding 50 1 pct cold work. All alloys were then chemically analyzed for the principal addition. The interstitial contents remained at the values of the starting material when checked on random alloy specimens. The rolled sheet was cut into 6.75 by 0.25-in. lengths and heat treated in a gradient furnace for 1 hr. The gradient was 250o to 900°C over the 6-in. length, recorded continuously by six thermocouples resting on each specimen. Control was 3oC, accomplished at the hot end. The recrystallization temperature was determined metallographically using polarized light. The criterion chosen was the point on the specimen showing the first recrystallized grain at a constant magnification, X200. Specimens were repeated, and the agreement was found to be 3°C. RESULTS Three different pure zirconium specimens were tested, and the recrystallization temperature was

Jan 1, 1962

By Donald Warren, J. F. Libsch

HIS investigation originated as a result of a pre-vious experimental study' of the magnetic properties of Fe-Co alloys fabricated by the powder metallurgy technique. Densities of powder compacts prepared for the magnetics investigation varied from 7.45 to 7.70 g per cu cm or from 93 to 95 pct of the experimental value of 8.08 g per cu cm for a fused alloy of the same composition.' While this range of density is considered sufficiently high for most applications, the highest possible density is to be desired for maximum magnetic properties. By applying a technique similar to the one described above to a pure electrolytic iron powder, Rostoker³ was able to achieve a density of 7.895 g per cu cm, which is the highest density ever reported for sintered iron. While Rostoker's work involved the sintering of an elemental powder rather than a mixture, it was believed that higher densities should also have been obtained for alloys using the above technique because of the recoining operation and the high sintering temperature. Consequently, it was decided to investigate the various factors affecting the density of this alloy with the idea that such a study might lead to higher densities and, as a result, powder alloys having magnetic properties identical with those of the fused alloys. It was believed that the principal reason that near-theoretical densities for the powdered alloy were not obtained was the interference of gases with the normal sintering mechanism. When present during the sintering operation, gases can exert several harmful effects: they can remain on the particle surface and interfere with surface diffusion and plastic flow; they can be released and, under certain conditions, expand the void spaces through gas pressure; or they can remain trapped in the pores and exert a hydrostatic pressure that retards elimination of the pores. Jones,4 Rhines,5 Goetzel," and others have given the effect of gases in the sintering of powder compacts an extensive treatment. Among the more important sources of gases in the sintering process are dissolved gases, adsorbed gases, air entrapped during pressing, and gaseous products of chemical reactions. During sintering adsorbed gases are partly released at a relatively low temperature, while those gases entrapped during pressing cannot escape until their pressure is increased sufficiently through increasing temperature to expand the interpartjcle openings. The remaining adsorbed gases, gaseous reduction products, and dissolved gases produce a similar effect at the higher temperatures. If, in the sintering process, gas evolution occurs after the interpore channels have been sealed, an exaggerated expansion of the void spaces results. This is particularly true if the temperature is high enough for extensive plastic flow. In his fabrication of powder bars from tantalum, Balke7 had to consider the effect of adsorbed hydrogen and provide for its escape during sintering by limiting the compacting pressure to a maximum of 50 tons per sq in. The effect of gases entrapped during pressing was first noted by Trzebiatowski8 when he found that gold and silver powders decrease in density with increasing sintering temperature if pressed at 200 tsi, while they exhibit the usual increase when pressed at 40 tsi. Recent investigators9-11 have also noted that entrapped gases have an effect on the expansion of copper compacts during sintering. Proper provision for the escape of gaseous products of reduction must be made in order to avoid deleterious effects. Myers" states that in the sintering of electrolytic tantalum powder, the temperature was gradually raised to 2600°F with a pause at 2000°F to permit reduction of the oxides. Experimental Details For the present study, 50 pct Co-50 pct Fe compacts in the form of circular disks 1½ in. in diam and 0.15 in. thick were fabricated by the pressing and sintering of a mixture of the elemental powders. It was decided to follow the sintering process by means of liquid permeability measurements, because it was thought that such measurements might serve as a measure of relative pore sizes, as well as a possible indication of the point at which most of the interpore channels become sealed. However, since the permeability as measured by the flow of a liquid, such as ethylene glycol, does not give an absolute indication of the point where the pores have become isolated, a method for determining the percentage of pores connected to the surface was set up. As an additional cross check on the permeability measurements, metallographic methods were used to study the relative pore size. Finally, the property of ultimate interest, the density, was measured. Raw Materials: The powders used consisted of an annealed, 99.9 pct pure, —150 mesh grade of electrolytic iron powder, and a 98 pct pure, —200 mesh grade of reduced and comminuted cobalt powder. The cobalt powder was not further processed either by hydrogen reduction or annealing. The screen analyses for the iron and cobalt powders are given in Table I, while the chemical analyses for each type of powder are listed in Table 11. Table 111 gives the hydrogen loss measurements for the powders according to the M.P.A. Standard Method and for a higher temperature as well. Preparation of Compacts: Equal amounts of the elemental powders were mixed by rotation for 1 hr and then pressed into compacts approximately 0.15

Jan 1, 1952

By P. R. Sperry

In an investigation of the decomposition of the solid solution in a cold worked high-purity aluminum alloy containing 7 pct Mg, aged at temperatures from 30o to 82°C, the nucleating sites at the earliest stages of precipitation were observed to be of two types. Nucleation occurred at the high angle grain boundaries both when the alloy was initially cold worked and when solution annealed. Nucleation also occurred at certain unique deformation markings which began to appear in abundance at approximately 30 pct reduction in thickness by cold rolling. These deformation markings were identified as deformation (kink) bands rather than as the usually assumed "slip planes." Zn material that was cold rolled 15 pct, only the grain boundary Fig. 2—A1-7 pct Mg alloy, cold worked 60 pct and heated at 230° C for 5 min. Etched with Perryman's reagent. X500. Reduced approximately 25 pct for reproduction. (a) Bright field illumination, precipitate deeply pitted. (b) Phase contrast, showing slip markings.

Jan 1, 1962

By Hsun Hu, R. S. Cline

A detailed studj) of texture formation in 2 pet Al-Fe single crystals with initial orientations of approximately (111) [112], (112) [111], and (112) [111] was made by examining the textures developed on the surface and at various interior sections of the crystal after rolling to various amounts. Depending' upon the initial orientation of the crystal, the surface and interior textures may differ only in sharpness, or may differ essentially in orientation. The orientation of the (111) [112] crystal does not change upon rolling up to 70 pet, but after rolling more than 90 pet a distinct component of (001) (110] orientation is developed. The texture formed in the two (112) (1111 type crystals consists of (111) (1121 and (001) (1101 components. The latter, however, is largely confined to the surface layers. The textures formed on both sides of the crystal are identical, and the texture composition profile is approximately symmetrical with respect to the central section of the strip thickness. The formation of these texture components is analyzed. DURING the past seven or eight years, deformation and recrystallization textures in rolled Si-Fe single crystals have been extensively studied by various investigators.1-7 From these studies, much knowledge on texture formation in bee crystals of various initial orientations was obtained. However, these results also raised many questions, regarding particularly the correlation between deformation and recrystallization textures, as well as the deformation texture itself of some particular crystals. To take a (111) [112] type crystal as an example, it was shown by Dunn and Koh2, 3 that this orientation does not change during deformation by rolling. This finding is consistent with the conclusion reached by Barrett and Leven-son8 with respect to iron crystals that (111) [112] is one of the stable end orientations. However, different recrystallization textures were observed by Dunn and Koh3 in (111) [112] type crystals of different initial thickness, which widened differently during rolling even though their deformation textures were identical. Another interesting example, also from the results of Dunn and Koh2'3 is that of texture formation in a (112) [111] crystal. This crystal developed a two-component deformation texture of (111) [112] plus (001) [110]. Its recrystallization texture, however, was found to be predominantly (110) [001], which is related to the (111) [112] component by a simple [110] rotation. This crystal, therefore, behaved as if the other deformation texture component, (001) [110], were not present. There are also discrepancies among the results of different investigators, as well as numerous unexplained fine features of the deformation texture of crystals of various initial orientations. In order to have a better understanding of all of these points, a detailed study of deformation textures is greatly needed. One of the obvious things that has been completely overlooked in previous texture studies is the possible effect of surface texture. All past work on the texture of Si-Fe single crystals was conducted in a rather simple manner, i.e., the rolled crystals were etched to a very thin sheet; then their textures were examined by transmission X-ray techniques. For recrystallization texture studies, unless precautions are taken by etching off a sufficient amount of the surface layer before annealing, the texture developed in the interior may be affected by the surface layer, which may well have a different initial texture and which may have undergone recrystallization earlier than the interior of the specimen. Because of this effect, it is now planned to reexamine the texture of various rolled and annealed single crystals at the surface, and at various sections below the surface by using reflection techniques. In some cases, both surfaces of the rolled crystal will be examined. In one of Dunn's early papers,9 he noted that at an early stage of rolling the crystal seems to divide roughly through the middle to become a sample which in effect consists of two layers having some what different orientations. This effect has never been further explored. The investigation described in the present paper constitutes the beginning of a series of thorough investigations of texture formation in deformed bee single crystals designed to clear up some of the uncertainties which have been discussed. We have chosen a high-purity 2 pet Al-Fe alloy for this investigation. It is known that the allotropic transformation of iron is eliminated by alloying with approximately 1petAl. Such an alloy, being very similar to silicon ferrite, can be heated to the solidus temperature without phase transformation. One reason for choosing A1-Fe instead of Si-Fe for the present investigation is that we have been able to make single crystals of a vacuum-melted high-purity A1-Fe alloy by the strain-anneal method without much difficulty, but were not successful in doing so with a vacuum-melted high-purity Si-Fe alloy. For many research purposes,

Jan 1, 1962

By A. Dubé, G. Letendre, C. E. Beaulieu

An experimental study has been made of the time dependence of internal .friction and modulus of rigidity in- freshly quenched steels at room temperature. The effects of frequency, composition, and various thermal treatments are given. The kinetic 1aws observed cannot be fully explained by the so-called first stage of tempering and the transformation of retained austenite. It is suggested that the observed phenomena are due to the progressive immobilization of dislocations introduced by the martensitic transformation. It is generally agreed that the conversion of tetraginal martensite into cubic ferrite and ce-mentite occurs in three stages which at moderate rates of heating take place in the following temperature ranges:'-3 a) The first stage involves mainly a partial loss of tetragonality of martensite and the formation of ?-carbide between 95" and 175oC. b) The second stage consists of the decomposition of retained austenite between 230 and 290' C. c) The third stage covers the formation of ce-mentite between 290o and 400' C. The kinetic laws of these heterogeneous reactions have also been the subject of isothermal studies. Thus, Roberts, Averbach. and cohen3 report a very low reaction rate with a eutectoid steel at room temperature. For example, less than 10 pet of the contraction associated with the first stage is observed after 50 hr at room temperature. Hollonlon, Jaffe, and Buffum4 show that under the same conditions less than 10 pet of the tetragonality is lost. These results have led to the belief that martensite is a relatively stable phase at room temperature. On the other hand, it is well known that important structural changes occur in martensitic steels during the first few minutes at room temperature after quenching. This pretempering has at least two important consequences. In the first place, freshly quenched steels have a tendency to crack at room temperature, a fact which leads to the necessity of tempering as soon as possible after the quench. Another important consequence of pretempering a steel for short periods of time at room temperature is the stabilization of the retained austenite. Thus, as shown by Cohen,5 a very pronounced stabilization is effected with holding periods of 30 min at room temperature. Since these two effects are apparently not caused by the heterogeneous reactions mentioned above, they must be related to the rearrangement of structural defects within the martensite and retained austenite. According to the modern theory of dislocations, the shears required to effect the austenite-marten-site transformation may be realized through the motion of dislocations at the austenite-martensite interface and within the martensite plates.6 In this way, a martensitic transformation closely resembles a plastic deformation. In cold-worked solids, high concentrations of dislocations are left immediately after the plastic deformation and it seems reasonable to assume that appreciable densities of dislocations should also appear in the wake of a martensitic transformation. A considerable part of the high hardness of martensite would then originate in the obstruction of dislocations in analogy

Jan 1, 1961

By F. H. Wilson, M. L. Kronberg

The low temperature recrystalliza-tion of very heavily rolled copper produces a fine grained structure with a high degree of preferred orientation. Additional heating to within a few hundred degrees of the melting point may induce an abrupt and pronounced increase in the grain size, with the resulting crystals having new orientations. This behavior at high temperatures is commonly termed "secondary recrystallization." Several investigations have dealt with the phenomenon arid have served to bare many features of the beha~ior.1-4 In general,observations have been made on the sizes and shapes of the grains, and data have been presented showing the existence of an induction period in isothermal experiments. Although it has been well established that the orientation before the change is statistically (100) 10011, the so-called "cubically aligned" texture, there is no such agreement on the orientation after the change. For example, Dahl and Pawlek1 describe it as being equivalent to an approximately 30" rotation about the [l00] axis of the ideal cubic texture which is parallel to the rolling direction, the resulting orientation being near (210)[001]; and Cook and Richards2 find an orientation of approximately (110)[L12]. Since the completion of most of the work to be reported in this paper, Rowles and Boas3 have published their ver] illuminating paper on "secondary recrystallization," in which they present convincing evidence for a third orientation and show that their esperiments give no evidence for either of the other two orientations. The orientation is described as equivalent to an approximately 30° rotation about a [ 111] pole of the ideal cubic orientation. The existence of a variety of reported orientations is not unique for copper, for a similar state of affairs exists for other systems that have been studied— aluminum, nickel, nickel-iron alloys, and others. It seems therefore that the existence of this variety does not necessarily constitute a contradiction, but rather indicates that different experimental conditions yield different results. The fundamental nature of the phenomenon has not been elucidated. However, it has been generally recognized that the large grains could be the end product of growth of a few select grains already existing in the sample in minor amounts—too small to allow detection—or that entirely new ones could be formed by a process of nu-cleation and growth. Existing experimental evidence does not distinguish between these two most apparent possibilities. Nevertheless, the former has been more generally favored largely because our current understanding of the state of an annealed metal has not made it seem reasonable to expect a nucleation event to occur at temperatures above those required for the primary recrystallization. Observations on the Preparation and Heating of Twin-bearing Cubically Aligned Copper The starting material used throughout. the investigation was a bar of OFHC copper, forged and annealed at 950°C. Visual inspection showed the grain size to be around 0.5 mm, and did not disclose any preferred orientation. A chemical analysis showed the following composition: Cu + Ag— 99.99 Pct S — 0.005 pct 0 — <0.005 pct For the preparation of cubically aligned copper, ¾ in. thick slabs were cut from the bar, heavily pickled in concentrated HNO3 and cold rolled to sheets about 0.012 in. thick. The reduction in thickness was approximately 98.5 pct. Standardized annealing techniques were followed. Samples to be heated were lightly dusted with alumina in order to prevent sticking and then sandwiched between 1/16 in. copper plates. The resulting sandwich was heavily wrapped with copper sheet, and then annealed in air. The protection was such that only very thin films of oxide were formed. That the associated light oxidation of the samples had no specific effect on the recrystallization behavior was shown by the similar results that could be obtained on annealing in highly purified and dried hydrogen. Two methods were used in bringing samples to temperature: (1) by placing the package directly in the furnace at temperature and (2) by placing the package in the furnace at room temperature, and then slowly increasing the temperature. The corresponding heating rates are illustrated in Fig 1, and will be referred to as "rapid" and "slow," respectively. Unless specified otherwise, all anneals will be of the former type. Metallographic examination was made on samples prepared by electrolytic polishing and etching as described in the Metals Handhook.* STRUCTURES FOUND BEFORE "SECONDARY RECRYSTALLIZATION" OCCURS Annealing the rolled material for 1 hr at 400°C produced a heavily twinned, cubically aligned structure, the grain size being of the order of 0.03

Jan 1, 1950

By Jean Howard

RECENT attempts to produce secondary recrystalli-zation in high-purity iron have given conflicting results. Coulomb and Lacombe1&apos;2 did not find it but Dunn and Walter3,4 did. The latter workers have stated that (100) [001] and/or (110) [001] orientations develop depending on the oxygen content of the annealing atmosphere. This Technical Note records results which are in agreement with Dunn and Walter in so far as it shows that secondary recrystallization can be produced in high-purity iron, but does not confirm that both types of orientation are obtainable. Similar observations have been made on chromium-iron and molybdenum-iron, although when this technique is used on 3 1/4 pct Si-Fe, both types are obtained as in the work of Dunn and alter.&apos; Pure iron strip was cold-rolled from sintered compacts prepared from Carbonyl Iron Powder-Grade MCP of the International Nickel Co. (Mond) Ltd. The powder contains about 0.5 pct 0, 0.01 pct C, 0.004 pct N, (0.002 pct S, $0.005 pct Mg and Si, and 0.4 pct Ni—that is, it is substantially free from metallic impurities other than nickel, which is thought to be unimportant in the present work. The iron powder was (a) pressed at 25 tons per sq in. into blocks measuring 3 by 1 by 0.3 in., (b) deoxidized in hydrogen (dewpoint -60°C) by heating first at 350°C and then at 600° C until the dewpoint returned to -60°C at each temperature and (c) sintered in hydrogen (dewpoint -40°C) at 1350°C for 24 hr. (when dewpoint is referred to in this Note, it is the value as measured on the exit side of the furnace). The sintered compacts were cold-rolled to 1/8 in., annealed in hydrogen (dewpoint -60°C) at 1050°C for 12 hr and cold-rolled to 0.004, 0.002, and 0.001 in. with inter-anneals at 900°C for 5 hr and a final reduction of 50 pct. Final annealing of strip between alumina or silica plates at 875" to 900°C in hydrogen with dewpoints of -20°, -55" and -80°C produced secondary grains with the (100) in the rolling plane; the extent of secondary recrystallization was greatest when the dewpoint was -55°C. Annealing in a vacuum of 2 x 10"5 mm Hg at the same temperature produced no secondary recrystallization at all. With strip thicker than 0.002 in. very few secondary crystals developed whatever the conditions of annealing. Using a processing schedule somewhat similar to that described above, secondary recrystallization was produced in two bcc alloys of iron, viz. 80 pct Fe + 20 pct Cr and 96 pct Fe + 4 pct Mo. The former was reduced to final thicknesses of 0.001 to 0.004 in. and the latter to final thicknesses of 0.001 to 0.016 in. With the chromium-iron, a final anneal at 1250°C (found to be the most effective temperature for developing secondary crystals in the 0.004-in material) with a dewpoint of -25°C produced a greater degree of secondary recrystallization than with dewpoints of -50°C or -20°C. Secondary crystals developed in strips of all thicknesses from 0.001 to 0.004 in. Final annealing in vacuum produced no secondary crystals at all. For the molybdenum-iron a temperature of 1200°C was most effective. It was found that a dewpoint of -50°C during the final anneal gave better results than a dewpoint of -25 "C on the 0.008 in. material. Final annealing in vacuum gave slightly worse results than annealing in hydrogen with a dew-point of -50°C. Secondary crystals were developed in strips of all thicknesses up to 0.008 in. The experiments show that the extent of secondary recrystallization is a maximum for certain critical values of oxygen content of furnace atmosphere and annealing temperature, and that these values are different for different alloys. The thinner the material, the less critical these values are. The general conclusions are that secondary recrystallization can be obtained in high-purity iron, chromium-iron, and molybdenum-iron, using a processing schedule similar to that which will cause the phenomenon to take place in high purity 3 1/4 pct Si-Fe. Unlike the silicon-iron, however, only the (100) (0011-- orientation has been produced in these alloys, irrespective of the temperature of final annealing and the oxygen content of the furnace atmosphere. The information used in this Note is published by permission of the Engineer-in-Chief of the British Post Office.

Jan 1, 1962

By T. V. Philip, R. E. Lenhart

When commercial silicon iron sheets of varying magnetic quality are isothermally annealed at high temperatures, extremely large grains develop in the material having good magnetic properties. These grains are of the (110) [001] orientation and are formed by secondary recrystallization. The primary driving force for this secondary recrystallization is grain boundary free energy. For the secondary grains, activation energies of 103 kcal per mole for nucleation, and of 75.5 kcal per mole for growth, were obtained. The activation energy for nucleation of the secondary grains is consistent with a model involving redistribution of a precipitate acting as the primary grain growth inhibitor. SINGLY oriented silicon iron sheet was first produced in 1935.1 The material as commercially produced today has a very highly developed preferred orientation or texture; up to 95 pct of the grains are crystallographically oriented with their (110) planes in the plane of the sheet and their [loo] directions parallel to the rolling direction. This texture, usually written as (110) [00l], is referred to as the "GOSS" or the "cube-on-edge" texture. Because the magnetic properties of this material are superior to those of the nonoriented sheets in the direction of rolling, the oriented silicon iron has acquired tremendous industrial importance especially in the manufacture of transformer cores and other electrical equipment. The commercially produced material is essentially an iron-silicon alloy containing about 3 1/4 pct Si with minor impurities totaling less than 0.15 pct. The silicon steel heat is melted in the open hearth or electric furnace. The ingots are hot rolled, with or without being slabbed, to strips of 0.100 to 0.080 in. thickness. They are then cold reduced to an intermediate thickness, recrystallized, cold reduced to final thickness, decarburized, and finally annealed at a high temperature. During this high-temperature anneal, extremely large grains with the cube-on-edge texture are produced in the sheet. Several papers have appeared in the literature2-10 relating to the production of the Goss-textured material. Most of these describe the textures produced on cold rolling and on subsequent annealing of single crystal or polycrystalline silicon iron. May and Turnbull11,12 have recently shown the necessity of a second-phase dispersed impurity in the material for the production of the Goss texture. However, none of these papers describes in detail the nucleation and growth kinetics of the (110) [001] grains during the final high-temperature anneal.* The present work, therefore, is an attempt to understand the nucleation and growth kinetics of the cube-on-edge grains in the silicon iron sheet during the final high-temperature anneal.

Jan 1, 1962

By Jean Howard

ALTHOUGH zone melting has found favor in recent years because of its convenience and its faster rate of production of single crystals, the older technique of strain annealing still has a number of advantages. It has been reported1 that the lattice of a crystal prepared in this manner has fewer defects than one grown from the melt and, of course, the control of the external geometry is easier. Also, the diameter of the crystal which can be grown by zone melting has a theoretical limit determined by the surface tension, thermal conductivity, and specific gravity of the material, while the size of that which can be grown in the solid state is limited only by practical considerations. In a program for the study of the structure-sensitive properties of niobium and its alloys it was desirable, for ease of handling, to have available single crystals of large diameter. This requirement dictated the choice of the strain-anneal technique. Induction heating was chosen in the present work in preference to other methods because of its deep penetration of large-diameter sections. A five-turn coil, powered by a motor generator operating at 10,000 cps, is contained in a vacuum chamber. The work is lowered through the coil for both the recrystallization and the crystal-growth steps. Starting with electron-beam melted material, the bars are cold-swaged, recrystallized, strained in a tensile machine, and then subjected to the growth step. Single crystals have been grown under the following conditions: Reduction in area during swaging— 79 to 99 pct, recrystallization temperature—1500o to 1667°C at the rate of 1.25 in. per hr, strain—1.0 to 2.5 pct, growth temperature—1600o to 2400°C at rates from 0.15 to 1.25 in. per hr. Starting grain sizes achieved after the recrystallization step varied from 0.6 to 1.55 mm. The starting grain size was found to be critical; if it is too fine and has any residual cold work, as shown by the presence of a fiberlike texture, a single crystal cannot be grown. Using this technique niobium single crystals have been grown from 0.250 in. diameter and 12 in. long to 1.00 in. diameter and 5 in. long as shown in Fig. 1. The 1-in. crystal is the largest to be reported for a refractory metal as compared to 0.500 in. for molybdenum grown by zone melting.2 As with zone melting, control of orientation is possible by the use of special procedures. Other investigators, see for example Williamson and Smallman,3 have reported that orientation control may be achieved by a bending technique. In the present work the strained rod is partially lowered through the coil to start the growth of the crystal. Then it is removed and bent at a point ahead of the interface between the single and polycrystalline portions. Finally, it is returned to the chamber and growth is continued "around the corner". The amount of bending which can be imparted to the rod is limited by coil geometry which up to now has been 10 deg. However, by repeating the bending and growing operations it should be possible to attain any desired orientation. The perfection of these single-crystal specimens as a function of process variables is being measured by X-ray and metallographic techniques and the results will be reported in a forthcoming paper. This work was partially supported by the Advanced Research Projects Agency.

Jan 1, 1964

By Jean Howard

ThE formation of the (100) [001) texture in 3-1/4 pct Si-Fe strip was first reported by Assmus ef a1.l in 1957. Since then much experimental work has been carried out with a view to establishing the mechanism involved. The papers cited above state that the (100) [001] texture was developed in strip rolled from material melted and cast in vacuum. (The impurity content of the ingot is reported as 0.005 pct.) The present note records that similar results can be obtained in material processed by powder metallurgy. A processing schedule is described.which enables the texture to be formed in strip up to 0.010 in. thick, but there seems no reason why this should not be achieved in thicker strip, provided that large grains are developed after sintering. The materials were prepared from Carbonyl Iron Powder Grade MCP (particle size 5 to 30 p) of the International Nickel Co. (Mond) Ltd. The powder contains about 0.15 pct 0, 0.01 pct C, 0.004 pct N, <0.002 pct S, $0.005 pct Mg and Si, and 0.4 pct Ni— that is, it is substantially free from metallic impurities other than nickel, which is thought to be unimportant in the present work. The silicon powder was 99.9 pct purity, or material of transistor quality (ground in pestle and mortar). The mixed powders (3-1/4 pct Si to 96-3/4 pct Fe) are heated in hydrogen at 350" and 650°C to deoxidize the iron before sintering loose at temperatures between 1350" and 1460°C (depending upon the ultimate thickness of strip required) for up to 24 hr. The object of the high-temperature sinter is to develop a large grain size at this stage. Alternatively, the loose sintering can be done at a lower temperature followed by rolling or pressing and then annealing at temperatures between 1350" and 1460°C. Both methods produce large grains, which remain large throughout the process. The compact is then hot-rolled to approximately 1/8 in. with high-temperature interstage anneals if necessary. This step is taken to avoid intercrystalline cracking which would occur if the material of such large grain size were cold-worked. The bar is then annealed at 1050°C and reduced to its final thickness by approximately 50-pct reductions and 1050°C interstage anneals. Throughout the process the dew point of the hydrogen furnace atmosphere is maintained at about -40°C. Samples were annealed in hydrogen at various temperatures and times. Secondary recrystalliza-tion to (100) [001] was developed on the thinner material (i.e., up to 0.002 in.) by annealing in hydrogen at 1050" to 1200°C with a dew point of - 40°C or in vacuum (10-5 Torr) at 1050°C. With the thicker materials (i.e., up to 0.010 in.) the best results were obtained by annealing in hydrogen at 1200°C with a dew point of - 55°C. Complete secondary recrystal-lization to (100) [001] textures was obtained. Above these temperatures secondary recrystallization to (110) [001] tended to develop. The final annealing of samples was normally carried out with the samples placed between recrystal-lized alumina plates, but some experiments were performed with the samples suspended so that their surfaces were not in contact with anything except hydrogen, and these were equally successful in developing secondary crystals. An approximate determination of the proportion of material (before secondary recrystallization took place) having crystals with the (100) or (110) planes in or near the rolling plane showed that 11 pct of the sample had (100) and 16 pct (110). The method used for the determination is described below. A sample was annealed at a temperature just below the secondary recrystallization temperature and etched to reveal the (100) planes. The approximate area covered by crystals having (100) or (110) in or very near the surface was measured on the screen of a Vickers projection microscope. This was repeated for twenty positions chosen at random and a mean of the results calculated. The main hindrance to developing the secondary crystals in the thicker materials was the difficulty of obtaining a large enough initial primary grain size before secondary recrystallization. This was overcome by increasing the particle size of the silicon powder used. During the course of the work, it had been observed that the larger the grain size after sintering the more likely it was that the material would be successful in developing secondary crystals at a later stage. An experiment was therefore carried out to determine whether the material with the larger grain was more successful in developing secondary crystals due to the large grain produced at the sintering state per se or whether it was due to the greater reduction of silica brought about when the sintering temperature was raised in order to increase the grain size. A comparison was made between two compacts, one of which was made with silicon powder of 60 to 100 mesh, the other with silicon powder which was finer than 200 mesh. F?r this experiment, use was made of a phenomenon previously observed that the larger the particle size of the silicon powder employed in making a compact, the larger is the grain size of the compact. The silicon powder was ground

Jan 1, 1964

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:&apos; 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&apos;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&apos; 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&apos; 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&apos;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.&apos; 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"&apos;-&apos; 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.&apos; 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&apos;8 = 1, and the experimental fact that DJDn in magnesium was always less than 1.25.

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-&apos;. 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&apos; 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