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By N. J. Grant, H. Brunner

This paber is concerned with the determination of equations relating elongation to the amount of shear taking place both along grain boundaries and in slip planes of poly crystalline aggregates during creep. Certain discrepancies with previously used equations are pointed out. Grain boundaries were observed to become serrated during creep, but it is shown that this does not necessarily prevent further grain boundary sliding. Direct obser-vations of subgrain boundary ingration lead to the conclusion that this migration facilitates sliding along serrated grain boundaries. It is bointed out that the state of stress at triple boints is still unknown. MOST of the mechanisms of deformation contributing to elongation are shear processes, such as slip, kinking, grain boundary sliding, and twinning. For quantitative investigations of individual deformation mechanism it is necessary to know the equation which permits the calculation of speci-tnen elongation from measured amounts of shear. This calculated elongation must then be compared with the observed total elongation. The authors' special interest concerned grain boundary sliding during creep. Although this subject has already been investigated quantitatively by McLean,' Rachinger,' and Fazan, Sherby, and Dorn, calculations indicated that none of the equations used thus far to relate shear with elongation were sufficiently well founded. A basic study of this relationship was thus made and the results of this study (which do not entirely agree with those previously used) are presented. Most of the ideas set forth apply not only to grain boundary sliding but to other mechanisms of shear as well. THE SPEAR-ELONGATION RELATIONSHIP Basic Models—The relationship between shear and elongation is trivial in the simplest case of shear, which is shown in Fig. l(a). The vector A; designates the displacement across the shear interface, and Au, and Aut are its components parallel and normal to the tensile direction, respectively. It is evident that the specimen elongation due to shear is equal to the longitudinal component of the shear vector, and it should be noted that the normal component does not contribute to the elongation of the specimen (there are, of course, two normal components in a three-dimensional model). The model shown in Fig. l(b) may be applied to mechanical twinning and to subgrain boundary tnigration. In this case the width (h) of an already existing shear band increases by the migration of an interface, but the shear angle y (angle of mis-orientation in the case of a subgrain boundary) remains constant. The geometrical relationships indicated in Fig. l(b) permit this case to be reduced to the one shown in Fig. l(a). For the resulting elongation A6 we find: where AV/V = fraction of the volume of the specimen swept by migrating interfaces , and 1 = length of specimen. Thus, assuming for example that the angle of mis-orientation is 1 deg, and that P = 45 deg, we find that the specimen elongates 0.87 pct of its length if the entire volume of the specimen is swept once by such a subgrain boundary. An example of deformation by migration of subgrain boundaries is shown in Fig. 2. The specimen shown was repolished after 9.8 pct creep strain and the test then continued for another \ pct. Since the shear vector has, in general, a component normal to the surface, subgrain boundary migration results in the formation of an inclined band delineating the region swept by the subgrain boundary. These inclined bands become clearly visible when observed with oblique illumina-

Jan 1, 1960

By W. C. Thurber, C. J. McHargue

THE deformation textures of metals have been extensively studied because of both the practical implications in metal fabrication and the fundamental insight into the behavior of the metal during deformation. Most studies have been concerned with pure metals or solid-solution alloys and relatively little attention has been directed toward more complex alloy systems. Barrett' and Brick2 have summarized work on multiphase systems in terms of the relative ease of deformation of the phases. Thus, if the phases are deformed about equally, each develops its usual texture for the particular fabrication process. This behavior has been reported for Ag-Cu and Cd-Zn alloys3 and 62-38 brass.4 A dispersion of hard particles in a softer matrix interferes with the normal reorientation of the matrix lattice during deformation, thus distorting the texture or in some cases preventing its development. Increasing the amount of carbon in steel has been observed to increase the randomness of the ferrite5 and almost random textures have been reported for A1-12 pct Si eutectic alloy wires.6 It has also been noted that if the second phase is platelike, deformation causes the platelets to line up in a common direction. The present work concerns a quantitative study of the deformation textures in aluminum-uranium alloys containing 5 or 13 wt pct U. Alloys in this composition range are characterized by a pure aluminum matrix in which the intermetallic compound UA14, is dispersed. From a fundamental standpoint, this system affords the opportunity for studying the effects of a dispersed phase on texture development in an essentially pure metal matrix. Further, these alloys are commonly used as fuels for nuclear research and testing reactors, and a knowledge of the preferred orientation may be useful in evaluating physical and mechanical properties as well as response to fabrication. The deformation textures in sheets of aluminum (99.996 pct), Al-5 pct U alloy, and Al-13 pct U alloy were determined for reductions in thickness of 90 pct by cold rolling. The texture in an alloy rod of the latter composition which had been extruded at 455°C was also determined. It can be readily ascertained from the aluminum-uranium phase diagram that the 5 pct U alloy is hypoeutectic and contains 7.3 wt pct (3.4 vol. pct) UAl4. The 13 pct U alloy has the eutectic composition and contains 18.9 wt pct (9.4 vol. pct) UAl,; however, because of nonequilibrium solidification conditions, the typical eutectic microstructure was not developed. The alloys were prepared by open-air melting in graphite crucibles. The slab castings were cropped and cold reduced 90 pct in thickness on a two-high mill. The slabs were reversed after each pass. Although the uranium-bearing alloys exhibited edge cracking, they could be cold rolled to the desired thickness. Small coupons 1.5 by 0.75 by 0.1 in. thick were sheared from the center of the rolled plate with a major axis parallel to the rolling direction. To obtain a specimen of sufficient thickness for machining of the X-ray diffraction specimen, three coupons were laminated into a single three-ply sandwich with a suitable adhesive. Adhesives which could be cured at room temperatures were selected in order to prevent recrystallization during bonding. Bondmaster M-648 (Rubber and Asbestos Corp.) was used for the pure aluminum laminate and Armstrong A-6 (Armstrong Products Co.) was used for the alloys. The alloy for extrusion was cast in a cylindrical graphite mold! cropped and machined into a 3-in. diam by 4-in. long billet. This billet was preheated to 455°C, upset to 3.125 in. diam, and extruded on a 700-ton hydraulic press at a speed of 6 fpm through a flat-face, 1-in. diam die. The rod was quenched with a water spray as it emerged from the die. Pole-distribution data were obtained using the diffractometric method described by Jetter and Borie.7 A spherical X-ray diffraction specimen of

Jan 1, 1961

By M. N. Shetty

LARGE copper whiskers (-100 p) of 11111 orientation were tested in a floor-model Instron testing machine, at liquid nitrogen temperature. (Testing methods will appear elsewhere.) Whiskers deformed by twinning after some initial deformation. A load-elongation curve at the onset of twinning is reproduced in Fig. 1. Twinning was confirmed by taking a back-reflection Laue picture, using a slit colli-mator, which showed distinct splitting of reflections. The tensile stress reached just before twinning is about 1.4 x 107 g per sq cm (-7.0 x106 g per sq cm—resolved shear stress) which drops to 1.2 x107 g per sq cm (-6 x 106 g per sq cm—resolved). This twinning stress is about five to ten times larger than the value for bulk single crystals of copper deformed at 77°K (-106 g per sq cm—resolved). Twinning models based on Cottrell-Bilby's pole mechanism are discussed in detail by Venables.' In the present work a mechanism based on the idea of failure of a Lomer-Cottrell barrier by recombination will be proposed. An L-C barrier may fail either by recombination or by dissociation.3 Fig. 2 provides the necessary information. It shows that the stress necessary to break such a barrier is about 1.8 x 107 g per sq cm by recombination and 4 x 107 g per sq cm by dissociation at 77°K. The twinning stress reached by whiskers is comparable to the stress level required for failure of an L-C barrier by recombination. (Stroh himself points out that his calculations should not be taken too literally.) We consider a segment of the L-C dislocation which has recombined (AB in Fig. 3) over a length to form the total dislocation which then glides in the

Jan 1, 1965

By W. N. Roberts

Hadfielcl steel has been studied by transmission electron microscopy to determine the microsl.rtic-ture of the cold-worked material, which has been a subject of controversy for many years. The presence of fcc deformation twins in specimens deformed in tension, by hamnzering, and by explosive -shock loading at room temperature lzas been established by electron diffraction. No evidence of a mar tensite was detected in any of the speciwens. Small amounts of E martensite were idenLified in the hamnleved specimens. DESPITE numerous researches on Hadfield steel since its discovery in 1882, there is still disagreement on the nature of transformations in the cold-worked material. Collette el al.,' using X-ray and electron diffraction, have found evidence for stacking faults, E martensite, and a martensite in Hadfield steel deformed in tension at room temperature. Nishiyama and Simizu,' using electron microscopy, have found stacking faults and E martensite in hammered Hadfield steel. White and Honeycombe have concluded from X-ray diffraction that Hadfield steel remains fully austenitic even after severe cold work at -196 Previous work by the author, indicating the presence of a, martensite in deformed Hadfield steel, was in error due to a faulty interpretation of the electron-diffraction patterns. Various workers,5'7 over the years, have speculated on the presence of deformation twins in Hadfield steel, largely from such circumstantial evidence as the persistence of slip bands with repeated polishing and etching, the presence of serrations in the stress-strain curve, and the absence of evidence of a martensite by X-ray measurements. The advent of electron-transmission microscopy and se- lected-area diffraction has made possible the positive identification of fine deformation twinning. PROCEDURE For tensile tests, standard ASTM specimens of 2-in. gage length, ground from 0.12-in. Hadfield steel sheet, were solution-treated at 1050°C for 30 min in a salt bath, to avoid decarburization, and water-quenched. The grain size was about 0.01 sq mm. Chemical analysis of the steel after heat

Jan 1, 1964

By R. Maddi, I. R. Kramer

The delay time for the initiation of slip was studied in single crystals of a brass, aluminum, and ß brass. A delay time for slip was found in ß brass when the specimens were tested below room temperature; however, one was not found for a brass or aluminum. A general theory for the existence of the brittle transition temperature is proposed. A LTHOUGH a considerable amount of effort has A been devoted to the study of the deformation and fracture of single crystals, the vast majority of the work was concerned with static tests or with tests carried out at relatively slow strain rates. The necessity for the study of a possible incubation time for slip becomes apparent when the various theories which have been postulated for the elucidation of the mechanism of slip are considered. The existence of an incubation period would strongly indicate that slip occurs by a process of nucleation and growth; whereas the absence of an incubation would present rather convincing evidence that slip occurs by a cataclysmic process. In addition to shedding light on the process of plastic deformation, an understanding of the early stages of plastic deformation may be helpful in finding an explanation for the brittle behavior of the body-centered metals under certain conditions. It is well known that these metals, such as iron, molybdenum, tungsten, ß brass, etc., will become brittle as the test temperature is lowered or the strain rate is increased. In spite of the fact that this subject has received considerable attention since the turn of the century, no adequate theory exists today which explains the phenomenon. In the ductile temperature range the metal breaks with a "fibrous" fracture after considerable slip has taken place. In the brittle temperature range the metal fails essentially by cleavage on the {loo) planes: however, some plastic flow is always present even in the most brittle fractures. It is possible, as will be explained later, to ascribe this brittle behavior to the length of the incubation time for slip. Clark and Wood,' using polycrystalline metals, showed that a delay time existed for the yield point in mild steels and that the delay time depended upon the applied stress. These authors stated that the delay time was observed only with those materials for which the stress-strain curve showed a definite yield point. In their work only the mild steel specimens exhibited a delay time at the yield point, while the other materials studied-type 302 stainless steel, SAE 4130 normalized steel, SAE 4130 quenched and tempered steel, 24s-T aluminum—did not show a delay time. These authors' in an extension of their work, found that as the temperature was lowered the delay time was increased. It is, then, the purpose of this investigation to measure or to set an upper limit on the delay time for plastic flow in single crystals of a brass, aluminum, and ß brass. The delay time will also be studied as a function of temperature. The incubation time may be measured by determining the length of time the specimen will support a stress without slip occurring when the stress is greater than the static critical resolved shear stress. In order to accomplish these measurements use was made of a pendulum which was so designed that a single crystal specimen could be placed at various positions along its length. When a pendulum is struck by another pendulum of the same length, an elastic wave is transmitted down the bar with the velocity of sound in the material and is reflected from the far end of the bar. The reflected wave then travels back and unloads the stress until it reaches the impacted end of the bar and the two pendulums separate. The length of time that the specimen is subjected to the stress is equal to the time it takes for the stress wave to travel twice the distance from the specimen to the end of the bar. The stress applied to the specimen is governed by the velocity of impact of the two pendulums. The stress at which the specimen first suffers plastic: deformation was determined in these experiments by examining the specimen under the microscope for the first appearance of slip lines and by measuring the residual strain after each impact. In these experiments the critical resolved shear stress was approached from the low stress side and no attempt was made to determine it exactly. To determine it exactly, it would have been necessary to find that stress at which slip would have just started. However, since the stresses were increased in rather small increments the critical stress is believed to be approached rather closely, as will be seen from the experimental results. The critical stress will be taken as the highest stress obtained before the onset of plastic deformation. The stresses

Jan 1, 1953

By R. Maddi, I. R. Kramer

C. S. Roberts (Dow Chemical Co., Midland, Mich.)— In this study we have seen another example of how modern electronic instrumentation can be of great value to metallurgical research. The authors have shown much ingenuity in their experimental work. However, I wish to point out that anelasticity theory tells us that we must be cautious when we use pulse methods for measurements which are to be correlated with knowledge of static stress-strain behavior. The basic stress calibrations used by the authors depend on the use of static moduli combined with the pulsed strains. No recognition of a possible modulus defect has been indicated. The general agreement of critical resolved shear stresses may indicate that a

Jan 1, 1953

By I. R. Kramer

The delay time for single crystals of iron, zinc, and pre-strained aluminum was measured under conditions of high-speed deformation. The delay time of aluminum was found to be affected by the orientation of the crystal. Under the dynamic conditions employed, tile calculated "activated volume" term appears to be very small for the three metals studied. IN a previous paper,1 it was shown that under dynamic testing conditions at 78° K, there was a delayed yield in single crystals of aluminum and copper which had been cold-worked prior to testing. The experimental results also indicated that the delay-time effect was not due to the interaction of dislocations with impurity atoms or vacancies, but rather to a dislocation-dislocation interaction since aluminum which has not been prestrained shows no delay-time phenomenon. In this paper, some data are reported on the effects of orientation on the delay time of aluminum single crystals; the delay time of zinc single crystals saturated with nitrogen and the delay time of iron single crystals also were measured. EXPERIMENTAL PROCEDURE Aluminum (99.997 pct) and zinc (99.999 pct) crystals, 1/2 in. in diam and 8 in. long were grown by the Bridgman technique. The iron single crystal was supplied by Dr. R. Maddin. The zinc crystals containing nitrogen were prepared by melting high-purity zinc in a graphite crucible and the nitrogen was introduced by additions of ammonium chloride. The liquid zinc was then drawn up into glass tubes of 1/2 in. diam and allowed to solidify. The rods were cooled to room temperature before the transfer to the mold for conversion into single crystals. The orientation of all specimens was determined by the Laue' back-reflection technique, Fig. 2 and Table I. To prepare for the delay-time measurements, the crystals were cut with a fine jewelers saw and the ends carefully machined. The specimens then were electrolytic ally polished to remove the cold-worked metal, mounted in a special fixture and hand-lapped. As a final step, the crystals were annealed in evacuated tubes. Specimens of aluminum crystals, Nos. 24 and 26, were compressed 0.5 and 2 pct, respectively, in the direction of the later impact. The zinc specimens were aged at 50°C for 15 min, In the case of iron, only two specimens could be obtained. To obtain sufficient data, it was necessary to resort to a reaging treatment. After each delay-time test, the specimens were aged at 65° C for 100 min. This treatment, according to Clark,2 is sufficient to restore the original delay time. It is believed that although the specimens were plastically deformed approximately 10-4 pct, after each test the delay-time values are reliable. The delay-time measurements were made in an apparatus similar to that described previously.' Single crystals approximately 1 in. long and having a diameter of 1/2 in. were placed in a pendulum which consisted of a bar 1/2 in. in diam and 8 ft long, designed with a crystal holder to accommodate the specimen at low temperatures. The crystal was held at a position 2 ft from the front part of the pendulum. This portion of the apparatus was supported on a fine molybdenum wire. A projectile bar of the same diameter and length comprised the other portion of the apparatus. This bar was supported on

Jan 1, 1962

By L. B. Harris

Continuous cyclic unloading during tensile work hardening of polycrystalline zinc at room temperature enables specimens to sustain greatly increased extension. Such enhanced ductility is associated with creep-type extension, during which the cyclic component appears to promote relaxation of internal strains. It is possible to trace the transitions from tension, through enhanced cyclic extension, to fatigue and relate the observed behavior to simpler types of deformation. DISTINCTIVE deformation behavior has been shown to occur when loading includes both cyclic and unidirectional components. For aluminum and copper extended by a sequence of progressively biased strain reversals, coffin1 observed greater fracture ductility and lower flow stresses than during monotonic tension. This may be compared with the reduction in hardness obtained from conventional fatigue softening. But fatigue softening is accompanied by enhanced fatigue life,' whereas Benham3 found that fatigue life was reduced when copper continuously extended during axial load cycling. The corresponding specimen elongation, for large cyclic load amplitudes, was greater than during normal tension. Under different conditions, Bendler and wood4 found that torsional fatigue initiated extension in copper under low tensile loads previously in equilibrium with the specimen; fatigue life was again reduced. Thus there is a type of cyclic softening which is associated with reduced fatigue life and which occurs when the cyclic loading is accompanied by a unidirectional strain component. Further, the fracture ductility or extension obtained from the unidirectional component can exceed that obtained in the absence of cyclic load. Specimen extension was not initiated by axial fatigue at small load amplitudes;3 hence Benham's work distinguishes between fatigue at large and small amplitudes, the former often being linked with unidirectional deformation because of similarities in strain Structure. The initiation of tensile extension during torsional fatigue,4 however, occurred with small amplitudes. Comparable changes in behavior have been ob- served during creep. kennedy' found that combined cyclic and creep stresses on lead at 32°C increased the rate of elongation over that for simple creep, the consequence being a reduction in creep life. It was also demonstrated that small cyclic stresses applied after creep deformation initially increased recovery, but that prolonged application produced only normal fatigue hardening. It is clear that physical properties can be changed by interaction between the cyclic and unidirectional deformations, but owing to the number of different ways in which the deformations can be combined and the large number of possible variables for each combination, trends of behavior become easily obscured. One definite conclusion is that enhanced ductility or increased extension can be obtained by cyclic action, and it is this process that has been investigated for the tensile test by measurements of the extra tensile strain produced by the addition of a cyclic tensile component. EXPERIMENTAL PROCEDURE Material. Specimens were 99.99 pct Zn wire of 1.6 and 2.0 mm diam. Mean grain diameter was 0.02 mm, sufficiently small to give a ductile necked-down fracture under all loading conditions. All experiments were conducted at an average temperature of 20°C. Normal Tension. Unidirectional tensile curves at different strain rates were obtained from an In-stron testing machine, on which load-time curves were recorded autographically, using gage lengths of 5 and 10 cm. Straining was at constant cross-head velocity, and quoted strain rates are with reference to initial specimen length. Measurements of total elongation under simple tension were also made on the tensile machine that had been modified to incorporate an added fluctuating load. Combined Tension and Rapid Cyclic Load. An electromagnetic vibrator was coupled to the elastic beam of a Hounsfield ensometer- and driven sinus-oidally from a power amplifier at frequencies from 20 to 360 cps, the flexible connecting links on the tensometer being replaced by rigid fixtures to eliminate lateral vibration in the specimen. One end of the specimen was pulled by the normal extension drive of the tensometer while the other end, fixed to the elastic beam and vibrator, was subjected to rapid oscillations of load. It was thus possible to apply cyclic load to a tensile test without altering the rate of extension of the specimen

Jan 1, 1964

By Roman Šejnoha, Karel Mazanec

A pronounced tendency for delayed fracture zoas observed in the martensite structure of low-alloy steels in the as-quenched condition. Cracks of predominantly intercrystalline nature nucleated and propagated at stresses substantially lower than the short-titne tensile strength of- the steels, and were observed even in hydrogen-free speciunens. The occurrence of delayed fractures in the as-quenched condition is interpreted as a supevposition of the effect of free dislocations generated during the martensite transforlnation, and of a weakening of the prior austenite grain boundaries caused by dynamic shocks exerted on the boundaries by growing martensite plates. AN important metallurgical problem, connected with the production and use of high-strength steels, is delayed fracture in martensitic structures. Such fractures occur in quenched steels as a result of prolonged loading with external stresses far lower than the short-time tensile strength of the steel. The same effect can be produced by sufficiently high internal stresses: it is well-known that quenched structures will in some cases crack intergranularly at room temperature if not tempered quickly enough even in the absence of any externally applied stress. In Troiano's papers1,2 on delayed fractures in high-strength steels, the fundamental role of hydrogen migrating under the influence of multiaxial stress towards the nuclei of cracks was found. Fig. 1 shows the typical relationship between stress and the time to fracture found by Troiano in hydrogen-charged high-strength steels. On the other hand, Shurakov 3,4 explains the realization of delayed fractures in martensite as due to a "quasi-viscous" behavior of the austenite grain boundaries immediately after the martensitic transformation. 1) MATERIALS AND EXPERIMENTAL METHODS Two low-alloy steels of commercial purity were used for the experiments reported in this paper. Their chemical composition is shown in Table I. The heats were melted in a laboratory furnace, cast to ingots, forged to bars of 3/4 in. diameter, and annealed. Machined test pieces were heat-treated as follows: Ni-Cr-Mo steel held at 900°C for 30 min and quenched in oil; Mn-Si-Cr steel held at 900°C for 30 min and quenched in water. For the delayed-fracture tests, notched cylindrical test pieces, Fig. 2, stressed in torsion, and unnotched cylindrical tensile-test pieces, 1/4 in. diameter, were used. The specimens were normally loaded with a constant static load 45 min after quenching for the torsional tests and 10 min

Jan 1, 1965

By J. E. Dorn, L. A. Shepard

LOW and Gensamer' demonstrated a number of years ago that the yield point phenomenon in mild steels was associated with the presence of fer-rite soluble carbon or nitrogen. More recently the yield phenomenon in body-centered-cubic metals containing interstitials was rationalized by Cottrell' in terms of a simple dislocation model. Interstitial atoms interact with dislocations in two ways; they cause not only local expansions but induce local tetragonality in the lattice. Consequently, interstitial~ interact with the hydrostatic tension and shear components of the stress about dislocations. They tend to migrate toward the expanded regions of edge dislocations and to assume sites that relieve the shear stresses of screw dislocations. Thus, a dislocation saturated with solute atoms constitutes a lower free energy state than that obtained when the dislocation threads through the average composition regions of the matrix. A greater stress will be required to separate the dislocation from its atmosphere than to move the dislocation through the matrix. This factor gives rise to the upper yield stress, which is required to unleash a series of dislocations in a localized region. This local yielding is propagated across the specimen to form a thin band of plastically deformed material known as a Lueder's band, making an angle of about 45" to the stress axis. Once the band has formed, deformation continues at the lower yield stress by the spreading of the Lueder's band in the direction of the applied stress. Undoubtedly the spreading of Lueder's bands at the lower yield stress is accomplished by the high stress concentrations at the band fronts, which serve to induce continued unlocking of new dislocations in advance of the migrating band fronts. Cottrell and Bilby have shown that the dependence of the yield point on temperature can be deduced by assuming that thermal fluctuations aid the stress in unlocking small dislocation loops from their solute atmospheres. Once a loop that exceeds a critical size has been nucleated, the entire locked diqlocation is released and can migrate. Fisher4 simplified this analysis by assuming that the locking forces were short range, so that if the dislocation loop were displaced only one Burgers vector from its atmosphere, it would be unlocked. Applying his model to the special case of delayed yielding under a constant stress of the order of the upper yield strength, he demonstrated that the delay time 7 for yielding should depend on stress and temperature according to where A and B are constants, G is the shear modulus, and u and T are the resolved shear stress and absolute temperature, respectively. Cottrell and Bilby, Fisher, and Fisher and Rogers' have shown that the above deductions are at least in qualitative harmony with the experimental facts. A number of investigators5-0 have shown that the yield point phenomenon can also be induced in sub-stitutional alloys of face-centered-cubic metals. In general such yield points are not as pronounced as those encountered in body-centered-cubic metals containing interstitials. The yield point phenomenon in these materials is usually enhanced by prestrain-ing at low temperatures and aging at intermediate temperatures. Undoubtedly the yield point phenomenon induced by strain aging substitutional alloys also results from locking of dislocations. But the locking of dislocations in substitutional alloys of face-centered-cubic metals differs somewhat from interstitial locking of dislocations in body-centered-cubic metals. Substitutional elements in face-centered-cubic lattices cause only radial displacements of the adjacent lattice points. Consequently, only the edge components of dislocations can be locked by the mechanism suggested by Cottrell. Additional locking, however, can be obtained by the Suzuki mcchanism.10 In face-centered-cubic metals, dislocations exhibit lower energies when they are present in the

Jan 1, 1957

By F. N. Rhines, B. H. Alexander

MUCH attention has been directed to the effects of grain size upon the properties of alloys, but there has been scant study either of the conditions that determine the pattern and dimensions of den-drites in metal systems, or of the influence of their shape and size upon the overall properties of cast-ings. The aim of the research that is about to be described has been to investigate the effect of vari-ous factors upon the mode of formation of dendrites in alloys by measurements of the distance between adjacent dendrite arms (dendrite spacing). Early investigators, including Grignonl and Tschernoff,2 showed that a metal dendrite is com-posed of a tree-like system of stalks and branches arranged in a simple geometrical pattern. North-cott and Thomas3 demonstrated that, in the face-centered cubic solid solutions of copper-base, these stalks and side arms all lie in (100) directions in the crystal. Several investigators, including Sauveur and Chou,0 Sauveur and Reed,' and Martin and Mar-tina have reported that the addition to steel of alloy-ing elements, such as nickel, chromium, and molybdenum, not only makes the dendrites easier to reveal by etching, but makes them coarser. The latter authors8 proposed that the coarsening of the dendrites is roughly proportional to the increase in the temperature range of freezing, caused by adding the alloying elements. Sauveur and Chou6 showed, in addition, that the dendrites are coarsened by a decreased rate of cooling of the casting. Measurement of Dendrite Arm Spacing Among the physical conditions that could be ex-pected to have an influence upon the dendrite arm spacing, that appears in a cast metal, are: composi-tion, rate of freezing, crystal structure, and type of constitution. The relationships obtaining between these variables and the dendrite dimensions have been examined, in the present research, by measur- ing the arm spacing in a wide variety of alloys, listed in tables II through VI. Alloy compositions are recorded in the tables by showing the symbol of the major metal followed by the percentage and symbol of the alloying agent; thus, "Al-10Ag" is an aluminum-base alloy containing 10 pct of silver. Although none of the alloys were analyzed, an im-pression of their degree of purity may be obtained from that of their component metals given in table I. Five hundred grams of each alloy was made by melting in small clay-graphite crucibles in an elec-tric muffle furnace. After alloying the temperature was adjusted to 50" to 75°C above the liquidus and the melts were poured into cast iron molds, at room temperature, the molds having a wall thickness of 1 in. and a cavity 11/2 in. sq in cross-section. Each ingot, thus cast, was sectioned at mid-height and the sectioned surface was polished and etched for metallographic examination. Dendrite spacing meas-urements were made at three positions, namely, ad-jacent to the mold wall, midway between the wall and the center of the ingot, and at the center (desig-nated e, m, and c respectively, in the tables). A typical series of microstructures is presented in fig. 1. For each measurement, the average was taken of the dendrite spacing of several grains covering a zone about 2 mm wide. Only those grains which had a major dendrite axis nearly in the plane of polish were selected in order to eliminate corrections for orientation differences from grain to grain. Although the dendrite spacings were measured to the nearest thousandth of a millimeter, the values listed in the tables are thought to be significant only to the nearest hundredth of a millimeter. The larg-est difference in readings found, when various ob-servers rated the same specimens, was 0.012 mm; the largest difference between corresponding meas-urements upon duplicate specimens was 0.027 mm.

Jan 1, 1951

By W. G. Lidman, H. J. Hamjian

' I HE fabrication of many materials from powders involves a sintering process. A mass of powder will sinter because of the excess free energy over the same mass in the densified state caused by the higher total surface area of the powder. An understanding of the kinetics and mechanism of sintering should assist in improving the properties of such materials. The present investigation conducted at the NACA Lewis laboratory deals with the sintering of chromium carbide. Dry sintering (sintering at a temperature below the melting point) was divided into two stages by Shaler:' the first stage, during which the particles preserve much of their original shape and the voids are interconnected, and the second stage, during which densification occurs and the pores are isolated. The mechanism of forming interfaces between particles, or welding together of particles, has been investigated by Kuczynski2 and may be described by any one or a combination of the following mechanisms: viscous flow, evaporation and condensation, volume diffusion, or surface diffusion. The mechanism by which pores are closed or eliminated (densification) during sintering, is of interest. Grain growth observed during sintering may be attributed to the variation in the surface energies of individual grains, causing some grains to grow at the expense of others. Grain boundary migration occurs presumably by a diffusion process, therefore the rate of grain growth would be expected to increase exponentially with increasing time and temperature. Thus, for practical sintering times of less than 1 hr, a certain minimum temperature may exist at which major structural and property changes will occur. Densification and kinetics of grain growth during sintering under pressure of chromium carbide were investigated to provide additional information which will aid in describing more accurately the sintering process and the mechanisms involved. This material was selected for this study because of the current interest in high strength, oxidation resistant refractory materials, such as carbides, which are sintered to produce solid, dense materials from powders. Sintering under pressure is a process where the heat and pressure are applied to the compact simultaneously, specimens for this work were prepared by sintering under pressure at different temperatures and for various time periods. Experimental Procedure Preparation of Specimens: Chemical analysis of the commercial chromium carbide used in this investigation was as follows: Cr 86.19 pct, C 12.14 pct, and Fe 0.2 pct. X-ray diffraction powder patterns gave characteristic diffraction lines of Cr3C2 crystal structure. Powder particle size was determined microscopically and the average initial particle size was 6 microns with 85 pct between 2 and 10 microns. Specimens sintered under pressure were formed in graphite dies3 heated by induction. Sintering temperatures were measured with an optical pyrometer by sighting into a 3/8-in. hole drilled 1 in. deep at the midsection of the graphite die. A load of approximately 1 ton per sq in. was applied to the powder. The die assembly was heated in 20 min to the highest temperature (2500°F') at which no increase in grain size could be observed, and less than 2.5 min were required to heat from this temperature to the maximum temperature (3000°F). Sintering temperatures and times for the specimens of this investigation are indicated in Table I. Analysis of Specimens: Specimens polished with diamond abrasives were etched to reveal the grain boundaries with a 1:1 mixture of 20 pct potassium hydroxide and 20 pct potassium ferricyanide heated to 160°F. Representative areas of each sample were photographed at 1000 diameters. The largest diameters of all well-defined grains were measured, but only the measurements of 15 of the largest grains were averaged in order to determine an index of grain size on the assumption that they were among the first to begin growth. Densities were determined from differential weighing of the samples in air and water. The reported density values are considered correct within ±0.01 g per milliliter. Results and Discussion Metal compacts have exhibited grain growth when sintered at temperatures about two-thirds of the absolute temperature of their melting point.' Grain growth also occurs during the sintering of chromium carbide and is illustrated by the micrographs shown in Fig. 1. These micrographs were prepared from specimens sintered for 90 min at temperatures ranging from 1371°C (2500°F) to 1648°C (3000°F). Average grain size and density measurements of specimens investigated are presented in Table I. The relationship between grain size and sintering tem-

Jan 1, 1954

By R. W. Heckel

A method is described whereby the relationship of both the "at-pressure" powder compact density and the "zero-pressure" compact density to the applied pressure may be obtained from continuous measurements of punch movement during a single compaction operation. The rate of density increase with applied pressure for the metal powders is found to be proportional to the volume fraction of pores for pressures exceeding a lower limit which varies from 15,000 to 30,000 psi, depending on the powder. 1 HE compaction of powdered materials is carried out primarily to increase the density of the material. If the ultimate goal of the over-all process is the attainment of minimum porosity, compaction is responsible for most of the densification. For example, loose powdered metals have porosities of about 65 to 75 pct. Axial loading in a die or hydrostatic pressure may effectively reduce the porosity of most powders to 20 pct or lower with pressures of 50,000 psi and greater. The relationship between the density of a powder compact and the pressure needed to achieve that density is most commonly obtained by pressing several compacts, each at a different pressure. Measurement of the densities of the individual compacts when they are removed from the die then provides the density-pressure relationship. However, this method suffers from several disadvantages. Because a large number of compacts and pressing operations are required, it is inherently slow. Furthermore, since density measurements are made after the specimens are removed from the die, data obtained refer only to pressures greater than those necessary to form a coherent compact. The third disadvantage is the inability of this method to provide information about the compact density at the applied pressure in the die. Because the determination of density-pressure relationships has been a slow, tedious process, investigators have sought to express the compaction behavior of powders by other means. The general terms "comparability" and L'compressibility" have been used to rank powders qualitatively according to their compaction characteristics. To restore a quantitative nature to the subject and to prevent confusion, Schwarzkopf1 has proposed that compac-tibility be defined as the minimum pressure needed to produce a given green strength, while compressibility should be used to indicate the extent to which the density of a powder is increased by a given pressure. Probably the most widely used of the compaction parameters is the "compression ratio,'' which is generally defined as the ratio of the compact density obtained by pressing at a given pressure to the apparent density of the loose powder.2 However, the description of the compaction behavior of a powder by these parameters provides only limited information about the process because of their applicability to just one specific condition such as a given green strength or a given pressure. The method of obtaining density-pressure relationships which will be described in the present paper was designed to eliminate the shortcomings of the previous techniques while maintaining equivalent accuracy and precision. EXPERIMENTAL TECHNIQUES The general principle employed makes use of the fact that the linear movement of the punch during a

Jan 1, 1962

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

Solid-solubility limits at 1500°, l000q and 500°C for carbon, nitrogen, and oxygen in high-purity tantalum were determined by X-ray lattice-parameter methods. For carbon, the solubility was found to be 0.17 at. pct at 1500°C, and less than 0.07 at. pct at 1000°C. A nitrogen solubility of 3.70 at. pct at 1500° C decreases linearly with temperature to 2.75 at. pct at 1000°C, and 1.8 at. pct at 500°C. In the case of oxygen, the solubility was found to be 3.65 at. pct at 1500°C, 2.95 at. pct at 1000°C, and 2.5 at. pct at 500°C. The phases Ta2C, the low-temperature modification of Ta205, and Ta,N of unknown composition but which has a superlattice structure based upon the original bcc tantalum lattice have been identified as the initial precipitates in the respective systems. Metallographic methods were employed to verify the X-ray analyses. The etching behavior of Ta is discussed in terms of lattice i?rzperfections and precipitate phases. The excellent fabricability, high melting point, and nuclear properties of tantalum are responsible for interest in this refractory metal. Data on the solid solubility of the interstitial elements (oxygen, nitrogen, and carbon) in tantalum and on the precipitate phases are somewhat limited. The significant contributions are discussed below. Because the purity of electron-beam melted tantalum (only recently available) is considerably higher than that used in previous studies, the present investigation was initiated. Gebhardt et all-3 have investigated the tantalum-oxygen and tantalum-nitrogen systems with particular reference to the changes in physical properties and to the rates of reaction between these gases and the metal. The solubility of oxygen in tantalum was reported2 to be 3.7 at. pet at 1500°, 2.3 at. pet at 100O°C, and 1.4 at. pct at 750°C. Schonberg4 reported that several oxide phases (Ta40, Ta,O, TaO and Ta,05) exist while X-ray studies by Gebhardtl showed only two oxides, Ta,05 and an unidentified phase which was associated with a platelet-type precipitate. La-gergren and Magneli,' however, questioned the existence of compounds other than the two allotropic modifications of Ta,05 for the tantalum-oxygen system. In the case of nitrogen, the solubility was estab- lished by Gebhardt3 to be of the order of 7 at. pct at 1800°c. The solubility was reported to decrease rapidly with temperature, and, although no limits were established, a precipitate phase was observed by Gebhardt except when the high-nitrogen specimens were cooled very rapidly from the reaction temperature of 1800c. He reported the initial precipitate phase to be a tetragonal distortion of the bcc tantalum lattice while Schonberg6 reported the phase lowest in nitrogen Jo be a cubic super-lattice with a cell size of 10.11 A. Two other nitride phases, Ta,N and TaN, were reported; these appear to be isomor-phous with the carbides of tantalum. The tantalum-carbon system was investigated by Ellinger7 and by Lesser and Braurer. Two compounds, Ta,C and TaC, were reported to exist, each with a range of composition. The solubility of carbon in tantalum was found to be practically nil at all temperatures. Thus, of the interstitial elements which are present in small amounts in high-purity tantalum, carbon might be expected to form precipitates. The present investigation was initiated to obtain additional data on the solid-solubility limits of these interstitials at 1500°, 1000°, and 500' with particular emphasis on the distribution and the identification of the precipitate phases. EXPERIMENTAL WORK AND RESULTS In the present investigations of the solid solubility and of the precipitate phases in the systems tantalum-nitrogen, -oxygen, and -carbon, high-purity tantalum was reacted with high-purity gases, homogenized at 1800°c, and annealed at and quenched from 1500°, 1000,

Jan 1, 1962

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 Barbara A. Thompson

A previously reported high-resolution method for the location of boron-rich areas in metallurgical and biological specimens was been adapted for general use on a routine basis. The rnetlzod utilizes neutron activation and autoradiograpizy. Alpha-particles emitted by boron nuclei upon neutron capture are recorded on a photographic emulsion. The resulting a-particle tracks show the location of boron-rich areas. Experimental techniques, interferences, and limitations of the method are discussed in detail. The method is most useful where there is marked segregation of boron. In this type of sample, the segregation can be observed when the nominal boron concentration is as low as 0.0006 pct. THE positive identification and location of boron-rich areas in metals is frequently of great interest in metallurgical work. Unequivocal identification is often difficult to make by conventional metallo-graphic methods. Recently, a method has been described which accomplishes this objective by neutron activation and autoradiography.l-3 The method can be described briefly as follows. Upon neutron capture, a -particles are emitted by boron nuclei according to the following reaction: ,Blo + n - ,a4 + 3Li7 + 2.4 mev The energy is dissipated as kinetic energy of the products. By irradiating a boron-containing sample in contact with a photographic emulsion and subsequently developing this emulsion, a-particle tracks are obtained whose location corresponds to the location of boron-rich areas in the sample. Two factors combine to make the reaction extremely specific for boron. The first is the unusually high (755 barns) cross section of boron for thermal neutron capture. The second is the higher neutron energy required to produce (n, a ) reactions in essentially all other nuclei except lithium. These two factors make the method specific for boron by six to seven orders of magnitude when a predominantly thermal neutron source such as the Brookhaven reactor is used. The reported limit of detection of this method is of the order of 0.01 pct B., The present work was originally undertaken to determine whether this limit could be lowered by use of a thinner emulsion. However, initial experiments showed that in order to use the method at all, it was necessary to reestablish the optimum experimental conditions in terms of the available irradiation facilities. It is the purpose of this paper to describe these experimental conditions in detail, to discuss the factors influencing sensitivity, and to evaluate several techniques for increasing sensitivity. EXPERIMENTAL A) Preliminary Experiments—The first measure-ments were made using samples of crystal oriented silicon steel containing various concentrations of boron. In the later experiments, samples of various high-temperature alloys such as M-252, hcoloy 901, Nichrome V, and so forth, were used. Faraggi, et al.,2 reported that the lower limit of sensitivity in this type of sample was about 0.01 pct B using nuclear emulsions of 50- u thickness. but that it should be possible to extend this limit by the use of thinner emulsions. Accordingly, we first used Kodak Auto-radiographic Stripping Film (Permeable Base) which has an emulsion thickness of only 5 µ. This was mounted on the metallographic specimens according to the technique described by Boyd.4 The emulsion remained in contact with the metal surface throughout exposure and development. Since the emulsion is transparent after development, the autoradiograph and metal surface can be viewed simultaneously and any correlation between film blackening and structure of the metal can be made directly with no problems of realignment. Because the silicon steel is readily attacked by moisture alone, it was necessary to apply a protective coating to the metal surfaces before mounting the emulsion. The coating was made extremely thin in order to absorb as few a-particles as possible. Boyd4 and Gomberg5 have discussed various plastics used for this purpose; however, none was sufficiently impermeable to prevent chemical attack of the steel during the developing process. This attack resulted in the production of gross chemical artifacts in the emulsion. It was, therefore, necessary to use the method of Wolfsberg and John6 as follows. A very thin (approximately 1 µ) coating of Plexiglas II was applied by dipping the sample in a 2 pct solution of Plexiglas II in dichloroethylene. Then, because the emulsion will not adhere to Plexiglas 11, a thin coating of Parlodion was applied in a similar manner using 2 pct Parlodion in iso-amyl acetate. No protective coating was necessary with the high-tem-

Jan 1, 1961

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's re- quest but some authors of papers that I have found of special interest are mentioned.

Jan 1, 1940

By Carl F. Lutz, Robert F. Mehl

A layer of brass was formed on 0 brass using a vapor-solid reaction technique. The variation in composition with distance within the phase layer and across the a -ß interface was determined by an electron probe. The diffusivities were calculated as a function of concentration; the diffusion coefficient in brass was found to change by a factor of twenty-five over a compositional range of 8 at. pct. An explanation is proposed to account for the large change in the diffusivity, based on possible stresses in the diffusion zone; it is suggested that the concentration dependence of the thermodynamic factor might decrease the activation energy with increasing zinc content. ALTHOUGH the body of data on diffusion coefficients (D- values) in terminal solid solutions and in isomorphous systems is quite large, there is but little quantitative information for intermediate alloy phases. This paper recounts measurements of D-values for the ? phase in the Cu-Zn system. The experimental method employed consists in the forming of alloy layers and determining and analyzing the concentration-distance (c-x) curve. The experimental method employed could have been applied to several systems; the Cu-Zn system was chosen because the D-values in the a and ß phases are well known, and can thus be used for purposes of comparison. The rates of growth, of intermediate alloy layers are known for a number of systems. In nearly all cases the thickness varies parabolically with time, as to be expected if the rate of growth is controlled by the D-values. In a few cases, nonparabolic behavior has been noted.1 Nonparabolic growth may be the result of a) a variation of the composition at the phase interface with time, b) interface-controlled kinetics, c) short diffusion times coupled with long vacancy lifetimes (in vacancy diffusion),2 and d) crystal reorientation during diffusion in anisotropic systems.3 In the Al-Ni system4 and in the Al-u5 system parabolic growth kinetics are slowly approached after an initial transient period. In general those phases stable at a given temperature in a system A-B appear as separate phase layers when A and B are put in contact and given a diffusion he at-treatment. In most cases the compositions at the interface of adjacent phase layers are those read from the phase diagrams for the termini of the respective phases. This discontinuity in concentration is taken as independent of time, and the growth of one phase at the expense of another is assumed to be independent of interface kinetics, i.e., the rate of interface movement is controlled by volume diffusion in the phases concerned. wagner6 has given many solutions for multi-phase diffusion processes, assuming that the chemical diffusion coefficient, D, is independent of concentration, as have others. Jost7 has pointed out that the familiar Boltzmann-Matano solution is as valid for a (c-x) curve exhibiting concentration discontinuities at phase boundaries as for the usual single-phase case. Heumann and associates8,9 have applied this solution to the multi-phase case, but lacking concentration data within the several layers were forced to assume linear concentration gradients, thus calculating only average D-values. The purposes of the present study were: 1) to determine the dependence of D on concentration, 2) to calculate the intrinsic diffusion coefficients D?Cu and D?Zn, 3) to establish the time-law for the movement of the interface, 4) to determine the concentration limits at the ß-? interface, and, 5) to attempt to clarify the mechanism of diffusion. EXPERIMENTAL PROCEDURE The ? phase is exceedingly brittle; conventional solid couples and conventional sectioning methods were thus inapplicable. Vapor-solid couples were accordingly employed. Unfortunately the equilibrium vapor pressures of Zn for the ? phase are unknown; to escape this awkwardness, samples were enclosed in a capsule containing powder of an alloy of known composition, sufficiently large in quantity as to be effectively an infinite source, maintaining the concentration of Zn at the sample surface constant with time. The sources of Zn-vapor which can be employed in reaction with Cu, or a brass, or ß brass, to form a layer of ? brass satisfactorily wide in concentration range, are alloys of the phases ?, or ? + E or ? + d (depending on the temperature).

Jan 1, 1962