Search Documents

By C. H. Li, R. J. Stokes

This paper compares the fracture behavior of tungsten rods in three conditions: recrystallized. recovered, and wrought. Notched specimens suhjected to a 50 in.-lb impact load showed ductile-brittle transitions at 700, 4.90°, and 440°C, respectinely. The recrystallized material had an equiaxed pain structure and jracbred by simple cleavage from a grain boundary source at all temperatures up to 700°C. The wrought and recovered material had an elongated fibrous structure and at low temperatures fractured by cleavage originating from the notch. As the transition temperature was approached cleavage was preceeded by more and more intergvanular splitting which deflected the crack front into planes parallel to the tensile axis. The enhanced toughness of wrought and recovered tungsten was attributed both to its inability to initiate cleavage because no pain boundaries were suitably oriented perpendicular to the tensile stress and to its inability to maintain cleavage because of intergranular splitting ahead of the crack. It has been appreciated for a long time in a qualitative manner that the room-temperature brittleness of fully recrystallized tungsten may be alleviated by working the material at relatively low temperatures.' More recently this difference in mechanical behavior between wrought and recrystallized tungsten has been examined quantitatively by measurement of the tensile properties as a function of temperature. In these experiments brittleness has been expressed in terms of ductility or reduction in cross-sectional area upon tensile fracture or in terms of the bend radius before fracture under bending.' This work has shown the existence of a fairly sharp transition from brittle to ductile behavior with an increase in temperature. The ductile-brittle transition temperature for recrystallized material is approximately 200°C higher than for wrought material. An increase in strain rate, small additions of impurity,' or an increase in grain size4 shift the respective transition temperatures to higher values, but the difference between them remains approximately the same at 200°C. A number of explanations for this embrittlement by recrystallization have been given. It has been blamed either on the concentration of impurity at the grain boundaries, the increase in grain size, or the change in texture which occurs upon recrystallization. The present paper examines the effect of different heat treatments on the notch-impact behavior of commercial powder-metallurgy tungsten rods. The change in the ductile-brittle transition temperature for this method of loading and the fracture mode has been related to the different mi-crostructures produced by heat treatment. EXPERIMENTAL PROCEDURE Commercial swaged powder-metallurgy tungsten rods 1-3/8 in. in length and 1/8 in. in diameter were machined to introduce a sharp V notch 0.030 in. deep. To change the microstructure from that of the as-received wrought material some of the specimens were subjected to an anneal in nitrogen either at 1300° or 1400°C for 8 hr or at 1600° or 2000°C for 1/2 hr. The notched rods were then placed in a miniature Charpy-type impact machine and struck at their midpoint (opposite the notch) with a hammer designed to deliver 50 in.-lbs of energy. The strain rate at the base of the notch was estimated to be approximately 100 sec-1 at the instant of impact. The specimens were heated in situ to the desired impact temperature. The microstructures produced by the various anneals were studied by both X-ray diffraction and metallographic techniques. Fig. 1 reproduces the microstructures observed metallographically following a 10-sec electroetch in a 10 pct KOH solution. Fig. l(a) shows the elongated fibrous grain structure of the as-received material. Following the anneal at 1300" or 1400°C the grain structure was still elongated as shown in Fig. l(b) but the etch pits delineated dense polygonized dislocation arrays within many of the grains. Occasionally a relatively dislocation-free recrystallized grain was found growing into the matrix. The anneals at 1600° and 2000°C resulted in complete recrystallization and some grain growth. The grains produced at 1600°C were still slightly elongated as shown in Fig. l(c) whereas the anneal at 2000°C produced equiaxed grains. The changes in grain size produced the expected changes in the X-ray back-reflection patterns; there was no indication either in the as-received material or the annealed material of any preferred orientation. RESULTS a) Impact Behavior. Fig. 2 reproduces the ductile-brittle transition curves measured in the manner described in the previous section. It can be seen that under these testing conditions the as-received

Jan 1, 1964

By J. B. Newkirk

ABOUT twenty-seven years ago W. bergl discovered that interesting detail could be seen in an X-ray diffraction spot made with a rock-salt crystal if the recording photographic film were held very close to the reflecting crystal. He also showed that much of this detail could be explained in terms of the deformation structure of the specimen. In the same year, 1931, Fox and parr2 reported that X-ray reflections from a quartz crystal were much more intense while the crystal was undergoing piezoelectric oscillation than when it was at rest. This observation was soon confirmed (and explained in terms of X-ray extinction) by Barrett3 in the United States and by Nishikawa et a1.,4 in Japan. During the next few years Barrett refined Berg's method for making X-ray diffraction micrographs and applied it to the study of metallic crystals. He reported this work in the 1945 annual lecture of the AIME.5 Since 1945 relatively little use has been made of the Berg-Barrett (B-B) method for making diffraction micrographs, though considerable interest in investigating subcrystal structures by other methods has developed. Some of these methods depend upon evaporation6 or chemical etching7 and, therefore, suffer from the occasional intrusion of subtle artifacts such as those recently reported by Hooker for leada and Welsh for aluminum.9 Other methods require the introduction of foreign elements which "decorate" the substructure in some way, thereby rendering it detectable by direct" or indirect1'. visual examination. Still others depend upon complex and often highly questionable analyses of X-ray diffraction line profiles. There have also been a number of related X-ray techniques, such as the Lambot,12 Schulz13 and Merlini and Guinier,14 which have proved to be quite useful for specific applications. Some of these methods give a picture of the substructure which is more or less directly related to the shape and the topography of the specimen. The Berg-Barrett method carries this desirable feature to the limit. Closely related to the B-B method are three photographic X-ray techniques recently described by Lang.15 These methods give beautiful pictures of the internal structure of crystals but are limited by the facts that the required apparatus is rather complex, exposure times are long, and the specimen crystals must be thin. An experimental appraisal which I have recently made of the original B-B method has shown that this simple technique is not only inexpensive and convenient, but can give more information than was apparently realized by its inventors. For example, first-order subgrains in iron-silicon crystals were clearly delineated and their relative orientation subject to description. Also defect structures could be seen within the subgrains and in some materials slip bands could be clearly seen with respect to the topography of the rest of the specimen. This much had already been described by Barrett. However, in the present study it was found that the actual sites of individual dislocations which emerge upon the crystal surface could be located. Furthermore, by a simple procedure, the direction (but not sign) of the dislocation Burgers' vector could be defined as well.

Jan 1, 1960

By A. E. Gorum, I. Cornet

Fatigrle of ionic crystals has been studied primarily in magnesinm oxide. under cyclic stress dislocations move irrreversibly; they multiply; slip bands form and grow; cracks mucleate and propagnte, and failure occurs. The use of ionic crystals such as MgO is advantageorus in such investigations because they are optically transparent. Individual dislocation Intersections with {100} surfaces may be observed with a standard microscope, using etch-pit techniques. Slip, deformation, crack .formation, and fracture in MgO crystals under cyclic stress are compared with cotrresponditzg processes in metals. ThE effect of cyclic loading in metals has been studied for many years. The appearance of slip lines is readily observed and the ensuing fracture may also be seen. From these observations it is possible to predict the behavior of a material and make an educated guess as to what is happening internally, but the actual changes taking place within the structure are not readily apparent. If one could obtain a material in which the individual glide components could be observed, it would be invaluable in determining the actual slip distribution resulting from cyclic loading as well as the distribution of slip in the neighborhood of a growing crack. Such a material is magnesium oxide. Dislocation arrays may be observed by means of etch pits

Jan 1, 1961

By R. E. Hook, H. J. Garrett, A. M. Adair

X-ray diffraction and metallographic techniques were employed to examine the impurity phases occurring in as-swaged and recrystallized chromium produced fvom high-purity iodide chromium crystals. Chromium oxides are found to form in a consistent manner associated with the temperature of recrystallization. Microscopically observable second phase particles of Cr203 are observed to form intergranulurly beginning at 1300T. Beginning at 1500°C. Cr30, is formed intergvanulurly, atzd at 1600°C and above Cr30, is also formed in association with migrating grain boundaries. Geometrical traces formed by particles of this high temperature oxide uithin the grains rez)eal the histmy of grain boundary motion. X-ray evidence is presented which suggests the existence of a high temperature form of Cr203. Other impurity phases in addition to the oxides of chromium are also present. THE partitioning Of impurity elements between grain boundary aid lattice sires, either as solutes in solution or as second phases, may exercise an important influence on the mechanical behavior of metals and alloy systems. This partitioning of impurities could have a direct bearing on the iecrys-

Jan 1, 1963

By R. F. Hehemann, D. J. Cometto, G. L. Houze

The w transformation in the Zr-Nb system was studied using X-ray diffraction, dilatometric, re-sistornetric, hardness, and metallographic techniques. w forms in a diffusionless, completely reaersible manner on quenching and in a diffusion-controlled manner- on aging. The temperature at which w begins to form on quenching was determined as a Junction of composition and was found to decrease with increasing solute content. w formed bv aging establishes a metastable equilibrium with an enriched ß phase. The ß/w + ß transus has been determined for this metastable equilibrium and employed to rationalize retrogression and reversion phenomena observed in these alloys. The decomposition mechanism is discussed in terms of a gradual or continuous transformation from ß to the w state. BETA- stabilizing alloying elements lower the MS temperature of the martensitic bcc (ß) to hcp (a') transformation in zirconium and titanium alloys. In certain titanium alloys, a lower symmetry modification of the martensitic structure, termed (a"), also has been reported.1,2 These martensitic transformations are suppressed when the amount of the ß-stabilizing element exceeds a critical level. However, the high-temperature ß phase cannot be quenched to room temperature without change. At alloy contents just above the critical level, |ß trans-forms to the w phase when cooled rapidly.3-6 The amount of w in quenched alloys is reduced by increasing alloy content, and this phase virtually disappears above a critical composition.5 In addition to the transformation during cooling, w also can be formed by aging ß at temperatures below approximately 500°C, and significant alloy enrichment of retained 13 accompanies the isothermal transformation.1-8 The structure of LC is closely related to that of the ß from which it forms.9-15 The bcc (ß) lattice can be generated using a hexagonal cell with three atoms located at (000) and ±(2/3, 1/3, 1/3). This cell has an axial ratio of 0.612 and is oriented with respect to the cubic cell such that (0001)H (111)C and [1120]H [101]C. Consequently, there are four possible orientations of the hexagonal cell, associated with the four (111) planes of the bee lattice. Formally w can be obtained from 0 by allowing the two atoms at the ±(2/3, 1/3, 1/3) positions to approach the coordinates ±(2/3, 1/3, 1/2) and there are four equally probable orientations of w for each 0 grain. In titanium alloys w retains the cubic axial ratio of 0.612" and hence also can be indexed as triply cubic, but this is not the case for aged Zr-Nb alloys where w is clearly hexagonal with an axial ratio of 0.622." The lattice parameters and atomic positions of w depend on thermal history and alloy content. The atomic positions (000), ±(2/3, 1/3, 1/2) provide reasonable agreement between calculated and observed diffracted intensities for w in the fully aged condition.10,14 In the quenched condition, on the other hand, the atoms appear to be displaced from the central plane12,13,15 and assume positions ±(2/3, 1/3, Z = 0.42-0.48) rather than ±(2/3, 1/3, 1/2). This results in a structure with trigonal rather than hexagonal symmetry. The readily detectable parameter and axial-ratio changes of w in Zr-Nb alloys make this system especially attractive for studying the structural changes that occur in the formation and aging of w. Particular attention in this investigation has been directed to the relationship between the structure of w in the quenched and aged conditions, and to certain aspects of the reaction kinetics. MATERIALS AND PROCEDURE Zr-5, 12, 17.5, and 25 pct Nb alloys were prepared by a double arc-melting practice, encased in stainless-steel cans and hot-rolled to 1/8-in.-thick sheet.* Charged weights have been employed for the niobium contents and interstitial analyses are reported in Table I. Dilatometric, X-ray diffraction (filtered CuK, and MoK, radiation), metallographic, and hardness techniques have been employed to follow the transformations during isothermal and quench-aging heat treatments. In quenched specimens, the electrical resistivity also was studied. Betatizing was conducted for 1 hr at 900°C. With the exception of the isothermal dilatometric studies, samples were

Jan 1, 1965

By Paul A. Beck, M. N. Parthasarathi

The vecrystallization texture. formed by selective growth of random nuclei in an 80 pct volled 99.997 pct A1 crystal of initial orientation mear (123) (41.21 was found to consist of components related to the single-component rolling texture by 40 deg. rota-tiows around [111]axes. The relative-volume fractiovz of the various recrystallization-texture componezts may be accouzted for 012 the basis of the Lou) mobility of twist boundaries, if it is assumed that the mobility of the tilt boundaries also varies with their orientation. Similar results with a, aluminum-alloy cystal of the (110) [112] orientation, containing iron, silicon, and zinc, show that these solute contents do not impair the effectivezess of the oriented growth mechanism of re cry s-tallization- texture formation. In a previous investigation1,2 it was found that a sharp recrystallization texture is formed as a result of the oriented growth of random artificial nuclei in an aluminum crystal rolled to 80 pct RA, on the (110) plane in the [ 112] direction. Four recrystallization-texture components were found to occur, with orientations corresponding to 40-deg rotations around [111 1 axes of the deformation texture. Reorientations of this type were already found in earlier work,3,4 where the presence of random nuclei could be reasonably assumed, but was not rigorously documented. The same orientation relationship was found also by Lucke and Liebmann, who actually measured the orientation dependence of boundary-migration rates in the recrystallization of A1 crystals slightly deformed in tension.5,6 The occurrence in the recrystallization texture of only four of the eight crystallographically equivalent orientations of the type referred to above remained unexplained,1,2 although it was clearly not a result of the absence of suitable nuclei. Recently Burgers7 suggested that this effect may be due to the aniso-tropy of boundary mobility observed2'6; it was found that the recrystallized grains of the 40-deg [111]-rotated type grow much faster in directions perpendicular to the [ 111] they have in common with the matrix than parallel to this direction, i.e., the tilt boundaries have much higher mobility than the twist boundaries. The four orientations corresponding to

Jan 1, 1962

By J. J. Kramer, K. Foster

The orientation distribution of surface-energy -induced secondary recrystallized grains was determined. This work was conducted on thin sheets of a 3 pct Si-Fe alloy annealed under environmental conditions that furor grouth of grains with a (100) plane in the surface of the sheet. The texture was found to be extremely sharp and almost independent of sheet thickness. The distribution varied exponentially with the angular deviation from the {100} plane. It was possible to relate the distribution to the nu-cleation rate of the secondary rains as influenced by the surface-energy difference. THE role of surface energy in the secondary grain growth of cube-oriented grains (grains with a (100) plane in the plane of the sheet) in thin Si-Fe sheets has been previously discussed.1-4 In high-purity sheet material normal grain growth usually occurs until the grains have extended through the sheet. Further grain growth is inhibited by the thermal grooving of the boundaries at the sheet surface. However, additional growth of cube grains can occur by a secondary grain growth process under conditions where the (100) plane has a lower surface energy than other orientations. Apparently for these alloys, cusps exist in the polar plot5 of surface free energy with the lowest cusp energy occurring at the (100) orientations. This has been reported to be the result of preferential adsorption of sulfur on the (100) planes.6 As a result of this process, a distribution of orientations could arise from two possible mechanisms. First, when a cusp is present in the polar plot of surface free energy, there are orientations inside the cusp that have a lower surface energy than elsewhere on the polar plot. Also, at sufficiently high temperatures, flat surfaces whose orientations are inside or just outside the cusp (depending on its shape) can often thermally etch, yielding a microscopically stepped surface of even lower surface energy. As a result, grains oriented close to cube would also have a lower surface free energy, either because of the cusp shape or by thermal etching, and could possibly grow as secondary grains by the surface-energy phenomenon. One should thus observe a distribution in the surface orientation of the cube grains comprising the secondary structure. It is the purpose of this paper to investigate this orientation distribution experimentally and to discuss the factors involved in its formation. For this purpose, the surface orientations of a large number of secondary grains in various sheet thickness were determined by means of the Laue back-reflection X-ray technique. PROCEDURE A vacuum-melted 3 pct Si-Fe alloy containing a nominal impurity content of 0.005 wt pct was processed into strip. A single cold-rolling step of 90 pct reduction was used for each strip regardless of the final sheet thickness. Final strip thicknesses of 0.60, 0.30, 0.15, and 0.075 mm were used. Care was taken to insure that the final strip surface was smooth and flat. All strips of a given thickness were annealed together at 1200°C in dry hydrogen (dew point -70°C) to develop the desired secondary structure and to insure identical environmental annealing conditions. The annealing time was selected to develop a complete secondary structure in the thinner sheets but to permit the thicker sheets (0.60 mm) to have residual primary grains remaining. This was necessary to determine whether growth impingement could lead to one secondary grain consuming another at a greater angular deviation. For the X-ray determination of the surface orientation of the secondary grains, a special specimen holder was used. The camera and holder arrangement could be aligned by X-raying a grain in three positions rotated 180 deg to each other. Thus, with a small beam X-ray focus (1 mm), the surface orientation of any grain could be determined to within one-half a degree. The surface orientations of one hundred cube secondary grains were determined for each sheet thickness. The criteria of a secondary grain were its size relative to the sheet thickness and the number of sides of the grain observed in the sheet surface. (A primary recrystallized grain extending through a sheet will generally have six edges visible in the plane of the sheet, whereas a secondary grain will have many more when growing entirely into primary grains.) Grains were selected as randomly as possible by X-raying every secondary grain found along a line drawn on the strip. No attempt was made to determine the exact orientation of the planes of the surface, as many strips from randomly selected sheets were used. On1y the angular deviation of the surface plane from {100} was measured. In order to assess the volume distribution in the

Jan 1, 1965

By R. Maddin, C. H. Mathewson, W. R. Hibbard

According to conventional crystal mechanics, a face-centered cubic single crystal slips on the system {111} <110> which receives the highest shear stress in terms of the stated orientation of the stress axis of the crystal.l However, in brass, the slip process is never as simple as this conventional analysis indicates. There is always a second cooperating plane which contains the same slip direction as the primary plane.2&apos;3 There is still another cooperating slip system commonly called the conjugate system3 previously observed to function with considerable lag only after the rotation due to the action of the first plane had produced a symmetrical condition of equal shear stress on the two systems. In the 1943 Campbell Lecture,4 a slip mechanism was outlined in which the {111) planes moved step-wise in two adjacent <112> directions integrating into the <110> slip direction. "... the slipping process would be visualized as a succession of steps 30" to the right and left of the resultant, microscopically observed, slip direction; a first step setting up the twinned configuration in the single spacing involved and an ensuing slip returning the atoms to the untwinned configuration while completing a fully integrated <110> movement."4 This process is shown diagrammatically in Fig 1 which shows two close packed layers of atoms at a slip site. A movement of the full circles through the "valleys" into the adjacent sites would produce a twin configuration with respect to the open circles. The term, "twin fault," seems most appropriate to define this faulted condition of the lattice. Annealing twins in face-centered cubic metals may arise from preformed nucleii which could be described as twin faults produced by the first movement of this two stage slip process. However, it is clear that this kind of slip does not take place so as to embrace a measurable number of adjacent planes because careful X ray examination has not conclusively shown the existence of ponderable twin lamellae (as in the case of Neumann bands in the body-centered ferrite). In view of the imponderable character of these hypothetical twin faults, the search for evidence of their existence seems restricted to indirect methods. The most obvious experimental technique serving this purpose is the determination by micrographic and X ray methods of the alignment of the composition planes of annealing twins with the former slip planes in axially strained and recrystallized single crystals. In previous attempts of this sort not all of the annealing twins could be traced to slip planes known to be operative in the conventional sense and hence evidence appeared negative or inconclusive. With the discovery of additional slip systems2&apos;3 operating in conjunction with&apos; the major system of highest resolved shear stress in axially strained brass it became apparent that the simple technique outlined above might be re-employed with more gratifying results. If, on annealing single crystals of alpha brass previously strained in tension, twins are found with their composition planes parallel to all three operative slip planes and with no participation of the fourth plane there is good evidence in favor of the existence of twin faults and of the two stage slip process. Experimental Procedure and Resuits Single crystals of alpha brass of the 70-30 composition were grown by solidification from the molten state.

Jan 1, 1950

By P. E. Doherty, B. Chalmers

Subboundaries may be revealed in aluminum by the formation of pits on the surface during cooling from elevated temperatures. The pits do not form in the vicinity of high- or low-angle boundaries. They are attributed to the condensation of vacancies from a super saturation produced during coolirzg. Using the vacancy pit and Schulz X-ray techniques for observing low-angle boundaries, a study was made of the transition from the nearly perfect seed to the striated structuke characterist-ic of aluminum crystals grown from the melt. It was found that the individual striation boundaries develop by the coalescence of very small-angle boundaries, as well as by the addition of individual dislocations. Several mechanisms for the formation of striations are discussed. Evidence was found suggesting that a super-saturation of vacancies exists near a growing interface, and it is proposed that the resulting climb of existing dislocalions produces "half&apos;-loops" at the interface, which combine to form the low-angle striation boundaries. LINEAGE, or "striation" boundaries, have been studied in detail by Teghtsoonian and Chalmers 1,2 in crystals of tin grown from the melt, and by Atwater and Chalmers3 in lead. They found that single crystals grown from the melt consist of regions which are separated by subboundaries that lie roughly parallel to the growth direction. A difference in orientation of 0.5 to 3 deg exists between the striated regions; the misorientation is such that the lattice of one region could be brought into coincidence with the lattice of its neighbor by a rotation about an axis approximately parallel to the direction of growth of the crystal. They observed an incubation distance for the formation of striations which increased with decreasing growth rate. They also found that in any crystal, the sum of all rotations of the lattice in one sense, in going from one striation to the next, is very nearly equal to the sum of all the rotations in the opposite sense. A striation boundary, which is a low-angle grain boundary, can be described as an array of dislocations. If it is assumed that suitable dislocations are introduced into the crystal during solidification, the formation of striation boundaries can be explained as a result of the migration of the disloca- tions into arrays. The formation of arrays is energetically favorable since the energy of an assembly of dislocations can be reduced by the interaction of the stress fields when a suitable array is formed. This investigation presents and interprets new information concerning the nature and origin of striation boundaries in aluminum. EXPERIMENTAL TECHNIQUE Single crystals of high-purity aluminum (Alcoa 99.992 pct) were prepared by horizontal growth from the melt.&apos;&apos; The specimens were subsequently electropolished in a solution of 5 parts methanol to 1 part perchloric acid kept between -10° and 0°C in a bath of dry ice and alcohol. The current density was approximately 6 amps per sq in. Doherty and Davis9 have shown that in aluminum sub-boundaries with misorientations of not less than several seconds of arc may be revealed by the vacancy pit technique. During cooling from elevated temperatures pits form on electropolished surfaces of aluminum crystals as a result of the condensation of vacancies.11 Pits do not form in the vicinity of small- or large-angle grain boundaries, presumably because such boundaries act as sinks for vacancies. Boundaries of misorientations down to 3 sec of arc are revealed as pit-free regions, see Fig. 1. The Schulz X-ray technique12 was used to determine the angular misorientations of subboundaries. In this method, white radiation from a micro-focus X-ray tube is used to produce an image of a fairly large area of a single crystal surface. Subboundaries cause splitting in the diffracted image, see Fig. 2. Misorientations down to about 15 sec of arc may be observed with this technique. OBSERVATIONS AND DISCUSSION Figure 1 shows a striated aluminum crystal grown at 10 cm per hr etched by the vacancy pit technique. An incubation distance of about 1 cm is observed before the initiation of striation boundaries. Fig. 2 is a Schulz X-ray photograph of a striated crystal similar to that shown in Fig. 1. A large area of the crystal was studied by means of a series of photographs. Fig. 2, which is a reflection from the (100) plane, included about the first 4 cm of crystal to freeze. There is an incubation distance of about 1 cm, and a distance of about 2 cm over which the angle of misorientation builds up to its final value of approximately one degree. Some twist component can be seen in Fig. 2 at the right side of the photograph. From Fig. 2 it can be seen that the sum of all rotations of the lattice in one

Jan 1, 1962

By D. Walton, B. Chalmers

A preferred orientation is known to occur frequently in the columnar zone of castings. This has been attributed to a preferred direction of growth. However, no satisfactory mechanism was proposed by which the preferred direction of growth led to the preferred orientation. The purpose of this work has been to establish this mechanism. It has been found that in general the observed preferred orientations only develop when the preferred directions of growth reveal themselves by dendritic growth. A mechanism based on this premise is found to be in agreement with the experimental data obtained in the course of this work. WHEN a liquid metal is allowed to solidify in a mold, it usually freezes in three stages, distinguished from each other by the size and shape of the grains. The first zone to freeze (the chill zone near the mold wall) consists of relatively fine grains that are equiaxed in shape and random in orientation. The next zone consists of crystals that are elongated in the direction of heat flow, i.e., normal to mold wall. These crystals are much larger in cross section than the crystals of the chill zone and have a very strongly preferred orientation. This is the columnar zone. The final zone, which is absent in very pure metals, is again equiaxed and randomly oriented, but usually has a much coarser grain size than the chill zone. The purpose of this study is to describe and account for the crystal size and orientation in the columnar zone. The occurrence of a preferred orientation in the columnar zone is well known, and in 1940, Greninger&apos; suggested that it is apparently related to dendritic growth although at that time the only data were for metals with the face-centered-cubic structure. Table I shows that the direction of dendritic growth and the crystal axis that follows the heat flow direction coincide in all cases so far studied. The term "dendritic growth" is used here to represent the branched type of morphology that is characteristic of growth into supercooled melts.&apos; In addition to the supercooling which is necessary before nucleation will occur at the mold wall, the necessary supercooling for continued dendritic growth can be provided in a mold by heat flow into the already formed solid at an interface whose Liquidus temperature is depressed by an accumula-

Jan 1, 1960

By R. D. Reiswig, J. M. Dickinson

The 0s-Ir equilibrium diagram was determined. The diagram is of the simple peritectic type, with a peritectic temperature of about 2660°C. The solid miscibility gap is narrower than previously reported, the nearly vertical solvus lines occurring at about 42 and 63 wt pct 0s. Widmanstaetten figures resembling martensite in some of the two-phase alloys account for a previously suspected transformation. In view of the long history of use of such alloys, it is surprising that the 0s-Ir equilibrium diagram has not yet been completely determined. The boundaries of the miscibility gap in this system have been estimated to be between 24 and 39 wt pct 0s and 79 and 100 wt pct OS. It has been predicted3 that alloys of ruthenium, osmium, and rhenium with the fcc platinum metals should solidify peritectically in their two-phase regions. The metallographic examination of natural osmiridium alloys has been said4 to indicate, by the presence of a martensitic structure, the existence of a transformation or a phase separation. On the basis of superconducting transition temperature measurements, a 70 at. pct 0s alloy was found5 to be two-phase prior to annealing. EXPERIMENTAL The elemental components used in this work were obtained from several suppliers as sponge. The purities, stated by each supplier to be in excess of 99.8 pct, were confirmed in each case by a semiquantitative spectrographic analysis. The pure components were premelted in an inert-gas tungsten arc furnace with the evolution of some fume, crushed, and pickled for use as alloy melting stock. Upon arc melting to the final compositions, no fume evolution was observed. Because weight losses of the order of 15 mg or less were observed in preparing alloy buttons weighing 15 g, "synthetic analyses" were used in determining the compositions of the alloys. Alloys used in this investigation contained 15, 20, 33, 40, 42, 43, 45, 50, 55, 60, 63, 64, 66, 70, 79, and 80 wt pct 0s. Heat treatments of the alloy buttons and pieces thereof were performed in a previously described6 tungsten tube furnace under pressures of 105 torr or less. It was found that homogenization treatments on the specimens were essential to remove the severe coring which was present, a 3-hr treatment above 2300°C removing all the metallographi-cally visible evidence of coring. Following the various heat treatments, the specimens were "vacuum-quenched" by melting a tungsten fuse wire and allowing them to drop onto a water-cooled copper plate. In a few instances, specimens were quenched into molten tin for comparison, but no difference was apparent. Vacuum-quenched specimens cooled from 2400°C to below a red heat in less than 60 sec. Typical equilibration times varied from 3 hr above 2300°C to 88 hr near 1100°C. The utilization of successively longer equilibration times and the approach to equilibrium from both directions indicated that the times used were sufficient to give a close approach to true equilibrium. Heat-treatment temperatures were measured with a calibrated Leeds and Northrup optical pyrometer through a 0.120-in. lateral sight hole in the tungsten heater tube. It was known that the assumption of black-body conditions inside the 1-in.-diam by 10-in.-long tube was unwarranted. The empirical results of work with thermocouples and melting

Jan 1, 1964

By T. Johnston, B. Cox

The results of oxidation and corrosion experiments on niobium in oxygen and steam at temperatures of 350° to 650°C, and in dilute sulphate solutions at 300°C are presented. The oxidation of niobium in oxygen can be explained in terms of a pre-transition period, which obeys an approximately parabolic rate law, and a post-transition period in which a more rapid linear rate is partially stifled by restriction of the gas flow due to the gvowth of the porous outer film. Due to changes in the porosity of the outer layers the restriction presented by the porous outel. film attains a limiting value. Subsequent oxidation obeys a linear rate law and shows an almost linear dependence of the rate on gas pressure. liltimately a second failure of the protective film may take place leading to a further acceleration in the oxidation rate. In water vapor the oxidation of niobium follows a parabolic rate law and does not show a transition to linear kinetics. The higher oxide, Nba05, was usually absent from the NbO/NbO2 film which was formed. The addition of a small partial pressure of oxygen to the water vapo3, resulted in accelerated oxidation according to the normal kinetics for oxidation in oxygen. The oxygen reacted preferentially with the niobium, and the protective oxide film was reformed when all the oxygen had been consumed. This behavior supports the theory that nucleation of Nb205 on the surface of the protective NbO/NbO2 film is the cause of the accelerated oxidation. After oxidation in steam at high-pressure Nb2Os was found in the protective film. The mode of formation of Nb2O5 under these conditions did not produce a change in kinetics, but was thought to explain the comparatively large dependence on pressure of the oxidation rate. The kinetics of oxidation in oxygenated aqueous solutions at 300°C were similar to those for oxidation in oxygen. A penetrating attack on niobium sheet may be related to the second breakaway observed by some investigators of oxidation in oxygen.

Jan 1, 1963

By M. E. Wadsworth, I. B. Cutler, R. W. Bartlett

The oxidation kinetics of ZrC was studied between 450" and 580°C in oxygen pressures from 6.5 x 10-to 1 atm using a ther mogravimetric apparatus and sized powder samples. Two parallel rate controlling processes were observed. A surface reaction occurring at the ZrC-ZrO2 phase boundary accounted for most of the oxidation and had an activation enthalpy of 46 kcal per mole. The other process, believed to be diffusion of oxygen into the ZrC lattice partially replacing carbon, had an activation enthalpy of 53 kcal per mole. The enthalpy for chemisorption of O2 on ZrC was determined to be —13 kcal per mole. Water vapor in the presence of oxygen accelerated the surface reaction rate. THERE has been little reporting of formal rate studies or attempts to ascertain the mechanism of oxidation of carbides. MacDonald and Ransley1 studied the oxidation of titanium carbide which has the same structure as zirconium carbide, fcc. They observed an initial increase in rate with increasing temperature followed by a rapid decrease through a rate minimum and a subsequent second increase at higher temperatures. The discontinuity in the rate rise was attributed to a phase change in the oxide which changed the rate determining step from the surface reaction at the carbide-oxide interface to diffusion through the oxide layer. Samsonov and Golybera 2 studied titanium carbide and reported that during the initial period of oxidation a dense film of Tic-TiO was formed followed by the formation of less adhering layers of higher oxides. The purpose of this investigation was to study the kinetics of oxidation of zirconium carbide and to attempt to gain some knowledge of the mechanism by which oxidation occurs. EXPERIMENTAL PROCEDURE Measurement of the weight gain associated with the oxidation of ZrC was used to determine oxidation rates. The principal experimental parameters were surface area, temperature, and oxygen pressure. Although moderately sized crystals of ZrC can be grown by the Van Arkel method, the only commercially available ZrC is a powder. In using powders, the surface area must be controlled either by fabricating the powder into a sintered pellet with a measurable surface area, relatively fixed during oxidation, or by using sized unconsolidated powder and applying appropriate geometric considerations to the shape of the grains to correct for their diminishing surface areas as they oxidize. Both techniques involve some difficulties. pellets of binder-free zirconium carbide can be made by hot pressing, but it is difficult to obtain densities greater than 90 pct of

Jan 1, 1963

By E. W. Murbach

The oxidation of uranium carbide by oxygen at various pressures, and by air, has been investigated at temperatures up to 600°C. Arc-melted and cast uranium carbide displays oxidation behavior that appears to be dependent on its treatment after melting. ccReactive" uranium carbide, which results from exposure of freshly melted material to laboratory air, ignites in oxygen at about 275° to 350°C depending on pressure, and in air at about 350°C. The product of the initial oxidation appears to be UO2+.. Continued heating produces U30,. The initial oxidation rate is poportional, roughly, to the square root of the oxygen pressure. The activation energy determined for the initial oxidation reaction is 7.1 kcal, from 400° to 600°C in 10 mm of oxygen. AN investigation of low-decontamination methods for reprocessing uranium carbide reactor fuels is being carried out at Atomics International. One of the reprocessing cycles includes oxidation of the fuel at relatively low temperature (300° to 500°C) and reaction of the product oxide with carbon at elevated temperatures (above 1500°C) to produce uranium carbide. A number of small-scale experiments have been carried out in which uranium carbide was oxidized in air and oxygen at various pressures to measure reaction rates and to obtain other information concerning the oxidation process. In initial experiments with arc-melted UC, ignition was observed at about 275°C in oxygen or 350°C in air. However, similar experiments by Neymark&apos; at 426°C in air showed no ignition. It was soon determined that the difference in oxidation behavior was due to the treatment of the UC following arc-melting. Neymark&apos;s experiments were carried out with freshly melted UC while those reported in the

Jan 1, 1963

By S. T. Wlodek

The surface and subscale oxidation reactions were followed by means of continuous weight-gain and metallographic techniques over the range 1600" to 2200°F (871° to 1204 °C) for up to 400 hr. Full identification of all scale and subscale reaction products was obtained by electron and X-ray diffraction. At or below 1800°F (982°C) a linear rate of reaction (QL = 46.0 kcal per mole) governed the oxidation process, extending for up to 100 hr at 1600°F (871 "C). During linear oxidation the surface scale consisted of an amorphous SiO2 film overgrown with Cr 2O 3 and NiCr204. This initial linear process was followed, and above 1800°F completely replaced, by two successive parabolic rate laws (Qp = 60 and 57 kcal per mole). This parabolic reaction involved the formation of a complex scale consisting of Cr2 O3 and smaller amounts of NiCr2O4. Parabolic oxidation appeared to coincide with the disruplion of the silica film present during linear oxidation and was followed by subscale (internal) oxidation of crystobalite and NiCr2O4. The balance between the subscale and surface oxidation reactions controls the oxidation of this commercial alloy. The amorphous silica film appears to result in the linear rate and diffusion through Cr2O3 is the more likely rate-limiting step during parabolic oxidation. THE oxidation of a multicomponent composition is a complex phenomenon not presently amenable to a rigorous classical interpretation. Nevertheless, even a qualitative understanding of the scaling and subscale reactions that occur in a commercial composition can illuminate the reactions that limit its high-temperature stability in an oxidizing environment. This study of the oxidation of Hastelloy Alloy X presents the first of a series of studies with the above approach in mind. Hastelloy X exhibits one of the best combinations of strength and oxidation resistance available in a wrought, solution-strengthened, nickel-base alloy. Although during long time exposure some precipitation of M6C and M23C8 carbides as well as a complex Laves phase occurs, the amounts are probably small enough to have no appreciable effect on the chemistry of the matrix. Radavich has identified the oxidation products on Hastelloy X oxidized for 5 min to 10 hr at 1115°F as NiO and the NiCr2O4 spinel. Oxidation for 5 to 15 min at 1500°F produced a scale of spinel, NiO, and a rhombohedra1 phase, probably Cr2Os. Sannier et 2. have reported continuous weight-gain data for Hastelloy X at 1650" and 2010°F and internal-oxidation measurements after 150 hr at 2010°F. In addition, much of the data on binary Ni-Cr alloys recently reviewed by Kubaschewski and okins&apos; and Ignatov and Shamgunova4 as well as studies of binary Ni-Mo alloys5 are also pertinent to the oxidation of this composition. EXPERIMENTAL Continuous weight-gain measurements and metallographic measurements of subscale reactions were the main experimental techniques used in this study. X-ray and electron diffraction backed up by a limited amount of electron-microprobe analysis served to characterize the nature of the scale- and subscale-reaction products. Two heats of commercial sheet of the composition given in Table I and identified as A and B were used in the bulk of this study. Internal-oxidation measurements were made on a third heat of material in the form of a 0.5-in.-diam bar. In order to assure homogeneity, all heats were reannealed 4 hr at 2175°F prior to sample preparation. weight-Gain Measurement. All specimens (1.5 by 0.4 by 0.03 in.) were abraded through 600 paper, electropolished, and lightly etched in an alcohol-10 pct HCl solution. An electrolyte of 150 cu cm H,O, 500 cu cm HsPO4 (85 pct conc), and 3 g CrO3 at a current density of 0.9 amp per sq cm or a solution of 10 pct HaW4 in alcohol used at 4 v and 0.3 amp per sq cm was used for electropolishing. The resultant surface exhibited a finish of 3 ± 1 p rms. Continuous weight-gain tests were made at 1600°, 1700°, 1800°, 1900°, 2000", and 2200°F on auer&apos; type balances capable of recording a total weight change of 110 mg with an accuracy of k0.1 mg. All tests were made in air dried to a dew point of -70°F and metered into the 2-in.-diam reaction

Jan 1, 1964

By W. W. Smeltzer

The linear formation rates of wustite films have been determined over the temperature range 590° to 1030°C using a vacuum microbalance technique. These rates are dependent directly on the partial pressure of carbon dioxide, Activation energies for film and scale formation in carbon dioxide and oxygen atmospheres are equivalent to either the dissociation energies of carbon dioxide and oxygen, or the activation energy for the diffusion of cation vacancies in wustite. Of the metals, iron is the most widely used basic constituent of durable alloys despite its intrinsic property of converting at a relatively rapid rate to the oxides from which it is derived. This property has accounted partially for many investigations on the oxidation of iron at low and high temperatures. Interpretation of the results have been complicated by formation of multilayers containing the various oxide phases. To aid in elucidation of the oxidation kinetics, measurements have been carried out in this investigation on the growth of the wustite surface layer. There are several studies directly related to the objective of this investigation. The growth of multilayer scales has been demonstrated to be diffusion controlled in oxygen at atmospheric pressure over the temperature range 450" to 1200°C by Davies, Simnad, and Birchenall.&apos; To gain an insight into the diffusion mechanism, Himmel, Mehl, and ~irchenall&apos; determined the self-diffusion coefficients of iron in wustite, magnetite, and hematite. These results were used to evaluate the oxidation rates of iron and its oxides, taking as a basis the theoretical parabolic rate equation developed by Wagner., The evaluations were compared to experimental data and were shown to provide essential confirmation of this theory. Fischbeck, Neundeubel, and salzer4 have demonstrated that the oxidation of iron in carbon dioxide and other atmospheres at high temperature obeys a linear relationship. Because the Arrhenius temperature coefficients of the reaction rate constants changed at the A, point they concluded that the passage of iron into the oxide controlled the reaction. This viewpoint has been accepted by Benard and ~albot&apos; to explain the occurrence of linear rates in oxygen before the onset of diffusion-controlled parabolic oxidation. This basic premise of a rate-controlling reaction at the iron/oxide interface has been questioned recently by Hauffe and Pfeiffer.&apos; Since the formation of wustite may follow a linear or parabolic relationship depending on the pressure of the gaseous re-actant, they propose that linear oxidation is determined by a chemisorption reaction while parabolic oxidation is controlled by diffusion. As confirmation of this viewpoint, Hauffe and pfeiffer6 and Pfeiffer and ~aubmeyer&apos; have established that the linear scaling constants of wustite formation at 1000°C in carbon-dioxide or low-pressure oxygen atmospheres

Jan 1, 1961

By W. C. Hagel

In 1952, Hauffe and pfeiffer1,2 reported that parabolic rates of nickel oxidation are decreased by factors of two and four at 1100° and 1000°C, respectively, when Li2O vapor is present. Hauffe &apos;s3 explanation was that monovalent lithium enters the crystal lattice of p-type NiO to decrease cation-vacancy concentration and, hence, diffusion of Ni2+ ions across the growing oxide. After first succeeding in adding lithium directly to molten nickel, the purpose of this investigation was to determine whether alloyed lithium is a more effective oxidation inhibitor than the external vapor. Seven 650-g heats were prepared by melting carbonyl nickel inductively under 1 atm of argon. Various amounts of lithium were added by dropping small chunks into the melt. Only about 10-pct recovery was achieved with the remainder lost by spattering and volatilization. Nominal and actual

Jan 1, 1965

By S. T. Wlodek

The scale md subscale reaction products were identified and their rates of formation were studied in air over the range 1600" to 2000°F (871 " to 1149°C) for periods of up to 400 hr and for hoth the solution-annealed and aged conditions. The effect of prior sltrface preparation on suhscale oxidation was also studied The general oxidation behavior of both Ni-Cr-Mo-Al-Ti type alloys was similar. A surface film of a, Al2O3, forms immediately on exposure Subsequent oxidation continued at a linear rate (QL = 55 * 5 kcal per mole) as colonies of Cr2O3 nucleated at the A12O3/gas interface Further oxidation proceeded at a paraholic rate zvhiclz could he fitted to two successive rate constants. During paraholic oxidation, and depending on temperature, the scale consisted of Cr2O3, NiCr2O4 , and TiO2 with traces of NiO. In the case of Rene 41, the activation energy of both paraholic processes was 66 * 3 kcal per mole suggesting that diffusion of cations tlzrozrgh Cr2O3 was the rate -determining process. An unusual decrease in the oxidation of Udimet 700 at 1900°F where a spinel of Ni(A1,Crh0, zuas the predominant reaction product prevented the accurate assignment of activation energies for this composition. In both alloys internal oxidation of Al2O3 commenced shortly after parabolic scaling was observed. Prolonged exposure prod7tced intemal oxidation of TiN, and in Udimet 700 a complex Mo-Ni nitride was also found. At 1900oF, the subscale reactions in Udimet 700 undergo an inversion which parallels the decrease in surface oxidation; internal oxidation ceases hut is replaced by the formation of "spherodized" 3.&apos; colonies. Surface-preparation techniqtles which introduce appreciable working, such as coarse surface grinding or grit blasting. increase the amount of alloy depletion and internal oxidation in Reni 41. The reverse is true of Udimet 700 for which electropolished or mechanically polished specimens show much more subscale oxidation than strongly worked stirfaces. The strongest commercial nickel-base alloys presently available are generic to the Ni-Cr-Mo-A1-Ti base which exploits the precipitation of Ni3(A1,Ti) as the main strengthening mechanism, while relying on solid-solution strengthening by molybdenum and chromium reinforced by the pre- cipitation of carbides to attain maximum properties. This study characterizes the oxidation behavior of Rene 41, the strongest alloy of the Ni-Cr-A1-Ti type commercially available in sheet form, and Udimet 700, whose higher aluminum and titanium content allows it to exhibit one of the more attractive combinations of high-temperature properties available in a wrought product. The scaling processes of complex, type nickel-base alloys have received relatively little attention. Malamand and vidal as well as Poulignier et al.2&apos;3 have determined the composition gradients across the metal/oxide interface produced by high-temperature oxidation and considered the effect of surface perature, Limited weight-gain data has also been published by Fere 5 for alloys of this type and Radavich6 has identified the reaction products on Udimet 500 and Inco 702 after oxidation at 1832°F. Reference can, of course, be made to the excellent reviews of Kubaschewski and Hopkins7 or Ignatov and Shamgunova8 for a summary of the data available on the oxidation of binary and ternary alloy systems which are related to the more complex alloys considered here. EXPERIMENTAL The analyses of the different commercial heats studied are given in Table I. Using the experimental procedures previously established,9 continuous weight-gain data were obtained on both heats of Rene 41 sheet (A and B) and 150-mil-thick slices of cast Udimet 700. Subscale oxidation reactions were followed by static exposure of cylindrical specimens obtained from swaged Rene 41 (Heat C) and Udimet 700 (Heats E and F). In brief, continuous weight-gain tests were performed on specimens with a surface area of 10 to 12 sq cm. These were abraded through 600 grit Sic paper, electropolished to 2p rms in an electrolyte of 10 pct H2So4 in ethanol, and lightly etched in 10 pct HCl in ethanol before final washing and rinsing in ethanol. All continuous weight-gain data were obtained in dried (-70°F dew point) flowing (1 liter per min) air to an accuracy of +0.1 mg. Subscale oxidation processes were followed by the metallographic examination of 0.5-in-diam by 1.0-in.-long specimens. After an initial center-less grinding, various additional surface treatments were employed to determine the effect of surface preparation on subscale oxidation processes. Before exposure in zirconia crucibles, all samples were lightly etched in 10 pct HCl-ethanol, washed in ethanol, and dried. The depth of internal oxidation was measured to ±0.00025 in. on unetched specimens mounted so as to provide a taper mag-

Jan 1, 1964

By Donald E. Grimes

In conjunction with Inland Steel&apos;s development of lead-bearing steels possessing improved machin-ability because of tellurium and/or selenium additions, it was decided to determine liquidus and solidus temperatures in the Pb-PbTe-PbSe sub-ternary system. With the exception of alloys in the PbTe-PbSe system, it is believed that no previous study of this subternary has been performed. Thermal analysis was employed in a general survey of the subternary. In addition to PbTe, PbSe, and pure lead, ten ternary compositions were selected at intervals of ten at. pct. Sixty-gram alloys were prepared by sealing an appropriate mixture of the elements in quartz crucibles with a central thermocouple-well under a vacuum of less than 10 p. All three elements were 99.999+ pct pure with only trace impurities detected by spectroscopic examination. After the alloys had been heated at least 20°C above the liquidus in a Kanthal furnace, cooling and heating curves were obtained. Two or more cooling curves were employed both for the determination of each alloy liquidus and for the solidus of those al- loys containing greater than 50 at. pct Pb. Cooling rates were 0.5° to 3.5°C per min during the 5 min immediately prior to the start or end of solidification. For those ternary alloys containing 50 at. pct Pb, the solidus was determined from heating curves. Temperatures were measured with a Pt/Pt-10 pct Rh thermocouple which was calibrated in the same apparatus against the freezing points of zinc (A. D. MacKay—99.999 pct), antimony (A. D. MacKay-99.999 pct), and copper (ASARCO—99.999+ pct) both before and after the experimentation. The only interruptions in the continuous strip-chart recording of the temperature occurred for brief periods at significant points of interest when direct readings were made with a Rubicon Type B potentiometer sensitive to * 1 µv. The average liquidus and solidus temperatures obtained in this investigation are listed in Table I together with probable errors based on the accuracy of the thermocouple calibration and the reproduci-bility of the data. No chemical analyses of the alloys were performed because the synthetic or as-charged compositions were felt to be reliable. The melting points obtained for PbTe (924.7° ± 0.7°C) and PbSe (1084.0° ± 0.6°C) compare favorably with recent findings of other investigators.&apos;-&apos; As indicated in Table I, both the liquidus and solidus temperatures increase as selenium replaces tellurium for a constant atomic percent lead. As a result, the ternary liquidus and solidus temperatures for a given percent lead lie between the corresponding binary temperatures published in the literature. It should be noted that those ternary alloys containing 50 at. pct Pb exhibit a relatively narrow liquid-plus-solid region (<80°C) when compared with alloys containing greater than 50 at. pct Pb. Alloys with 60, 70, or 80 at. pct Pb not only have a much wider liquid-plus-solid region (>500°C) but also exhibit considerably lower and approximately constant solidus temperatures which thus form a virtually isothermal solidus "plane" slightly below the melting point of pure lead (327.3°C). For these alloys

Jan 1, 1965

By J. B. Clark

An exploratory study of the 60 wt pct Mg and 80 wt pct Mg sections of the solid constitution in the magnesium-rich region of the Mg-Al-Ca-Zn system was undertaken. The objective of the investigation was to determine the general configuration of the phase fields with respect to the magnesium solid solution in this complex system. The 335°C (635°F) tetrahedron was selected for study because the solid constitutions of the bounding ternary systems—Mg-Al-Zn,1 Mg-A1-Ca,2 Mg-Ca-zn3—were well known and, at least in these ternary systems, diffusion was rapid enough at 335°C for equilibrium to be reached fairly rapidly. Metallography and powder X-ray diffraction were selected as the best corroboratory methods for determining the solid phase equilibria. A total of forty-six quaternary alloys on the 60 wt Mg and 80 wt Mg sections were prepared, annealed to equilibrium at 335°C, and the phases present identified. Singly sublimed (99.99 pct) magnesium, electrolytic (99.99 pct) zinc, high-purity (99.99 pct) aluminum, and USP calcium were alloyed in graphite crucibles under a chloride flux and chill cast into a split graphite mold. Alloy samples were sealed under argon in Pyrex vials and annealed at 335°C ± 1/2° for a minimum of 500 hr. At the conclusion of the anneal, the alloy samples were quenched rapidly in ice water. Standard metallographic procedures for magnesium alloys were used. Powder X-ray diffraction patterns were taken on a G. E. Camera with a diameter of 14.32 cm using nickel filtered copper radiation. The phase equilibria in the 60 wt pct Mg section of the 335°C (635°F) tetrahedron is shown in Fig. 1. The complex equilibria in the zinc-rich region were not accurately determined and are shown only tentatively with dotted lines. The equilibria of the three bounding ternary 335°C sections from pure magnesium to 60 wt pct Mg are also shown as though folded away from the tetrahedron. The 80 wt pct Mg section has the same configuration of phase fields as that shown in Fig. 1. Thus it is reasonable to conclude that in higher magnesium sections, the same relative configuration of phase fields is maintained though the relative proportions of the individual phase fields may change slightly as the magnesium solid solution is approached. Note that all the ternary phases present in these ternary diagrams enter into the quaternary equilibria with the exception of the phase of the Mg-Al-Zn system which becomes unstable with the addition of as little as 1/2 pct Ca. No quaternary intermetallic phases were found. No liquid phase was detected in any of the quaternary alloys annealed at 335°C suggesting that if a quaternary eu-tectic exists, it must lie between 335°C and 339°C, the temperature of the ternary eutectic in the Mg-Al-Zn system.

Jan 1, 1962