Search Documents

By J. W. Cunningham, W. A. Tiller, D. H. Lane

The effect of ultrasonic vibrations on ingot solidification has been considered both theoretically and experimentally. The theoretical section elucidates the mechanisms by which the ultrasonic vibrations might refine the ingot structure. The experimental section describes a very efficient means of introducing the ultrasonic vibrations to the freezing interface. The application of this technique to the consumable-electrode arc melting process shows that the columnar mode of freezing may be effectively suppressed yielding an ingot structure consisting predominantly of equiaxed grains. The results support the contention that the ultrasonic vibrations increase the nucleation frequency in the layer of liquid adjacent to the freezing interface. CERTAIN structural characteristics of as-cast ingots are undesirable since they create considerable difficulty for subsequent processing and often produce defects in the finished product. These structural defects are illustrated in Fig. 1(a), and are: 1) planes of weakness where columnar grains growing from the different mold faces meet, 2) strength anisotropy due to the preferred orientation of the columnar grains and 3) inhomogeneity due to segregation at dendrite boundaries within the columnar grains and at the columnar grain boundaries. The type of ingot structure that eliminates 1) and 2) and diminishes 3) is the fine-grained equiaxed structure illustrated in Fig. 1(c). Many attempts have been made to produce the desirable ingot structure illustrated in Fig. 1(c) by inoculating, casting with varying superheats, vibrating or stirring, or by irradiation with ultrasonic vibrations. These attempts have met with various degrees of success, the ingots generally having the structure illustrated in Fig. 1(b). All four methods have been the subject of numerous investigations,1"4 the latter producing the most erratic behavior and inconsistent success. The method of ultrasonic irradiation during ingot solidification has shown considerable promise on small-scale ingots (diam 2 in.) but has not yet been successfully adapted to large-scale operation. The present paper considers the application of ultrasonic radiation to ingot solidification both theoretically and experimentally. The purpose of the paper is to elucidate the mechanism by which ultrasonic energy refines the ingot structure and to describe a method for producing the desirable ingot structure in both laboratory scale experiments and in ingots of commercial size. THEORY Conventional Casting—Before discussing the possible effects of ultrasonic radiation upon ingot structure let us first briefly review the reasons for the breakdown of columnar crystallization to equiaxed crystallization during ingot solidification. The following is a slightly oversimplified description. In the conventional method of casting, the alloy having a certain degree of superheat, T, is poured to fill a cold mold which is at room temperature, Tc,. Due to conduction of heat through the mold wall the outer rim of liquid metal cools rapidly to the liquidus temperature and begins to supercool. At some degree of supercooling, nuclei of solid form at random in this supercooled layer at the mold surface. The grains in this chill layer begin to grow inwards producing a solute build-up, thus lowering the freezing temperature at the interface as illustrated in Fig. 2. As growth proceeds, the temperature gradient in the solid conducts away not only the latent heat of fusion evolved during growth but it also conducts away some of the superheat of the melt so that the temperature

Jan 1, 1961

By W. A. Tiller, D. H. Lane

A simple zone melting technique for investigating the effect of ultrasonic irradiation upon ingot solidification is described. The effect of i) ultrasonic power level, ii) freezing velocity, iii) constant or variable frequency, iv) direction of irradiation, and v) transducer-cozlpling bar joint upon the grain size of type 316 stainless steel have been investigated. The results of this study support the postulate that the ultrasonic vibrations increase the nucleation probability in the layer of liquid adjacent to the freezing interface. In the first paper of this series,l the possible mechanisms whereby ingot structure may be altered by irradiating a solidifying melt with ultrasonic vibrations have been discussed. A new technique for efficiently introducing the ultrasonic energy into the solid-liquid interface region was presented and applied to ingot preparation by the consumable-electrode arc-melting technique. The experimental results support the postulate that the ultrasonic vibrations may refine the ingot structure by increasing the nucleation probability in the zone of liquid adjacent to the solid-liquid interface. The present paper describes the application of the same technique to a relatively simple laboratory-scale zone-melting apparatus. This apparatus is found to be well suited to the detailed study of ultrasonic technology in this area and allows one to determine, in particular, the minimum ultrasonic power level needed to produce a certain grain size in a particular material. The results of this study support the nucleation mechanism for grain refinement, but do not provide any deeper insight into the specific nucleation mechanism responsible for the effect. EXPERIMENT The apparatus used in these experiments is shown in Fig. 1 and illustrated schematically in Fig. 2. The material to be studied, type 316 stainless steel, was in the form of a 3/4-in. sq bar 30 in. long. This bar was placed in a square open-topped mold with open ends made from high-purity graphite coated with a flame-sprayed Al2O3, skin. Surrounding the crucible was a molybdenum susceptor with 3/8-in. diam holes spaced at 1-in. intervals along its length to serve as sight ports. A tapered transducer horn was brazed to one end of the specimen. The entire assemblage was enclosed in a quartz tube, the transducer itself projecting out one end and resting in a cooling tank. A vacuum seal between the coupling bar and the end plate enclosed one end. A similar plate and seal enclosed the other end. The system is gas tight and can be operated under vacuum or an inert atmosphere. For these experiments, flowing argon at 15 in. of Hg pressure was used. The heat source for melting the stainless steel specimen was a 2-in. long 3-kc induction coil placed around the quartz tube; this source heated the susceptor, inductively melting about a 3-in. zone of the sample by radiation. To move the molten zone at a specified rate, the induction coil was moved down the tube at this rate with the aid of a simple pulling device. Thus, the sample could be irradiated at varying ultrasonic frequencies and power levels and could be solidified at varying rates. The power input to the transducer was measured using a "John Fluke Model 120 VAW-Meter." 1 The power delivered to the interface region is probably only about 50 pct of that measured on the VAW-meter. In a typical run, when the ultrasonic power was turned on, the interface of the molten zone closest

Jan 1, 1961

By W. D. Robertson, D. A. Koss, A. J. Goldman

THE significance of the hcp (E) structure, which appears when Fe-Cr-Ni alloys (stainless steels) are transformed martensitically, has been the subject of considerable study and speculation.'-7 It has been proposed that the hcp structure is an intermediate phase in the transformation: fcc (austenite) — hcp (E) -bcc (0, martensite). However, recent studies by transmission electron microscopy6,7 have indicated that the hcp structure may be a consequence of the large shear strain (10 deg) associated with the fcc to bcc transformation. That is, the transformation to a bcc structure is accompanied by extensive dissociation of dislocations in the parent austenite, which has a low stacking-fault energy.'-'' X-ray diffraction analysis of the transformed alloy reveals a pattern of lines corresponding to an hcp structure, together with the parent austenite and the bcc product. The fact that the hcp structure is observed only in association with the bcc product in these alloys1'4'6'7 lends support to the conclusion that the hcp structure is a secondary product of the transformation. But, the evidence is circumstantial and more definite resolution of the two possibilities mains to be obtained. If the hcp structure is an intermediate product of the transformation, as in 1) above, then two distinct Ms temperatures should be observed, Ms and To evaluate this possibility, three different techniques that are particularly sensitive to the structural changes accompanying such transformations have been used in an attempt to detect two transformation temperatures in an Fe-15.1 Cr-11.7 Ni alloy: 1) high-sensitivity differential thermal analysis, 2) the temperature dependence of resonant frequency (elastic moduli), and 3) internal friction of cylindrical specimens vibrating in either longitudinal or torsional modes. To obtain the necessary sensitivity, a differential thermal analysis technique was developed for the purpose, Fig. 1. The differential temperature between a nickel standard and the specimen was amplified to produce a sensitivity of 0.02OC (0.7 v) in temperature difference. The specimen and the standard were surrounded by a copper block and the entire assembly was immersed in a solution of methyl and ethyl alcohol, freezing point, - 140OC, which provided the necessary thermal stability to reduce temperature fluctuations to negligible proportions. A cooling rate of about 1.5OC per min was obtained by bubbling liquid nitrogen through the liquid bath. In order to calibrate the experiment with respect to the evolution of heat in the transformation from fcc to hcp structures, differential cooling curves were obtained for an Fe-19.8 Mn alloy, which transforms martensitically to E.'"-' a Ms(e) temperature of 145°C was clearly defined by a temperature

Jan 1, 1964

By R. W. Powers, M. V. Doyle

ThE solution of a diatomic gas such as 0, or N2 in a metal usually follows Sieverts' law; i. e., Here C is the solute concentration at equilibrium and P, the gas pressure. The proportionality constant Ks is also the equilibrium constant for the reaction 1/2 02 (at pressure, P) - 0 (in solution at [21 concentration., C). to use oxygen as an illustrative gas. Sieverts' law is therefore interpreted to indicate that diatomic gases go into metallic solution atomically and that the solute "gas" atoms interact negligibly with each other. Of course, this interpretation is strictly valid only over the temperature interval in which the reaction indicated in [Z] can be investigated. At temperatures several hundreds of degrees below this interval, the possibility of interactions between solute atoms is conceivable. Indeed, from internal-friction measurements some evidence for the existence of groupings of oxygen atoms in tantalum solid solutions was presented a few years ago.1,2 Over a range of solute concentration, the experimental oxygen internal-friction peak in tantalum, measured as a function of temperature at constant frequency of vibration, can be described as the sum of two elemental peaks, each corresponding to a separate relaxation process. At 0.7 cps, the height of the elemental peak found at 137°C is proportional to the oxygen content, whereas the height of the one at 162°C varies as the square of the oxygen concentration. The 137°C peak was presumed to arise from the stress-induced ordering of oxygen atoms among various classes of octahedral sites in the manner proposed by Snoek.3 The 162°C peak was attributed to a somewhat similar stress-induced ordering process, in which each oxygen atom was interacting with a neighboring oxygen atom. Similarly, the experimental peak due to nitrogen in tantalum can also be described as the sum of two peaks. The height of one varies as the nitrogen concentration and the other as the square of this quantity. In fact, some evidence of solute interactions exist for all oxygen and nitrogen solid solutions of Group V transition metals. However, the interaction energy was not obtained previously for any alloy. The determination of this quantity, as a part of a more intensive study of the interaction between oxygen atoms in solid solution in tantalum, is reported in this paper. PRINCIPLE OF THE EXPERIMENT Consider an equilibrium in a solid solution of tantalum between oxygen atoms which are bound together pairwise and those solute oxygen atoms which are not so associated. 20 (Ta) - O2 (Ta) [3]

Jan 1, 1960

By T. Yoshioka, Paul A. Beck

SILICON, germanium, and tin occur with both the white tine-type structure and the diamond cubic structure. In the latter form these elements are semiconductors; in the former they are metallic. The metallic form of germanium and silicon is obtained only under high pressure.' For all three elements the transition from the semiconductor to the metallic state is accompanied by a decrease in the atomic volume of somewhat more than 20 pctily2 Table I. At such a large compression the widening of the s and p bands is sufficient to make the energy gap of 1.1 ev, or less, of the semiconductor disappear, giving rise to the metallic state.*

Jan 1, 1965

By P. S. Rudman

The allotropic volume changes of the ,metallic elements are reviezoed with the conclusion that in general atomic volume is conserved to better than 1 pct in such transformations. A table of the atomic volumes of the metallic elements is given and its use in considering the size factor in alloys is discussed. The importance of the concept of atomic-size factor, due to Hume-Rothery and coworkers,' is firmly established. Most attempts at quantitative formulations of this concept have employed the atomic radius (half some interatomic distance) as the measure of size and innumerable tables of such radii exist. This is probably, however, an unfortunate choice of parameter. Firstly, discussion in terms of interatomic distances requires a knowledge of the crystal structure. While this is known, except for a few cases, for the elemental structures, there are still many undetermined alloy structures. Secondly, except for the simpler structures, face-centered cubic (Al),* body-centered cubic (A2),* and hexagonal-close-packed (A3).* with ideal axial ratio, there is no unique in- teratomic distance, an m y decision must be made as to which distance, or which average of the distances, should be used. However, the most important point is that for metals the dominant bonding parameter can generally be expected to be atomic volume and not interatomic distance. This is perhaps most explicitly stated in the Wigner-Seitz cellular method.' In this approximation, cellular polyhedra of atomic volume v are replaced by spheres of radius Y,: 4/3 ?rs3 = v. That is, there is no reference to the interatomic distances. If atomic volume is in fact the dominant parameter, then in allotropic transformations we might expect to find atomic volume approximately conserved. For example, in the A1 ? A2 transformation we would thus have

Jan 1, 1965

By M. G. Benz, J. F. Elliott

The austenite solidus of the iron-carbon system has been determined using a series of diffusion couples, each of which consisted of a specimen of austenite held in contact with a melt saturated with austenite. After the equilibrium distribution of carbon had been established by diffusion at a specified temperature, i.e. the austenite specimen had become austenite of the solidus conzposition, the diffusion couple was cooled, sectioned and anazlyzed for carbon. The solidus was found to be a straight line: A revised iron-carbon temperature-composition diagram is presented, COMPOSITION has a marked effect on the temperature at which austenite begins to melt and the austenite solidus of the iron-carbon system describing this effect has been the subject of many investigations.1-10 The significant results of these investigations are presented in Fig. 1. The experimental methods and purity of the materials used in them are summarized in Table I. In plotting the data in Fig. 1 no attempt has been made to convert these results to the International Temperature Scale of 1948," except for the data of Adcock,5 as this conversion would do little to reduce the uncertainty that exists as to the position and shape of the solidus. A point of major concern in evaluating these data is that the alloys studied, except those used by Adcock, were not binary alloys of iron and carbon, Table I. Also, it would appear that several of the methods did not permit equilibrium to be established through the system being studied. All that can be said for the results of these investigations is that they indicate only approximately the location of the solidus with the uncertainty as to its location at 1 pct C being approximately 100°C. The current investigation was undertaken to provide reliable data by which the austenite solidus could be established. It was hoped that information on the liquidus also could be developed at the same time, but experimental limitations prevented this as austenite segregated from the liquid on cooling. After a careful study of possible experimental methods and extensive laboratory tests, it was decided that the use of a series of austenite-liquid diffusion couples would provide the most reliable results. This paper describes the method and its results and also includes a complete iron-carbon temperature-composition diagram based on what are considered to be the best available data. EXPERTMENTAL METHOD The diffusion couple used for this investigation consisted of a small cylindrical pellet of austenite held in contact, at a specified temperature, with a melt saturated with austenite. The composition of the cylindrical austenite pellet was chosen to be approximately 0.1 wt pct C less than the estimated

Jan 1, 1962

By J. Tarwater

The torsional testing of cylindrical medium-carbon steel specimens, heat treated to a high strength level, revealed a stress-strain relationship that was dependent on the direction of torsional plastic pre-strain. This Bauschinger effect was observed in prestrained specimens both with and without subsequent elevated-temperature strain aging. Yield stresses in strain-aged specimens exceeded those of simply prestrained specimens and the difference in stress was greater when the prestrain direction opposed the test direction. This behavior is discussed in terms of the classical dislocation pile-up using Cottrell's equation, A plastically prestrained strain-hardenable member, loaded in a direction opposite to the direction of prestrain, produces a stress-strain relationship differing appreciably from the curve representing reloading in the prestrain direction. This phenomenon, referred to as the Bauschinger effect, will be discussed in terms of the stress differences ob- served at a specified strain. The effect, dating back to the 1880's, was first attributed to grain boundary stresses. When later work revealed that the effect was also present in single crystals, revised theories attributed the diminished applied reverse stress to assistance from internal long-range stresses. These stresses have been associated with dislocation pile-ups or with dislocation arrays having analogous stress patterns. The stress patterns are subject to alteration by interaction with interstitial solute atoms and acceleration of the interaction may be accomplished with elevated-temperature strain aging. As discussed herein, the interaction showed a directional effect with regard to the applied stresses necessary for small plastic strains. Aside from the rigorous Bauschinger stress-strai relationship, which compares prestrained members, it is interesting to compare the stress-strain curve of a member being prestrained with that of a prestrained member being reverse loaded. For small strains which are a fraction of the prestrain deformation, the applied stresses of the reverse reloaded member are smaller. However, as the reverse strain approaches the prestrain value, the stresses approach equivalence. It has been reported1 that the stress required to return a prestrained specimen to its initial "zero" position generally exceeds the prestrain stress because of the work hardening occurring on potential slip systems during prestrain.

Jan 1, 1963

By H. R. Peiffer

Composite alloys of silver and alumina are shown to resist flow above the melting point of the continuous matrix. The ability to resist flow depends on the fineness of the dispersion and the oxygen content of the silver. It is believed that the oxygen influences very strongly the bond between the molten silver and the finely divided alumina. RECENT needs for materials with high strength and creep resistance at high temperatures initiated mechanical property studies on dispersed phase materials to near the melting point of the continuous matrix material. Results' of these investigations have shown that certain of these materials do have promise for high-temperature applications. Experiments performed on composite materials of silver and alumina by the author have resulted in the discovery of an interesting effect above the melting point of the silver. In these materials the silver was continuous and the alumina very finely divided (Linde B). It was observed that these materials exhibited strength and resistance to flow above the melting point of the silver matrix. The purpose of this paper will be to describe these properties. METHOD OF PREPARATION The materials were prepared by mixing the proper amount of Linde B alumina and high-purity silver oxide. The alumina content was varied from 5 to 20 wt pct alumina in silver in 5 pct steps. The materials were mixed by blending the constituents in an ordinary food blendor using ethyl alcohol as a vehicle. Enough alcohol was added to the powders to form a mixture with the consistency of a thin mud. After blending for about | hr the material was dried and the silver oxide reduced by heating to 450 OC. The material was then pressed at 25 tsi into a -in. billets 3 in. long. EXPERIMENTAL PROCEDURE The specimens were horizontally supported at either end by knife edge supports of cold-rolled steel. This holder was then placed in a "globar" furnace and a chromel-alumel thermocouple placed very close to the specimen recorded its temperature to within 10°C. Each specimen was heated rapidly to 900°C initially. The specimens were held at temperature approximately 30 min and then the temperature was raised 50 deg. The procedure was repeated until deformation was noted. Photographs were made of the specimens at various temperatures and increments of time using a Polaroid Land camera. RESULTS Fig. 1 shows the 5 pct by weight "Linde B" alumina and silver material after reaching 980 °C. Failure occurred after 15 min at this temperature. There were two points of failure and silver collected at them. No additional flow of the molten silver was noted at any other place. Fig. 2 shows a 20 pct by weight "Linde B" alumina in silver specimen. After 30 min at 1400°C, bowing of this material was observed. Other concentrations of alumina were added to

Jan 1, 1961

By J. Rourke, F. S. Minshall, E. G. Zukas, C. M. Fowler, O&apos

The Hugoniot curves were determined for Fe-Si alloys containing up to 7 wt pct (13 at. pct) Si. The pressure of the transition increased as the silicon content of the alloy increased. Single crystals of 2.9 wt pct Si-Fe were also studied. The pressure of the transition was not dependent on crystallo-graphic orientation. All of the Neumann bands (mechanical twins) were attributable to (112) planes but not all of the {112} planes showed twin markings. A thorough study of the iron Hugoniot (the relationship between specific volume and pressure) under plane wave shock loading revealed a pressure transition at about 130 kbar shock pressure. The results of this investigation were reported by Bancroft, Peterson, and inshall1 in 1956. At the time of this discovery, it was felt that this was probably the a, to y transition normally found in iron and many of its alloys. Subsequently a number of iron alloy systems were surveyed in which the alloying element has a considerable effect on the normal a, to y transformation. The influence of carbon and nickel and/or chromium have already been reported.2,3 At the present time, there appears to be some doubt that this pressure transition is the usual a, to y transition In this study, Fe-Si alloys containing up to 7 wt pct (13 at. pct) Si were chosen for several reasons. To the present, the transition has been found only in iron-base alloys which were originally in the a, phase (bcc). Secondly, the y loop at atmospheric pressure extends to only about 2.5 wt pct Si. If the transition were a, to y, then one might expect a rather drastic pressure effect for alloys containing more than 2.5 wt pct Si. Finally, single crystals of Fe-Si alloys large enough for shock loading studies are readily available thereby making it quite easy to determine the effect of crystal orientation on the transition pressure and on the twinning behavior of the alloy. EXPERIMENTAL PROCEDURE Fe-Si alloys containing up to 7 wt pct Si were produced by normal vacuum casting procedures. Single crystals of Fe-2.9 wt pct Si were purchased from Monocrystals Co., Cleveland, Ohio. The orientations of these crystals were determined and samples cut so that the shock wave would be parallel (to within 1.5 deg) to either the (loo), (Ill), or (112) principal orientations. Three distinct experimental testing techniques were used. First, the pin technique, described elsewhere,4 was used to determine the transition pressure for the polycrystalline alloys as well as for the (111) and (112) orientations of the 2.9 wt pct Si single crystals. Secondly, the recovery studies, described in detail in an earlier paper,2 were used for determining the effect of alloy composition and crystal orientation on the plastic II compression-plastic I rarefaction interaction zone for several specific shock pressures. Finally, measurements of pressures above the two-wave threshold were made on the polycrystalline alloys so that more complete Hugoniot curves could be constructed for this alloy system. The optical techniques described by Rice et al.5 were used to measure the shock and free surface velocities of the samples from which the Hugoniot data were obtained. This method is applicable only in the single wave region, since velocities are obtained from the measured total transit times of the disturbances through measured sample thicknesses.

Jan 1, 1963

By M. Cohen, R. J. Teitel

There is considerable interest in beryllium because of its low density (1.84 g per cu cm), high modulus of elasticity (40 X 106 psi), high melting point (1280°C), and special nuclear characteristics. Moreover, it has fair resistance to corrosion and oxidation. However, the purest beryllium known to the authors is relatively brittle at room temperature, and cannot be fabricated readily. The search for improved properties leads naturally to investigations of beryllium alloys and the phase relationships upon which they are based. The present paper is concerned with the alloys of beryllium and iron, primarily from the standpoint of the equilibrium diagram. Iron was selected (1) because of its all-round importance in metallurgy, and (2) because the beryllium-iron system is known to be quite complex. The most recent diagram in the literature is that of Gaev and Sokolov,' and covers only the iron-rich end up to 16 wt pct beryllium. Beryllium markedly restricts the austenitic field, closing the gamma loop at about 0.4 wt pct (3 at. pct). On the other hand, beryllium is soluble in a-ferrite up to a maximum of 7.5 wt pct (34 at. pct) at the eutectic temperature of 1160"C. The eutectic composition lies at 10 wt pct beryllium (42 at. pct) and corresponds to a mixture of or and FeBez (called j3 in the present paper). The solid solubility of beryllium in the a phase decreases with decreasing temperature, and makes precipitation-hardening possible. These findings substantiate the earlier work of Oester-held,2 Wever and Mueller3 and Laissus.4 In addition to the FeBe2 (ß) mentioned above, Misch6 has reported on FeBes, and indicated evidence for another compound containing still more beryllium. A preliminary diagram by Gordon,5 not hitherto published, is given in Fig 1. Besides the phases previously named, there are shown a solid solution of extended range (e), a compound of limited solubility (t), and a high temperature phase (7). Beryllium is designated as 8. The t field contains the compound composition FeBea, and the f phase undoubtedly corresponds to the beryllium-rich compound found by Misch.6 The region around the { phase was proposed by R. J. Teitel based on Gordon's data. The details of the diagram are self-explanatory. It was the unusual complexity of this system that prompted the authors to undertake the present studies. By the same token, more emphasis was placed on the beryllium-rich than the iron-rich end of the diagram. Exprimental Details RAW MATERIALS The beryllium employed in this investigation was one of the purest grades available. Its chemical analysis after vacuum melting is given in Table 1. The metal assayed 99.4 wt pct beryllium. Vacuum melted electrolytic iron of purity shown in Table 1 was the source of iron.

Jan 1, 1950

By L. Ianniello

AMONG the more interesting peculiarities of plutonium is the brittleness of its room-temperature monoclinic phase, a, since the adjacent higher-temperature phase (transformation temperature, 112C), ß, is also monoclinic but very ductile. Other elements, e.g., tin and manganese, have phases which exhibit similar contrast in plasticity. However, it was considered unusual when the a phase which has less than 0.1 pet tensile elongation' was rolled to 90 pct reduction in thickness at room temperature.' Since brittle behavior often is a structure-sensitive property, but could also be the result of covalent-type bonding, further experiments reported here have been conducted in an attempt to illuminate the problem. Electrorefined plutonium was rolled under various conditions and examined to determine the strain-hardening characteristics and also to determine under what conditions rolling could be performed. The rolling mill had 6.0-in.-diam heatable rolls with a variable roll speed (6.25 to 445 in. per min). Microhardness measurements were taken using a square-base diamond indenter with loads from 50 to 1000 g. The method used for rolling plutonium at room temperature consisted of prior

Jan 1, 1964

By Allan E. Martin, Harold M. Feder, Irving Johnson

The cadmium-uranium system was studied by thermal, metallographic, X-7-ay and sampling techniques; special emphasis was placed on the establishment of the liquidus lines, The single inter metallic phase, identified as the compound UCd11 melts peritectically at 473°C to form a-umnium and melt containing 2.5 wt pct uranium. The cadmium-rich eutectic (0.07 wt pct uranium) freezes at 320.6°C. Solid solubilities in uraizium and cadmium appear to be negligible. Between 473°C and 600°C the liquidus line is retograde. NO publication relating to the cadmium-uranium phase diagram was found in the literature. The establishment of this diagram was of considerable interest to us because of a possible application of the system to the pyrometallurgical reprocessing of nuclear fuels. Analysis of liquid samples, metallographic examination, thermal analysis, and X-ray diffraction analysis were used to establish the phase diagram from about 300° to 670°C. Particular emphasis was placed on the establishment of the liquidus lines. The same system was concurrently studied in this laboratory by the galvanic cell method.' Both studies benefited from a continual interchange of information. MATERIALS AND EXPERIMENTAL PROCEDURES Stick cadmium (99.95 pct Cd, American Smelting and Refining Co.) contained 140 ppm lead as the major impurity. Reactor grade uranium (99.9 pct U, National Lead Co.) was most often used in the form of 20-meshspheres. This form was particularly suitable because it does not oxidize as readily as finer powder. The liquidus lines were determined by chemical analysis of filtered samples of the saturated melts. The liquid sampling technique is described elsewhere2 alumina crucibles (Morganite Triangle RR), tantalum stirring rods, tantalum thermocouple protecthecadmiumtion tubes, Vycor or Pyrex sampling tubes, and grades 60 or 80 porous graphite filters were used. Uranium dissolves in liquid cadmium rather slowly. In order to achieve saturation of the melts it was necessary to modify the procedure of Ref. 2 by the use of more vigorous stirring and longer holding periods (at least 3 hr) at each sampling temperature. The samples were analyzed for uranium by spectro-photometry (dibenzoyl methane method) or by polar- ography. The analyses are estimated to be accurate to 2 pct. Thermal analysis was performed on alloys contained in Morganite alumina crucibles in helium atmospheres. Standard techniques were employed; heating and cooling rates were about 1°C per min. For the determination of the peritectic temperature, Cd-10 pct U charges were first held for at least 50 hr at temperatures in the range 435° to 460°C to form substantial amounts of the intermediate phase. For the determination of the effect of cadmium on the a-p transformation temperature of uranium, charges of Cd-25 pct U (-140+100 mesh uranium spheres) were first held near the transformation temperature, with stirring, to promote solution of cadmium in the solid uranium. The holding times and temperatures for these treatments were 18 hr at 680°C for the cooling run and 28 hr at 630°C for the heating run. Alloy specimens for X-ray diffraction and metallographic examination of the intermediate phase were prepared in sealed, helium-filled Vycor or Pyrex tubes. Ingots from solubility runs and thermal analysis experiments also were examined metallographically. Crystals of the intermediate phase were recovered from certain cadmium-rich alloys by selective dissolution of the matrix in 20 pct ammonium nitrate solution at room temperature. Temperatures were measured with calibrated Pt/Pt-10 pct Rh thermocouples to an estimated accuracy of 0.3°C. However, the depression of the freezing point of cadmium at the eutectic is estimated to be accurate to 0.05°C because a special calibration of the thermocouple was made in place in the equipment with pure cadmium just prior to the measurement. EXPERIMENTAL RESULTS The results of this study were used to construct the cadmium-uranium phase diagram shown in Fig. 1. This diagram is relatively simple; it is characterized by a single intermediate phase, 6 (UCd11), which decomposes peritectically, and which forms a eutectic system with cadmium. The solid solubilities in the terminal phases appear to be negligible. An unusual feature of the diagram is the retrograde slope of the liquidus line above the peritectic temperature. The Liquidus Lines. The liquidus lines above and below the peritectic temperature are based on three separate solubility experiments. The data are shown in Fig. 1 and are given in Table I. It is apparent from the figure that the solubility data obtained by the approach to saturation from higher temperatures fall on substantially the same lines as those obtained

Jan 1, 1962

By A. G. Crocker

The positions of twin reflections in electron-dijjcraction patterns obtained from thin metal foils may he calculated for any twin in any crystal structure by means of an elementary application of vector algebra, General equations for the four classical orientation relationships are presented using the superscript and subscript notation of the tensor calculus, which is briefly described. As an example of the application of these expressions, the case of twinned rhomhohedral crystals, and hence as a special cased twinned cubic crystals, is examined. CONSIDERABLE interest has recently been shown in the interpretation of electron-diffraction patterns obtained from twinned regions of thin metal foils. In the present paper, it is shown that the necessary information may be obtained directly for all twins in any crystal structure by means of a very elementary application of vector algebra. The equations involved are most conveniently presented by making use of the very powerful superscript and subscript notation of the tensor calculus. The use of this notation will first be described and then applied to the problem of calculating diffraction patterns for any twinned crystal. Finally, as an example of the application of the method, the specific case of twinned rhombohedra1 crystals will be considered.

Jan 1, 1965

By P. A. Tucker, T. B. Rhinehammer, D. E. Etter, J. E. Selle

The Ce-Cu phase diagram was investigated by differential thermal analysis and rnetallography. Two congruent melting compounds, CeCu2 (817°C) and CeCua (938°C), and three incongruent cornpounds, CeCu (516°C), CeCu, (796°C), and CeCu, CERIUM and copper have been suggested as possible diluents in a liquid-plutonium fueled reactor. As part of the determination of the Ce-Cu-Pu ternary phase diagram, a review Of the Ce-Cu system (798°C), are present in this system. Eutectics exist at 28 at. pct Cu (424°C), 74 at. pct Cu (756°C), and 91 at. pct Cu (876°C). The purity of the cerium used has an important effect on the results obtained by differential thermal analysis. was considered necessary. Previous work by Hanaman was conducted with relatively impure metal: 96.7 pct Ce with 2.5 pct other rare earths and 0.5 pct Fe as major impurities. The metal had a melting point of 715°C as compared to the melting point for pure cerium of 804°C as reported by Spedding and Daane.2 Results presented in this work were obtained primarily by differential thermal analysis (DTA) and metallographic examination of slow-cooled or quenched samples.

Jan 1, 1964

By R. O. Williams

Measurements have been made of the internal energy of deformation in a Cu-A1 alloy and a Cu-Zn alloy as the deference between the work and the released heat. The method required the rapid compression of samples to reduce thermal interactions. The rate of energy storage is low initially but then becomes almost linear with strain. Both alloys stored about 60 cal per mole at a strain of 0.4 in the recrystallized condition. The fractional rate of storage increases at low strains reaching about 0.25 at a strain of 0.15 and then decreases slowly with increasing strains. As do pure metals, these alloys release appreciable energy immediately following deformation; in contrast with pure metals, however, the release continued for extended periods of time. This energy release is somewhat sensitive to the amount of deformation, the deformation temperature, and prior thermal & eatment. It is believed that this release is a composite of that observed in pure metals which has been attributed to dislocations and that due to the motion of vacancies which produces increased short-range order. IT is expected that changes brought about by deformation of a pure metal can be understood in terms of the three defects—dislocations, vacancies, and interstitials—along with the interactions possible between these defects. Frequently stacking faults are created and must also be considered. 1t is not immediately clear whether or not the stress fields which are created should be regarded as independent of dislocations. For alloys there is the important additional effect of atomic configuration, for example short-range order, which must also be considered and will, in general, interact with each of the above defects. While it is true that a complete understanding of pure metals is not yet possible, it would seem very valuable to establish the similarities and differences between pure metals and alloys. Such knowledge could contribute to the understanding of both. A study of the changes in internal energy resulting from deformation of two alloys is reported here. Although some information has been available for alloys almost as long as for pure metals, the volume of work has been substantially less. Sato' and Quinney and Taylor' were responsible for the earlier work, both using brass and annealing calorimetry. tizhnova' studied stored energy in Cu-Ni alloys by a method somewhat similar to the one reported here. Bever and his co-workers have made extensive studies of Au-Ag alloys4'5 and more recently CU-AU'U' using solution calorimetry. Clarebrough et a1.' have recently studied brass using annealing calorimetry. EXPERIMENTAL METHOD The present results were obtained by the rapid, adiabatic compression of a sample about 1/4 in, diam by 1/2 in. long between two tungsten carbide hammers. A vacuum provided thermal isolation and oil provided effective lubrication between the sample and hammers. The increase in internal energy is the difference between the mechanical energy and the heat liberated within the sample. The mechanical energy was determined from the velocity of the hammers (calculated from the height through which the hammers traveled) and was essentially constant for each deformation cycle. The heat was determined from the temperature increase of the sample which was measured by an embedded thermocouple. Specific heat data were calculated from Neumann's rule using tabulated data for pure metals.9 Since the fraction of the energy which is stored is large compared to that for pure metals, specific heat data of high accuracy are not required. Successive increments of deformation were carried out by repeating the procedure, the limit being determined mostly by the decreasing accuracy caused by the increasing corrections and the decreasing storage of energy. About five cycles were used to give a true strain of about 0.5 while the time interval between cycles was 1 to 2hr.

Jan 1, 1963

By F. P. Bullen

Empirical relationships between fracture stress, orientation angle, and diameter of crystal have been determined at 77°K. Orientation ranges of markedly different behavior were found—a law of constant normal stress&apos; of value a (diameter)-1/2 for the fracture of ductile crystals, and a condition of shear stress (or strain) for more brittle crystals. The observations are not consistent with current theories. An interpretation is advanced which is also applicable to observations on the effect of prestrain at room temperature on the subsequent fracture stress at 77°K and to the effect of cyclic stressing on the cleavage strength.&apos;&apos; The law of constunt normal stress&apos; and the brittle ductile transition are also explained. The interpretation is more consistent with the initiation of cracks by intersecting dislocations than with theories based on stress -concentration by dislocation arrays. ZINC single crystals are particularly suited to the study of cleavage because fracture occurs on the basal plane over a wide range of crystal orientations. Analysis of the conditions of stress and strain at fracture in crystals of different orientations should indicate which parameters control the cleavage process. Unfortunately, controversy has arisen over the correct empirical relationship between tensile fracture stress and orientation. Schmid&apos;s observations1,2 favored a &apos;law of constant normal stress&apos;, as observed in other materials.2 For zinc, however, the observed values are far below the theoretical strength and cannot represent the true limit of cohesion between neighboring atomic planes. Hence, the interpretation of such a &apos;law&apos; is not straightforward. Deruyttere and Greenough3,4 found a complex variation between tensile fracture stress and orientation; this variation did not agree with a &apos;law of constant normal stress&apos;. Two theories have been advanced to account for their observations: a) the propagation of cracks from low-angle boundaries,5 and b) the release of energy from piled-up dislocations during crack-propagation.4 The present work resolves the apparent discrepancy between the observations and shows that neither of the above theories are applicable to the tensile fracture of zinc single crystals. A phenomenological explanation, along the lines suggested by Gilman,&apos; is advanced and successfully applied to previously unexplained effects. EXPERIMENTAL DETAILS &apos;Crown Special&apos; redistilled zinc was used, except for one comparison series op tests using &apos;Tadanac&apos; electrolytic zinc. Crystals of 1 mm diam, subsequently called &apos;1 mm crystals&apos;, were grown from the melt in vacuo in precision-bore Pyrex tubes internally coated with graphite. Several specimens 1 in. long were cut from each crystal and chemically polished. Jigs were used to minimize handling strains, and crystals were mounted in the Polanyi machine the day prior to testing to allow recovery from any such strains. One-mm crystals were chemically polished for long periods to obtain 0.1 mm (approx) crystals. One-mm crystals were cemented into miniature gimbals by &apos;Araldite&apos; casting resin. The Appendix gives the reasons for using gimbals and the results obtained by other methods. More complete details of all techniques are given elsewhere.7 The symbols and terminology used are as follows: X = orientation angle (angle between tensile axis and line of greatest slope in the basal plane). T = tensile stress (on true cross-section) S,N = shear and normal stress (components of T with respect to the basal plane) ? = shear strain D = crystal diameter. The subscript &apos;f&apos; will be used to denote values at fracture. PART I-ANNEALED CRYSTALS EXPERIMENTAL OBSERVATIONS One-mm crystals were used to establish the variation of fracture stress at 77°K with orientation at fracture (Xf), Fig. 1. For 18 deg = Xf = 55 deg, a &apos;law of constant normal stress&apos; was observed. For Xf > 55 deg, the fracture condition approximated to a constant shear stress. At Xf< 18 deg, twinning occurred before fracture so that the results were not typical of homogeneous single crystals,4,8— such specimens will not be considered herein. The dependences of fracture stress upon Xf were of similar type for 6 mm,* 1 mm, and 0.1 mm crystals,

Jan 1, 1963

By D. S. Eppelsheimer, D. N. Williams

The cold rolled textures of iodide titanium and of three samples of commercial titanium were examined using the Schulz-Decker Geiger counter technique. The iodide titanium and two of the three samples of commercial titanium showed a (0001) [1010] texture rotated 30&apos; toward the transverse direction about an axis in the rolling direction. The third sample of commercial titanium showed a double texture. THE metals of the hexagonal system tend to deform similarly if the c/a ratios are similar. Thus titanium, zirconium, and beryllium, with c/a ratios of 1.601, 1.590, and 1.570, respectively,l should have similar cold rolled textures. The cold rolled texture of high purity iodide titanium has been described as (0001) [1010] rotated 30" toward the transverse direction about an axis in the rolling direction.&apos; The texture of zirconium has also been reported as (0001) [1010] with a transverse rotation from the ideal position of approximately 30" about an axis in the rolling direction." This texture differs from that reported for titanium however since a continuous spread of (0001) poles toward the transverse direction was reported rather than distinct (0001) maxima 30" from the rolling plane normal. Beryllium has a texture similar to that of zirconium although the angle of transverse rotation of the (0001) poles is much less.&apos; These three metals thus show a common type of cold rolled texture, as yet unexplained, which can be described as (0001) [1010] with various degrees of rotation toward the transverse direction about an axis in the rolling direction. Since titanium showed the greatest degree of rotation from the (0001) [1010] position, the cold rolled texture of titanium was re-examined using a semiquantitative Geiger counter X-ray technique to obtain more accurate experimental data from which a theoretical interpretation of this new type of hex- agonal rolling texture could be developed. The cold rolled textures of iodide titanium and of three samples of commercial titanium were determined. Table 1 gives the analyses of the titanium samples. Experimental Procedure Preparation of Samples: Prior to the final rolling operation each of the samples was given an initial reduction of approximately 50 pct and annealed to remove the gross effects of any previous treatments. Samples were annealed in vacuum, high purity helium, and air to determine whether annealing atmosphere had any effect on the cold rolled textures developed. All samples were annealed 1 hr at 800°C. Grain size determinations were made using the formula, 1.075 in which n is the number of grains counted in an area A (in sq mm) and M is the magnification of the area counted.&apos; This formula gives the diameter between opposite flats assuming hexagonal grains. At least three areas containing more than sixty grains each were counted in each grain size determination. Rockwell B hardness readings were made on the annealed samples. The results of the measurements of

Jan 1, 1954

By R. J. Walter, W. T. Chandler

The Ch-H phase diagram was determined for by-drogen concentrations up to ChHo.9 at temperatures below 400°P&apos;. The phase diagram includes a mis-cibility gap and a eutectoid transformation. A peri-tectoid transformation is postulated at the hydrogen-rich end of the diagram, Phase diagrams were determined for two levels oj purity, of the columbium. A single solid solution exists in the Cb-H system above 400°F. There has been considcrable disagreement among investigators concerning the system at temperatures below 400°F. Albrecht, Goode, and ~allett&apos; proposed a miscibility gap containing two bcc phases with the two lattice parameters converging at about 140°C (285-F), and Brauer and ~erman&apos; found a two-phase room-temperature region between 10 and 41 at. pct H. At sufficiently high hydrogen concentrations in the one-phase region, the hydrogen-rich phase was found to be face-centered orthorhombic. Wainwright, Cook, and Hopkills3 recently reported that the face centered orthorhombic hydride phase is derived from a unit cell which is slightly tetragonal with a small departure from 90 deg of the angle (y) opposite the r axis. The orthorhombic hydride phase was observed for hydrogen concentrations between 0.2 and 0.8 H/Cb atom ratio. Paxton and coworkers4 found that needlelike hydride plates formed in a hydrogen-charged columbium single crystal and suggested that this transformation possessed the characteristics of a diffusionless phase transformation. On the basis of room-temperature, X-ray diffraction data, komjathy&apos; suggested that an order-disorder or martensitic transformation occurs. In the present study, the Cb-H system was investigated to resolve the discrepancies found in the literature for this system. PROCEDURE The columbium specimens were prepared from two heats of wrought 1/2-in.-diameter electron-beam melted columbium rod and from two columbium powders of -80 mesh size of different impurity contents. The columbium bar stock was pur chased from Urah Chmg Corp.; the 99 and 99.5 pct purity colulnbium powders were obtained from Fansteel Metallurgical Corp. and Kern Chemical Co.. respectively. The chemical analyses of the columbium bar and powders are listed in Table I. Hydrogen charging was performed by exposing the columbium specimens to hydrogen at 1 atm pressure at various temperatures. After exposure the specimens were quenched to prevent the hydrogen pickup which would take place if cooled in hydrogen, or the hydrogen loss that would occur if cooled in an inert gas. Adequate hydrogen purity was achieved by passing high-purity tank hydrogen (maximum 5 ppm total impurities) through an Engelhard catalytic Deoxo unit, magnesium per chlorate desiccant, and finally through activated charcoal at the temperature of boiling nitrogen. Activated charcoal at -321°F has been reported6 to remove impurities from hydrogen to a nondetectable level. A schematic representation of the heat-treating apparatus is shown in Fig. 1. A metal-sheathed thermocouple embedded in the colun~bium specimen was used to control the temperature during heat treatment and to pull the specimen boat into

Jan 1, 1965

By D. G. Westlake

Polycrystalline tensile specimens of various Zr-0-H alloys have been tested at 298°, 178°, and 77°K. Solute oxygen and hydride precipitates in quenched alloys made individual contributions to the yield strength at 0.2 pct strain which combined to produce a resultant strength increment, a,., Ductility changes which were ohserved can he interpreted in terms of the various oxygen and hydrogen concentrations, testing tem -peratures, and dispositions of the hydride. ADDITIONS of oxygen in solid solution were known to increase the yield and tensile strengths of polycrystalline zirconium as early as 1951.&apos; More recently, the critical resolved shear stress (CRSS) for prism slip in zirconium single crystals was also shown to be affected by the solute oxygen impurity.&apos; This latter work also demonstrated that large increments of strength could be contributed by the finely dispersed zirconium hydride precipitates that are present in quenched Zr-H alloys.3 It was concluded that the combined strengthening due to alloying could be expressed by where to is the increase in the CRSS due to solute oxygen alone and TH is the increase due to finely dispersed hydride precipitates. Eq. [I] is analogous to one used to express the combined strengthening effects of work hardening and neutron radiation damage.4 Eq. [1] was verified only indirectly and for only small amounts of the impurities—up to 0.14 at. pct 0 and 0.63 at. pct H. The present investigation was undertaken to obtain a more direct verification of the validity of the form of Eq. [1] for this system and also to determine the combined effects of oxygen and finely dispersed hydride precipitates on the tensile strength and ductility of polycrystalline zirconium. EXPERIMENTAL PROCEDURE Tensile specimens were machined from the same rolled billet of Kroll zirconium used in the earlier study.&apos; These measured 38 by 4.7 by 0.5 mm and had 10-mm gage lengths which were 2.8 by 0.5 mm. Each specimen was ß-annealed in vacuo at 1173°K for 15.5 hr and a-annealed at 1073°K for 4 hr to D. G. WESTLAKE, Member AIME, is Associate Metal l ur-gist, Metallurgy Division, Argonne National Laboratory, Argonne, III. Manuscript submitted July 17, 1964. IMD______________ give an equiaxed structure with grain diameters averaging 0.06 mm. Oxygen was added by allowing the metal to react with a known quantity of oxygen during the 0 anneal and known quantities of hydrogen were added during the a anneal. Each alloy was encapsulated in Pyrex under vacuum, annealed at 873°K for 4 hr, quenched into ice water, and polished by immersion in a solution of 46.75 vol pct H2O, 46.75 vol pct concentrated HNO3, and 6.5 vol pct HF (49 pct) at 298°K. Special heat treatments given to a few specimens are described in the results below. Tensile tests were done on an Instron machine and were begun within 20 min after the quench, except where specified otherwise. Tests at 298°K were in air, at 178°K in acetone, and at 77°K in liquid nitrogen. All tests were at a strain rate of 8x sec-1. RESULTS AND DISCUSSION Yield Stress at 298°K. The compositions of alloys and the corresponding yield stresses (0.2 pct strain) are given in Table I. A plot of the yield stresses of the oxygen alloys, A, B, C, and D, indicates that varies linearly with CO1/2, where Co is the oxygen concentration, Fig. 1. This is in accord with Fleischer&apos;s6 theory for solution strengthening if the oxygen atoms do not cluster, or the cluster size remains constant with increasing oxygen concentration. In Fig. 1, it appears that if one could prepare some oxygen-free zirconium its yield stress would be very low. Therefore, we shall assume that for the oxygen alloys is equivalent to O0, the strength increment contributed by the presence of oxygen. The relationship between0.2and Co is expressed by 0.2 = 31.3 CO1/2, when the yield stress is in kg per sq mm and the concentration is in at. pct. Each of the hydrogen alloys, Al, A2, A3, and A4, contained 0.081 at. pct 0 as an impurity. In Fig. 1, it appears that this small amount of oxygen makes a significant contribution to the strength which cannot be ignored when we evaluate the contribution of the finely dispersed hydride. Let us assume the validity of the following equation: a0.2 = (a2o+a2R)1/2 [2] which is analogous to Eq. [I] for single crystals, and calculate values of UH for the hydrogen alloys by using the experimental values of 0.2 and o (0.081 at. pct) = 8.9 kg per sq mm. For 0.36 at. pct H, oH = 6.47; for 0.72 at. pct H, OH = 11.30; for 2.16 at. pct H, OH = 19.4; and for 3.60 at. pct H,

Jan 1, 1965