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By J. R. Hornaday, A. E. Morris, N. A. Parlee, D. C. Carmichael

Rates of absorption and effusion of hydrogen in solid iron were measurede by a Sieverts type of apparatus. With clean a iron these rates are diffusion controlled down to 420°C and are represented by the equation D = 6.70 x e-'100' crn2 sec-I Certain surface impurities can affect these rates at all temper-atuves. Thin oxide films lower, the apparent diffusivity of annealed iron markedly. Cold-worked iron (75 pct) annealed at 430°C has practically the same solubility and diffusivity as anealed iron. THE mechanism of absorption and evolution of hydrogen in solid iron alloys is not fully understood despite the large number of investigations on the subject. While there appear to be many instances of simple solid-state diffusion control of rate, there are many cases where investigators have either concluded that surface reactions are rate controlling or that some "nondiffusible" hydrogen resides in discontinuities. The purposes of this research were 1) to develop a sound method for studying this absorption and evolution behavior, 2) to examine it in pure annealed iron, and 3) to determine the effects of important variables, such as cold work, surface condition, and composition. This paper relates the progress toward these objectives. Much of the present knowledge of the movement of hydrogen through iron alloys comes from permeability studies which involve the measurement of the rate of passage (under steady state conditions) through membranes of the order of 1 mm in thickness. This method is open to question on various grounds. If surface reactions are involved, two different surfaces operating under two different conditions must be considered. The presence of defects in the membrane even of microscopic dimensions may lead to erroneous results. A few people have studied evolution of hydrogen into vacuum, under carefully controlled (unsteady state) conditions, and some of the best diffusivity data come from these sources. Most of these methods measure rates of evolution only and thus do not make a rigorous test for reversibility of behavior. It appeared that an "unsteady state" method that would permit the measurement of both rates of evolution and absorption under controlled temperature, pressure, and other conditions would offer several advantages. Accordingly the modified Sieverts apparatus described below was designed and built. APPARATUS This apparatus is shown in Fig. 1. The sample bulb is detailed in Fig. 2. Hydrogen of 99.5 pct purity and argon of 99.99 pct purity were used. The hydrogen was deoxidized and dried by means of a Deoxo unit followed by a "Dri-erite" tower. The argon was only dried. The gas burette was graduated in tenths of a cubic centimeter, and, with the aid of a travelling magnifier, readings could be estimated to the nearest 0.01 cc. The level of mercury in the burette was adjusted by means of a leveling bulb operated by a fine screw adjustment. An electrical system, consisting of two slightly separated platinum electrodes inserted in one leg of the manometer and a small light bulb was used to obtain rapid accurate adjustment of the pressure. The capillary tubing of the Vycor sample bulb was 3 mm bore as was all tubing back to the gas burette. The samples were discs made from vacuum-melted Ferrovac-E iron of greater than

Jan 1, 1961

By E. L. Swarts

In the course of a program on high-temperature processing and electrowinning of uranium at the Knolls Atomic Power Laboratory,'' it became necessary to give attention to the interaction of molten uranium with graphite. Although it is known3 that a protective interface layer may form, details of this reaction have not been reported. Unfortunately it was impossible to complete the planned experimental program. However, the general problem is considered of sufficient interest to warrant reporting those preliminary results actually obtained. EXPERIMENTAL PROCEDURE Interface carbide layers were formed by melting samples of cleaned uranium metal in small closed graphite crucibles. Equilibrations were conducted in vacuo or in an atmosphere of dry helium at temperatures ranging from 1150" to 1400°C and for periods of from 24 to 240 hr.

Jan 1, 1960

By E. T. Stephenson

Wert and Marx1 pointed out that a straight-line relationship exists between the activation energy of a relaxation process and the temperature at which the maximum relaxation occurs. The data available at the time indicated that this relationship held for a number of Snoek peaks, several grain boundary peaks, and pair relaxation in a brass. Theoretical justification for the observed relationship was found in the following equation, which Wert and Marx derived from the theory of interstitial atomic diffusion coefficients:' where AH is activation energy, R is the gas constant, T is the internal friction peak temperature, v is the interstitial atomic frequency, f is the frequency of the applied stress, S is entropy of activation. More accurate internal-friction data on interstitial diffusion in bcc metals have become available since Wert and Marx's paper. Table I gives activation energies calculated by several authors from a combination of elastic aftereffect data and the peak temperatures at several frequencies of measurement. (In the case of Fe-C and Fe-N, the referenced authors5'7'8'10 also used high-temperature diffusion data.) However, diffusion experiments at 150°C and above1'-13—rather than anelastic techniques—were used to determine the activation energy of hydrogen diffusion in Fe-H. In order to plot this recent data as a AH vs T graph we calculated the peak temperatures of the systems listed in Table I (with the exception of Fe-C, Fe-N, and Fe-H) by using published values3'' of AH and Do. These calculated peak temperatures varied by only a few degrees from experimentally determined peak temperatures. The calculated values were felt to represent the better average. A number of investigators have found the peak temperatures in Fe-C and Fe-N to be 38 to 40°C and 20° to 24°C, respectively. The values of 39" and 22°C (312° and 295°K in Table I) were determined by carefully executed experiments.6'8 The hydrogen peak temperature has been measured at 1 cps,12 20 cps,14 and 35,000 cps.15 All hydrogen peak temperatures were adjusted to 1 cps for Table I using AH = 3000 cal per mole. As Fig. 1 shows, the data of Table I fit a straight line at least as well as the earlier data used by Wert and Marx. Linear-regression analysis was applied to the data in Table I. The Fe-H data was omitted because the activation energy has not been experimentally determined in the temperature range of the peak. The analysis yields the equation: with a standard error of 860 cal per mole. The agreement of the data in Table I with the Wert-Marx equation is excellent. Strict application of Eq. [I] forces the linear regression analysis through the origin. In this case, the analysis gives a slope of 62.1 cal per mole per deg, and a standard error of *890 cal per mole. With this value, it follows from internal-friction theory that Hence, Do varies by only 30 pct among these bcc-interstitial systems. Thus, a concept suggested originally by Wert and Marx1 is confirmed by recently published data. The

Jan 1, 1965

By R. P. Smith

The carbon content of a number of alloys ranging (before carburitation) from purified iron to purified cobalt was determined for fixed activities of carbon by equilibration with each of six CO-CO2 atmosphere at 1000°C. At fixed carbon activity, the carbon content decreases continuously with increasing cobalt content. For concentrations of 0 to 50 at. pct Co the results can be expressed by a linear interaction equation of the type In y2 = 7.76n2/(n1+n3)+ 2.30 n3/(n1+n3) where y2 is the activity coefficient of carbon (standard state such that y2— 1 as n2 — 0 in the Fe-C binary) and n1, n2, and n3 are the number of atoms of iron, carbon, and cobalt per unit weight of alloy. The results are also given in terms of the a functions. In the same concentration range, the results are in accord with the regular solution theory of Alcock and Richardson. THE carbon content of Fe-Si, Fe-Mn, and Fe-Ni alloys at fixed activities of carbon has been reported previously.'-, The present work extends R. P. SMITH, Member AIME, is Research Chemist, E. C. Bain Laboratory for Fundamental Research, United States Steel Corp., Research Center, Monroeville, Pa. these measurements to a series of Fe-Co alloys. These alloys, like the Fe-Ni alloys, are fcc ("aus-tenitic") over the entire range of composition at 1000°C. EXPERIMENTAL PROCEDURE The alloys were made from electrolytic cobalt and Plast-Iron in a small vacuum-melting furnace. A small amount of graphite was added to each melt to keep the oxygen content low. The ingots were analyzed for iron and carbon: the amount of cobalt was obtained by difference. Analysis of the top and bottom of the ingots indicated that they were uniform in alloy content. Except for the pure cobalt the ingots were hot-rolled to approximately 0.15 cm thickness, cleaned by sandblasting, then cold-rolled to about 0.045 cm. We were not successful in cold rolling the pure cobalt; therefore it was hot-rolled to the final thickness. The last traces of surface oxide were removed by acid pickel, then the samples were treated in a hydrogen-2 pct water vapor mixture at 1100°C to remove carbon and most of the oxygen. The carburizing procedure was similar to that previously described.1,2,4 The alloys in the form of strips about 1.7 cm wide, 7.5 cm long, and 0.04 cm thick, together with a similar specimen of purified iron, were equilibrated with each of six CO-CO2 mixtures of fixed composition, then quenched in the

Jan 1, 1965

By W. Evans, C. E. Ells

The agglomeration of hydrogen in pure aluminum and A1-Mg alloys has been studied through use of hydrogen introduced into the metal by cyclotron proton irradiation. Both the growth and dispersal of the agglomerates have been followed by metal-lographic techniques. During the cyclotron irradiation, agglomeration occurs at temperatures i 100°C for hydrogen concentrations as low as 1 ppm. On heating at elevated temperatures, 300°C to 600°C, intragranular agglomerates first coarsen and then disperse. The agglomerates formed at grain boundaries are much larger than the intragranular agglomerates; with hydrogen concentra- tions > 10 PPm, heating for 1 hr at 500°C results in extensive grain-boundary cracking. The hydrogen agglomerates have been shown to inhibit grain growth, but no inhibition of recrystallization has been observed. The ability of hydrogen to enter aluminum at a free surface, combined with its high-diffusion rate at elevated temperatures, accounts both for growth and dispersal of the agglomerates. Irradiations at elevated temperatures give results consistent with the explanation proposed for agglomerate behavior on post-irradiation heating. 1 HE formation of hydrogen-filled bubbles, or blisters. in aluminum and its alloys has been studied for over' thirty years. The work up to 1952 has been reviewed by Kostron' and since then Ransley and

Jan 1, 1963

By J. M. Dupouy, R. A. Rawe, M. B. Bever

The aging characteristics of a titanium alloy containing 13 pct V, I1 pct Cr, and 4 pct A1 have been investigated by hardness measurements, X-ray diffraction, and metallography. The P phase decomposes into 0 + a, and 0 + a, + TiCr, above about 1050°F; below this temperature a transition phase, believed to be w, precipitates first, followed by a, and TiCr,. The observed hardening is attributed to these reactions. Cold working of solution-treated specimens accelerates hardening and raises the hardness level attained. A TTT diagram is proposed. NEW titanium-base alloys, designated as "all-beta," have recently been developed. These alloys contain large amounts of P-stabilizing elements such as molybdenum, chromium, or vanadium. When cooled from the solution temperature, they consist only of P; in particular, the martensitic a,' phase does not form.

Jan 1, 1961

By A. R. Kaufman, P. Gordon

THE large-scale manufacture and use of uranium in conjunction with the atomic energy development during the war led to a need for knowing the equilibrium diagrams of uranium with various other metals. The alloys of uranium with aluminum and with iron were among the first that were studied for this purpose. Much of the work was done in the manner of a survey since it was necessary to determine the important features of the phase diagrams rather than to obtain completely detailed results. For this reason no attempt was made to locate exactly such features as liquidus lines, solid solubility limits and compound and eutectic compositions. It is believed, however, that there are no great inaccuracies in the diagrams reported here and that no important points were overlooked. Earlier work on alloys of uranium with aluminum and iron is almost nonexistent and in each case is considered to have been of little value by M. Hansen. It is interesting to note, however, that the compound UAl3 was first reported in 1902 by L. Guillet. Experimental Procedure Materials: The uranium used for making most of the aluminum alloys was obtained from material prepared by Metal Hydrides, Inc., and melted in vacuum at M.I.T. Because of the lack of an adequate supply of metal, it was necessary to use material from several different batches and hence it is impossible to state an exact analysis. However, a few results indicated about 0.01 to 0.03 pct iron and probably about 0.03 to 0.05 pct carbon. Toward the end of the work a small amount of metal was obtained from Brown University and from Iowa State College and this was used in determining the transformations in pure metal and in some dilute alloys. All of the aluminum used in this investigation came from a supply of high purity metal (greater than 99.9 pct aluminum) which was obtained through the courtesy of Dr. Mehl of the Carnegie Institute of Technology. The uranium used for making the alloys with iron was produced by the bomb reduction process which has been described by J. Chipman.² This metal, after vacuum melting, contained about 99.9 pct uranium by weight with carbon and iron as the chief impurities. Electrolytic iron containing about 0.012 pct carbon, 0.020 pct nickel and 0.009 pct copper was used in making the melts. Melting Equipment: The melting of the alloys went through a stage of development which culminated in the use of beryllia or beryllia-lined crucibles and in the use of high frequency heating in either vacuum or in an atmosphere of argon. It was found that uranium at a few hundred degrees above its melting point would pick up aluminum and to a lesser extent silicon from an alundum thimble while aluminum above 1000°C would extract silicon from the impure alundum. No reaction of either metal with beryllia was noted at temperatures as high as 1800°C. The distillation of aluminum from the aluminum-rich alloys was quite troublesome at temperatures above about 1300°C and was only partially avoided by the use of argon instead of vacuum. Melting in resistance furnaces,

Jan 1, 1951

By A. R. Kaufman, P. Gordon, C. H. Schramm

AS a part of the general program on alloys of uranium carried out at the Massachusetts Institute of Technology under contract W-7405-eng-175 for the Manhattan Project during the recent war, it was considered desirable to investigate the boundary binary phase diagrams of the ternary alloy system uranium-tungsten-tantalum. Previous work on these alloys was practically nonexistent. A brief statement to the effect that tantalum and tungsten form a continuous series of solid solutions was found in a general paper on tantalum by W. V. Bolton1 but no information was available on the uranium-tungsten and uranium-tantalum systems. The research to be described in this paper has served to delineate the main features of the uranium-tungsten, uranium-tantalum phase diagrams and to check Bolton's work on the tungsten-tantalum diagram. Experimental Details Metals: The tungsten and tantalum used for preparing the alloys were 99.96 and 99.65 pct pure, respectively. The chief impurities in the metals were about 0.02 pct molybdenum in the tungsten, and 0.2 pct columbium, 0.05 pct tungsten, 0.02 pct barium and 0.01 pct silicon in the tantalum. The uranium used was 99.9 pct pure, with the main contaminants being iron and carbon. (An appreciable amount of magnesium was present in the uranium as received, but this distilled off during melting and so is not reported as an impurity.) The composition of specimens indicated in the subsequent figures and tables of this paper are the results of chemical analyses on the cast alloys except for the tantalum-tungsten alloys. For the latter, chemical analysis was not very reliable as a result of the difficulty of separating tungsten and tantalum chemically. Consequently, the nominal

Jan 1, 1951

By A. E. Deruyttere, J. Van der Planken, M. Laurent, Van den Bergen

FahRENHORST and schmid1 observed that zinc single crystals work hardened less rapidly when strained in liquid air (- 185°C)than in a bath at -82°C, whereas at higher temperatures the rate of work hardening decreased with increasing temperature, as would be expected. Cadmium and magnesium showed no such decrease at -185°C. At that time the observed anomaly for zinc at liquid air temperature probably seemed insignificant. However it later was confirmed2 by experiments in liquid nitrogen (-196°C) and in the mixture solid carbon dioxide-acetone (-77"C) and therefore appeared to be real. seeger3 then suggested that the anomaly might be due to the different wetting of the zinc crystals by the cooling media. Recently a new confirmation was obtained,4 however the cooling media again were different: the rate of strain hardening was found to be lower in liquid nitrogen and liquid oxygen than in pentane cooled to various temperatures down to -126°C. Ekperiments will now be reported in which the medium surrounding the specimen at the different temperatures was the same, namely gaseous air. The single crystals were made from "Overcor 99.99" zinc. They were grown in a vertical traveling furnace on seeds of nearly the same orientations. The diameter of the crystals was 5 mm and the length between shoulders 140 mm. The brass shoulders were stuck to the crystals by means of araldite. A thin steel wire was fixed to each shoulder and served to fasten the specimen to a Houns-field tensile testing machine. The crystals with the shoulders and part of the wires were surrounded by two concentric cylindrical containers. The coolant. either liquid air or ground solid carbon dioxide, was poured into the outer container only. During cooling the containers rested on a support which was removed when the straining was started. In order to check the temperature which the crystals would attain inside the inner container, a hollow bar of zinc in which a thermocouple was fitted was first mounted in the apparatus as a substitute for a crystal. It appeared that a constant temperature, respectively - 183° and -72°C, was attained inside the bar, if a soaking time of the order of 1 hr was allowed and if the outer container was constantly kept filled. Accordingly, this procedure was adopted for every tensile test. To take account of the large scatter, fourteen tensile tests were performed with liquid air and seven with solid carbon dioxide. The orientation of the crystals and the results are presented in the table, in which the symbols have the following meaning: 1 : temperature x : initial angle between basal plane and specimen axis : initial angle between slip direction and specimen axis a : shear strain at fracture 0: average rate of strain hardening = —-——- 100 t0 and Te representing respectively the critical shear stress and the shear stress at fracture. Despite the scatter of the a- and 8— values which is of the same order of magnitude as in the work reported by Seeger and Trzuble,4 it is evident that the strain hardening rate is significantly lower at -183°C thanat-72°C. The table also contains the average values calculated from Seeger and Trauble's results at the corresponding temperatures: z.e., four results at -183oC and two at-70°, -71°C. These authors calculated 9 in a slightly different way, but this is unimportant. The agreement between the a-values shows that both sets of experiments are comparable despite the differences in experimental techniques. The rates of strain hardening also agree and it may therefore be concluded that the anomaly is not

Jan 1, 1962

By A. H. Daane, B. J. Beaudry

The uranium-antimony system has been investigated by metal-lographic, therma1, and X-ray methods. There are four intermediate phases present: USbz and U,Sb, which undergo peritectic decomposition at 1355°and 1695OC, respectively, and USb and UPSbs which melt congruently at 1850"and 1800°C, respectively. There is a eutectic between U4Sbs and USb which melts at 1770°C. USb,, UsSb4, and USb are line compounds while U4Sbs has a solubility range of approximately 1.5 at. pct at 1770°C. Single crystal studies of the cmpo,und U.,SbS show it to have a hexagonal unit cell with a, = 9.268A and c, = 6.201b;. The solubility of uranium in liquid antimony increases from 0.1 at. pct at 650°C to 1.5 at. pct at 900°C. The solubility of antimony in a, P, and y uranium is approximately 0.02, 0.1, and 0.05 at. pct respectively. IN nuclear reactors, uranium has been used mainly in the form of solid-fuel elements of the pure-metal or uranium-rich alloys. However, in attempts to overcome some of the difficulties inherent in solid-fueled reactors, reactor concepts hive been proposed in which the fuel would be a liquid metal, such as a solution of uranium in another metal. The liquid-metal fueled reactor (LMFR) designed by the Brook-haven National Laboratory of the U.S. Atomic Energy Commission is an example. Fuel for this reactor is a solution of approximately 800 ppm enriched uranium in bismuth.' To design such liquid-fueled reactors, a background of information on the solubility of uranium in various metals is obviously necessary. The present study was undertaken to pro- vide information for such purposes, and in addition, to study the uranium-antimony system as a whole. A preliminary literature search showed that some work had been done previously on uranium-antimony alloys, but no attempts had been made to make a complete study of this system. The solubility of uranium in antimony was studied by Cammack and Bridger' up to 950°C and by Hayes and Gordon up to 900'-C. Their data are plotted in Fig. 1. Ferro, in an X-ray structure study of some uranium-antimony compounds, found USg to be tetragonal with a, = 4.2724 and c, = 8.471A, U3S4 to be b.c.c. with aO = 9.095A and USb to be f.c.c. with a,= 6.191A. Colani reported the compound UsSba; however, work by Ferro and by this Laboratory showed that this compound does not exist. foote' reported several intermediate phases in the uranium-antimony system, but did not identify them. Greninger' re-ported finding an intermediate phase in a 5 at. pct Sb

Jan 1, 1960

By G. Koves

The behavior of case-hardened AISI C-1213 free -machining steel under complex impact-fatigue -wear load conditions was investigated. The inherently poor dynamic properties of the steel are mainly affected by the stress distribution in the case, component shape, and tempering. Cold-riveted components showed unexpectedly high dynamic strength compared to basic parts. A compromise beatment—which provides good dynamic properties, reasonable wear resistance, and fair riveting characteristics—zuas developed. A number of mechanical components in data-processing machines are made of free-machining carbon steel. Although, selected primarily due to manufacturing requirements, components made of these grades frequently undergo complex heat treatment and must sustain impact-fatigue loads. A typical free-machining steel is the AISI C-1213 grade, which is a resulfurized and rephosphorized open-hearth steel. While the undesirable effects of sulfur and phosphorus on the mechanical properties are well-known, data on dynamic properties are scarce.1"3 Rapid rotating or oscillating motion while carry- ing a high cyclic load requires a combination of wear resistance with high endurance limit and impact toughness. The inherently poor dynamic properties of the free-machining steel are further degraded by the machining, which introduces local stress-concentration areas. While the heat treatment (usually case hardening) improves some mechanical properties, it necessarily impairs others. Another problem arises when components, such as studs, must be fastened by riveting. The high crack-sensitivity of the free-machining steel, especially in the presence of a hardened case, makes this operation difficult. In view of the preceding considerations, it is of interest to investigate the behavior of a typical component under complex impact-fatigue-wear loading conditions in order to explore the effects of material, machining, and heat treatment, to obtain specific data on the dynamic characteristics of free-machining steel, and to arrive at a process which would adequately utilize the inherent qualities of this material. EXPERIMENTAL PROCEDURE To simulate actual service conditions, a typical component was selected, based on frequency of application, complexity of load, and processing difficulties. The dimensions and shape of the component—a stud used in many electromechanical document-handling machines—are shown in Fig. 1.

Jan 1, 1964

By N. F. Foster

The use of piezoelectric semiconducting materials for the fahrication of ultrasonic transducers has raised the upper fundamental frequency limit for transducers from about 200 mc to above 10 kmc, Several types of semiconductor transducer configurations have been proposed and examined experimentally. Depletion-layer transducers have been made and operated at frequencies below 1 kmc hut they appear to he better suited for operation at considerably higher frequencies around 10 knzc. Diffusion-layer transducers have been made and operated in the range 50 to 1000 mc and have exhihited considerably improved conversion losses and bandwidths compared with other transducers available in the frequency range. A variety of novel structures are possible using these new types of transducers, some of which could lead to substantial advances both in research and in the fabrication of ultrasonic delay lines and memory elements. THE field of ultrasonics today spans some five decades of the frequency spectrum from the audible to the kmc range and finds applications ranging from fundamental research into the atomic structure of matter to the degreasing of machine parts. To cover this wide range it has been necessary to develop a great many types of ultrasonic trandsucers utilizing a variety of materials and physical phenomena. The first ultrasonic transducers were made during World War I for a submarine-detection system. They consisted of plates of single-crystal quartz bonded between metal plates and were one of the first applications of the phenomenon of piezoelectricity discovered nearly 30 years previously. Despite the many advances which have been made in transducer technology, piezoelectric transducers using single-crystal quartz are still used almost exclusively for application above about 30 mc. Transducers at these frequencies are normally made in the form of thin quartz plates which are then bonded onto the medium in which the ultrasonic wave is to be propagated. The crystallographic orientation and geometry of these plates determines the type of wave generated and the way in which the efficiency of the electromechanical conversion varies with frequency. Analysis of the design parameters shows1 that the frequency of maximum efficiency (the fundamental or resonant frequency) is that frequency at which the transducer is approximately half the wavelength of the ultrasonic wave in the material. As the frequency increases, the ultrasonic wavelength, and therefore the optimum transducer thickness, decreases and in practice the fabrication of quartz transducers with fundamental freauencies above 100 mc becomes extremely difficult due to the extreme thinness required. For frequencies above 100 mc quartz transducers can be used in overtone-mode operation, and for very high frequencies (500 to 24,000 me) a technique using a quartz rod inserted in a high-Q microwave cavity4 is available. These techniques, however, exhibit comparatively low fractional bandwidths and rather poor conversion efficiencies. The present trend in ultrasonics is towards high frequencies and greater bandwidth to allow the use of shorter pulses which can give increased discrimination in radar-system delay lines and greater storage capacity in computer applications. The increasing demand for more efficient transducers with greater bandwidth

Jan 1, 1964

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 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 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 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 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 A. D. Schwope, L. R. Jackson, K. F. Smith

Burghoff and Blank1 have pointed out that the creep properties of hard-drawn coppers are closely associated with their individual softening characteristics and have further shown that the creep resistance of various types of copper is improved, under certain circumstances, by cold stretching. In the design of certain types of electrical machinery, it is important to have the creep resistance as high as possible; furthermore, short-time creep strength is important since in many cases stresses are large only during warming-up and cooling-down periods. In this paper, data are presented showing the effect of cold work on the short time creep strengths of various types of commercial copper under several conditions. It is shown that trends from short-time creep tests are evident at longer times. Materials Used in the Investigation The coppers used in this investigation were commercial grade and of two basic types, oxygen free high conductivity (OFHC) and tough pitch. Additions of silver in amounts of 15 and 25 oz per ton were added to each of the two coppers. The analyses of these six coppers are given in Table 1. Originally, they started as wire bars 4 X 4 X 54 in. A. square rod was made by hot rolling the wire bars to 9/16-in. rod in 8 passes. This rod was then cold drawn to 0.445-in.-diam rod and annealed for 3 1/2 hr at 1000°F. It was then cold drawn to 0.325-in. rod and again annealed at 1000°F for 3 1/2 hr. Hard square rods were then made by cold rolling to 0.257 X 0.257-in. rod. Soft wire was made from the hard- drawn material by annealing at 650°F for 3 hr. The final rolling was performed using a set of 9-in. grooved rolls revolving at 30 rpm, which produced square wires. Reductions of approximately 5, 20, 30, and 40 pct were obtained using several passes in the same direction for the large reductions. The 5 pct reduction by drawing was accomplished using a steel die having 2 parallel bearing surfaces. The die angle was 7 1/2 degrees and the wires were lubricated with a paste of ceresin wax dissolved in carbon tetrachloride. The speed of drawing was 13 fpm. Since work was done on only two sides of the wire simultaneously, it was necessary to rotate it 90 degrees each pass to insure uniform deformation. The room-temperature tensile properties of the various tempers are given in Table 2. The grain size of the an- nealed 0.257-in. wires was uniform and averaged about 0.035-0.045 mm. Experimental Procedures for Short-time Creep Tests Standard creep-test frames (Fig 1) were used for the testing. Special fixtures were designed to apply axial compressive and tensile loads to the copper wires. The compression specimens were 1 in. long and the ends were ground flat and parallel. The creep in compression was indicated by the movement of reference marks s-ratched on intersliding platinum strips attached to the moving heads of the fixture. The movement was measured with an optical micrometer fitted with a filar eyepiece on which the smallest division was 0.00005 in. The tensile creep specirriens were 4 in. long which provided ample gripping surface for the jaw-type grips. The platinum strips were attached to a one-inch gauge length of the wire and the creep measured as previously described. The single-specimen furnaces were connected to individual power and control sources. The controlling equipment consisted of Foxboro controllers

Jan 1, 1950

By G. R. Purdy, J. G. Parr

The intermetallic compound Ti2Co was studied by X-ray diffraction and metallographic techniques. The phase occurs off stoickzometric composition, with its greatest variance at high temperature. The solubility limits of the phase have been cletermined, and an amendment to the titanium-cobalt phase diagram is suggested. THE first intermetnllic compound to appear at the titanium-rich side of the titanium-cobalt system was found by Laves and wallbauml to be Ti2Co. They described this compound as isomorphous with Ti2Ni and Ti2Fe, and demonstrated that it had a face-centered-cubic structure with 96 atoms per unit cell. This contention is supported by the work of Duwez and Taylor2 and Orrell and Fontana3 who also determined the lattice parameter to be about 11.30A. Rostoker4 believed that Ti2Co did not exist, and that the phase considered by the other workers to be Ti2Co was Ti,Co20. However, Orrell and Fontana determined oxygen and nitrogen contents and found that their alloys did not contain sufficient of these elements to produce significant quantities of a stoichiometric oxygen compound. The present investigation was initiated to determine the composition limits of the phase Ti,Co.

Jan 1, 1961