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By J. D. Lubahn

Prior tests by Dorn, where the strain rate in a tensile test was suddenly changed, have shown a small, but definite rate-history effect to exist. If this effect is neglected in the calculation of creep behavior from tensile results, an error should occur. This paper shows that this error is smaller than experimental scattering, and may be neglected. DORN1 has found a small but definite rate-history effect in the aluminum alloy 250 at liquid-nitrogen temperature using tensile tests with an abrupt rate change. Such an effect is to be expected from pre-viously known2-6 temperature-history effects, together with general experience that effects produced by changing the strain rate a large amount are simi-

Jan 1, 1959

By J. R. Mihalisin

THE application of electron-microscopic techniques to the study of high-temperature alloys has met with considerable success.' This is due, in part, to the submicroscopic nature of the phases present in this type of alloy making high resolution methods necessary. Among the newer electron-microscopic techniques, the extraction replica technique' has proven to be of great value. This method allows phases to be examined in situ in the microstructure and permits their identification by means of electron diffracticn. This technique eliminates the main disadvantage in using electrolytic extraction of residues as a means of phase identification; that is, the uncertainty of relating constituents identified in the residue to what is observed microscopically. In the course of work relating microstructure to physical properties in high-temperature alloys, it was found that the formation of grain-boundary carbide phases and intragranular precipitation of an age-hardening phase greatly influence strength and ductility at high temperature. In particular, it was found that the formation of a unique type of precipitate in Nimonic "80" (a nickel-chromium-aluminum-titanium type superalloy), termed cellular or discontinuous precipitate, at grain boundaries generally results in poor ductility at high temperature. However, this mode of precipitation can be avoided by proper heat-treatment. It was assumed that this precipitate was either a carbide or age-hardening type of phase. Using various etching procedures with the extraction-replica technique, it was found to be possible to extract the carbide and age-hardening phases preferentially in this type of alloy. Previous work has shown that the age-hardening phase can be extracted from superalloys merely by

Jan 1, 1959

By J. O. Betterton, D. S. Easton

A detailed investigation was made of the phase diagram of silver-zirconium, particularly in the region 0 to 36 at. pct Ag. The system was found to be characterized by two intermediate phases Zr2Ag and ZrAg and a eutectoid reaction in which the -zirconium solid solution decomposes into a-zirconium and Zr2Ag. It was found that impurities in the range 0.05 pct from the iodide-type zirconium were sufficient to introduce deviations from binary behavior, and that with partial removal of these impurities an increase in the a-phase solid solubility limit from 0.1 to 1.1 at. pct Ag was observed. The phase diagram of the silver-zirconium system is of interest as an example of alloying a transition metal from the left side of the Periodic Table with a Group IB element. Silver would normally act as a univalent metal, its filled 4d-shell remaining undisturbed during the alloying. However, there is a possibility that some of the 4d electrons might transfer to the zirconium. An insight into such a question can occasionally be obtained by comparison of phase diagrams. The silver-zirconium system forms part of a more complete review of various solutes in zirconium in which these valency effects were studied.' Earlier work on the silver-zirconium system was done by Raub and Enge1,2 who investigated the silver-rich alloys. After the start of the present experhents, work on this system was reported by Kemper3 and by Karlsson4 which for the most part agrees with the phase diagram presented here. EXPERIMENTAL PROCEDURE The alloys were prepared by arc casting on a water-cooled, copper hearth with a tungsten electrode and in a pure argon atmosphere. Uniform solute composition was attained by multiple melting on alternate sides of the same ingot. Progressive improvements in the vacuum conditions inside the apparatus during the course of the experiments reduced the Vickers hardness increase of the pure zirconium control ingot from 10 to 20 points, observed initially, to negligible amounts at the end of the experiments. Such hardness changes in zirconium are a well known indication of purity. For example, -01 wt pct additions of oxygen, nitrogen, and carbon increase hardness by 6, 10, and 3 VPN respectively. '9' Further verification that the final casting technique did not add a significant quantity of impurities was obtained when pure zirconium was arc cast and then isothermally annealed in the vicinity of the allotropic transition. The transition was always observed to take place over the same temperature range as in the original crystal bar. The alloy ingots were annealed in sealed silica capsules for times and temperatures which varied between 1 day at 1300°C and 60 days at 700°C. The best method found to prevent the reaction of the zirconium with the silica was foil wrapping of molybdenum or tantalum. With this method, samples of pure zirconium were found to be unchanged in hardness after annealing for 3 days at 1200°C. In most of the experiments the protection of these foils was supplemented by an additional layer of zirconium foil inside the molybdenum or tantalum foil. The alloys, foil, and the capsule were outgassed at pressures in the range 10 to l0-7mm Hg in the temperature range 800" to 1100°C before each anneal in order to remove hydrogen and other impurities, and to provide a suitable container for the high purity, inert atmosphere, which is essential in the annealing of zirconium. The temperature measurements were made with Pt/Pt + 10 pct Rh thermocouples calibrated frequently during the experiments against the melting points of zinc, aluminum, silver, gold, and palladium. For the longer anneals the sum of various temperature errors was generally well within ± 2°C. For short-time anneals and during thermal analysis the overall temperature error is considered to be within ± 0.5°C. The compositions of the alloys from the quenching experiments were determined by chemical analysis at Johnson Matthey and Company, Ltd., under the direction of Mr. F. M. Lever. The actual metallo-graphic samples were individually analyzed in every case, and prior to the analyses two or more sides of each specimen were examined to insure that the specimen was not segregated. The sum of the solute and solvent analyses was in each case within the range 99.9 to 100.1 pct. In the course of the experiments, minor impurities in the range 0 to 500 ppm were found to have significant effects on the zirconium-rich portion of the phase diagram. Similar effects had been encountered previously in other zirconium phase-

Jan 1, 1959

By A. G. Metcalfe, Koeneman

A study of the structure of chemically deposited nickel by Goldenstein, Rostoker, Scpssberger, and Gutzeit has been reported recently. In this work it was shown that the nickel deposit produced by the catalytic nickel-reduction process was an amorphous solid. Crystallization occurred at elevated temperatures when the original powder pattern which showed only a diffuse ring with a d-spacing of 2.01A became sharp, revealing nickel and nickel-phosphide lines. The phosphide was indexed provision%lly on a tetragonal lattice of parameters a = 9.01A and c = 4.42A, which is in reasonable agreement with the structure of Ni3P proposed by No-wotny and Henglein.3 The transformation from the amorphous to the solid state occurs abruptly (e.g., after 7 min holding at 400°C) with the evolution of considerably more than 1000 cal per gm-mole. A more detailed analysis of these effects requires a knowledge of the solubility of phosphorus in nickel. Konstanti-now3 mapped out the phase diagram in 1908 but did not determine the solid solubility. The eutectic was placed at 11 pct P and 880°C. The purity of typical catalytic nickel deposits is very high.' Spectrographic analysis for heavier elements showed only trace amounts of aluminum, calcium, iron, magnesium, lead, and silicon. The term "strace" is a qualitative definition for less than 0.1 pct and probably less than 0.01 pct. Analysis for the interstitial elements yielded 0.04 pct C, 0.0023 pct 0, 0.0005 pct N, and 0.0016 pct H. Some of this material with 7.5 pct P was used in the present work. EXPERIMENTAL METHODS Alloys were prepared from carbonyl-nickel shot and a master composition containing 7.5 pct P. Cold-crucible, nonconsumable-arc melting was used.

Jan 1, 1959

By E. A. Peretti

BEFORE embarking on a detailed investigation of the system indium-antimony-bismuth, experiments were carried out to determine the existence of quasi-binary sections. The bordering binary systems are known1 and show the occurrence of three intermetallic binary species corresponding closely to InSb, InBi and In2Bi. Attention was focused on the low-indium end of the ternary diagram where the possible quasi-binary sections, excluding ternary compound formation, would involve the pairs: InSb-Bi, InBi-Sb and InSb-InBi. The latter pair revealed itself as a true quasi-binary, so it was investigated fully by thermal analysis, x-ray and microscopic examinations. All compositions were made by proper combination of three elements involved. The indium had a guaranteed purity of 99.97 pet; the antimony contained 99.99 pet Sb, and the bismuth had a purity of 99.99 pet. Alloys were made by melting together antimony, bismuth and indium in evacuated, sealed pyrex-glass tubes at a temperature of 600°C with vigorous agitation. The melts, weighing about 80 grams, were allowed to freeze in the sealed tubes and finally were transferred to glass tubes for the taking of cooling and heating curves. A protective atmosphere of helium was used, and the melts were stirred mechanically while cooling at rates of from 0.5 to 3°C per min. Temperatures were measured with a calibrated chromel-alumel thermocouple and were recorded graphically on a Minneapolis-Honeywell extended-range recorder working in conjunction with a Leeds and Northrup type K-2 potentiometer. Conventional polishing techniques gave satisfactory results in preparing specimens for microscopic examination. Etching was carried out with Vilella's reagent or aqueous mixtures of chromic oxide with either nitric acid or sulfuric acid plus dichromate. Conclusions deduced from the thermal analysis and microscopic examinations were confirmed by X-ray photograms using Co-K alpha radiation. The phase diagram is shown in Fig. 1. The liqui-dus consists of an uninterrupted line running from the freezing point of InSb (525°C) to a eutectic point experimentally indistinguishable from the freezing point of InBi (110°C). X-ray patterns of the InSb show a slight expansion of the lattice with the addition of InBi, and microscopic work indicated the solid solubility of InBi in InSb to be less than 0.5 pet at room temperature. Acknowledgment We wish to thank the Indium Corporation of America for the loan of the indium used in this investigation. References 1 E. A. Peretti and S. C. Carapella, Jr.: Trans. ASM., 1949, vol. 41, P. 947. T. S. Liu and E. A. Peretti: Trans. ASM, 1952, vol. 44, p. 539. Metals Reference Book, vol. 1, 2nd ed., AIME, p. 345.

Jan 1, 1959

By W. Rostoker, R. F. Domagala, R. P. Elliott

The phase equilibria of the Hg-Th system over the composition range 0-100 pct Th and temperatures up to 1000°C have been studied for a small-volume, closed system. The solubility of Th in liquid Hg is about 5 pct at 300°C and decreases sharply with decreasing temperature. Two intermediate phases occur, Hg3 Th and HgTh. The structures of these are hexagonal (nonideally close-packed) and face-centered cubic, respectively. The HgTh phase decomposes eutectoidally at 400°-500°C. The solubility of Hg in solid thorium seems to be negligible. AFULL-phase diagram for this system would have to be defined on temperature-composition-pressure co-ordinates. This paper describes the pseudo phase diagram of a closed system, that is, where the alloy enclosed in a small volume equilibrates with a vapor pressure of mercury dictated by composition and temperature. Because of the experimental difficulties in studying a system of this nature, many of the phase relations can only be sketched. Alloy Preparation Alloys over the full range of composition were made from triple distilled mercury and one of two grades of thorium. For the bulk of the work, a calcium-reduced metal in sintered pellet form of reported 99+ pct total thorium content was used. Arc-melted specimens of this thorium gave a hardness of 135 VPN. The microstructure showed small primary dendrites of ThO2. A number of alloy compositions were made with a high-purity, iodide-decomposition thorium metal. The are-melted hardness of a button of this material was 35 VPN. Although the microstructure of the arc-melted specimens showed no dendrites of ThO2, there was definite evidence of an unidentified phase enveloping the grain bound-aries. There were no distinguishable differences between the constitution of alloys made with the two grades of thorium metal. Under normal conditions thorium is not wetted by liquid mercury. The film of ThO2 on all thorium metal cannot be penetrated by either liquid or vaporous mercury. It was therefore necessary to comminute thorium in the presence of mercury under such conditions that oxide films could not reform on the newly exposed metal surfaces. This was accomplished by the use of a high-speed, carbide-tipped rotary cutter incorporated in a chamber purged with argon and connected at the bottom to a demountable Vycor bulb containing a weighed amount of mercury. This experimental device is fully described in a separate paper.1 Alloy compositions were calculated by weighing the empty bulb, the bulb containing the mercury, and the bulb containing the mercury and the thorium chips. Many alloys were analyzed chemically for thorium and/or mercury after subsequent homogenization; the agreement between analyzed and calculated compositions was invariably very close. Bulbs containing the requisite amounts of mercury and fine thorium chips were clamped off, removed to a sealing unit, evacuated and sealed. Amalgamation under these conditions proceeded rapidly even at room temperature. To insure homogeneity, the specimens were annealed to 300-400°C. Alloys containing less than 30 pct Th remained pasty after all treatments, indicating an equilibrium condition of liquid plus solid. Alloys with more than 30 pct Th were transformed into a dark powdery product. These latter specimens were annealed for times of up to 1 week to complete interdiffusion. Many of the alloy compositions are pyrophoric. On exposure to air they oxidize with considerable evolution of heat to a mixture of ThO2 and free mercury. It was mandatory that alloy specimens be handled in a "dry box" purged thoroughly with argon. All X-ray diffraction specimens were powdered, screened, and sealed in capillary tubes within the dry box. Experimental Procedures Thermal analysis experiments, useful only in the mercury-rich region of the system, were conducted with the alloys in their original containers. A reentrant thermocouple well formed an integral part of the bulb. These bulbs were heated in a silicone oil bath and cooled in a dry ice-acetone mixture. The rates of heating and cooling were slowed by immersing the specimen bulb in a larger tube containing silicone oil. This provided a suitable thermal lag. In all tests, pure mercury was run as a basic standard. While the invariant reaction at about the melting point of mercury was detected by thermal analysis, the heat effect at the liquidus was not sufficient to produce an inflection in the cooling curve. It was necessary to determine the liquidus temperatures at the mercury-rich end of the system by "breaks" in electrical reslstivity versus temperature curves for individual alloys. The apparatus for this purpose consisted of a pyrex tube about 2 in. diam and 12 in

Jan 1, 1959

By L. C. Weiner

For zinc single crystals, xo = 3o, a surface coating raises both the cleavage and yield strengths over a large temperature range. The "brittle temperature," associated with slip after completion of twinning, does not coincide with the point of intersection of the flow and cleavage curves, which is associated with twinning. A surface film has no effect on the brittle temperature, while it lowers the intersection temperature some 20°. For crystals, yn = 83o, a coating decreases the cleavage strength, making it temperature independent, as well as increases the brittle temperature or its equivalent, the intersection temperature, 20°. These observations are described on the basis of a dislocation-pile-up-at-a-barrier model for brittle fracture; in crystals x,, = 3o the number and distribution of twins play a vital role. IN a recent investigation on the effects of solid environments on the brittle fracture of zinc single crystals,' it was demonstrated that the presence of a surface film changes the cleavage strength of these crystals, either increasing or decreasing it, depending on the crystal orientation. An increase in cleavage strength of some 43 per cent was found for coated crystals oriented x, — 3o K = 28",* while a decrease of 48 per cent was observed with crystals X" = y» — 83". Moreover, these effects were found

Jan 1, 1959

By J. W. Pugh

PREFERRED orientations in cold-rolled body-centered-cubic metals appear to have remarkable similarity. The as-cold-rolled textures in iron,1,2 silicon-iron,3 mild steel,4 molybdenum, vanadium,&apos; chromium,&apos; tantalum,&apos; tungsten,&apos; and a-zirconium-niobium alloys10 have been determined. These textures have, in some cases, been represented by congrUOUS pole figures and have all been described in one or both of two ways. They have frequently been reported as predominantly (100) <011> orientation

Jan 1, 1959

By W. D. Sylwestrowicz

In tests on polycrystalline copper and aluminum, the ratio of the yield stress to modulus of elasticity was found to be strongly dependent on tempemture. Also, it was shown that the change of the yield stress with temperature of a material at a given temperature and deformed to a given yield stress, but not necessarily to the same strain, does not depend on previous mechanical thermal history. Likewise, for a material at a given temperature and deformed to a given yield stress, the rate of work hardening is independent of the temperature of prior stressing. It has been shown by Los and Orowan1 and by Dorn, Goldberg, and Tietz2 that the temperature dependence of the yield stress-strain curves of crystalline materials reflects two effects: not only does the yield stress of a material in a given structural state depend on the temperature, but the structural state (and the corresponding strain hardening) after a given amount of plastic straining also depends on the temperature at which the pre-straining has been carried out. Thus, for instance, if a specimen of a ductile metal has been strained along the stress-strain curve 1 at room temperature to point A, Fig. 1, and then the straining continued in liquid nitrogen along curve NR, the yield stress A&apos; immediately after lowering the temperature is lower than the yield stress A" of a specimen that has been strained by the same amount in liquid nitrogen (along curve 3). AA&apos; represents the effect of the temperature change upon the yield stress of the specimen pre-strained at room temperature; A&apos; A" is the excess strain hardening acquired if the pre-straining has been carried out in liquid nitrogen instead of at room temperature. The dependence of the yield stress (i.e., of the structural state acquired during preceding straining) upon the conditions (speed, temperature) of a pre-straining is the reason for the nonexistence of a so-called "mechanical equation of state" for plastic deformation. A &apos;mechanical equation of state" is a relationship of the form F(s,E, e, T) = 0, or s = f(E, E, T) [1] It was first suggested by Ludwik3 that plastic deformation might obey such an equation; this, however, was conclusively disproved by experiments of Kochendorfer.4 Additional disproofs were given in

Jan 1, 1959

By A. H. Daane, J. F. Haefling

BECAUSE of the wide use of platinum in industry and research, the physical properties of this metal, including its vapor pressure, have been studied in some detail.&apos; The other members of the palladium-platinum group of metals have not been studied as extensively, and only qualitative information is available on the vapor pressure of palladium. Data given in literature by Vines1 and Brewer2 on the vapor pressure of palladium are based on the qualitative observations by Holborn and Austin3 and Crookes4 on the rate of volatilization of palladium filaments in various atmospheres. The general observation that palladium is the most volatile metal of the palladium-platinum metal group was corroborated by Bell, Love and Normand who studied the separation of isotopes of the platinum-group metals by a mass spectrometric method. We have measured the vapor pressure of palladium using the Knudsen effusion technique. In this work, the effusion vessel was suspended from a quartz-fiber microbalance into an induction furnace, and the amount of vapor effusing from the vessel was determined by direct weighing of the vessel during the measured heating times. This technique has been described in a report from this laboratory." The vapor pressure of palladium was calculated from these measurements using the equation P...... = 17.14 -W- (77m)&apos;u [1] a t where ? is the weight loss in grams of vapor of molecular weight m from a vessel having an orifice of a sq cm, during t sec. The derivation of this equation from kinetic theory has been described in a previous report from this laboratory: as well as in texts discussing the kinetic theory of gases.%" Test Vessel—In the search for a suitable material for the effusion vessel, it was found that tantalum reacted with palladium metal to form intermetallic compounds, and graphite was readily dissolved in palladium metal to form what appeared to be a liquid phase at a temperature several hundred degrees below the melting point of palladium. On cooling, the graphite gathered into spherical balls in the palladium, with crystals extending radially from the center of these balls, some of which were a millimeter or more in diameter. However, palladium metal vapor did not attack the graphite vessel, so graphite could be used where it did not contact condensed palladium. Tungsten did not appear to react with palladium vapor or molten palladium at its melting point, but it was not convenient to use a tungsten-vapor pressure vessel because of the difficulty of fabricating this metal. Since the vapor-pressure range to be studied (10 2 to 10 &apos; mm) did not appear to extend above the melting point of palladium, a combination of tungsten and graphite served to provide a very satisfactory effusion vessel. The lower half of the graphite vessel was lined with some strips of tungsten foil and the sample of palladium consisting of a coil of sheet was placed in the tungsten liner; in this way, no contamination of the palladium by carbon occurred. Procedure After outgassing at 1500C, the tungsten-lined graphite effusion vessel was loaded with 300 mg of

Jan 1, 1959

By A. H. Cottrel

SINCE metallurgy exists to provide strong, tough, engineering materials it must inevitably be perpetually concerned with the problem of brittle-ness. The steel-making industry was created because chemically unrefined iron is brittle. The steel-working and alloy-steel industries exist partly because hardness and ductility are mutually exclusive qualities in structurally unrefined steel. Yet, in spite of these immense industries, the brittle failure of steel ships hulls, bridges, pressure vessels, and pipelines, is still a contemporary problem. In fact, brittleness is a normal property of most solids, including metals and alloys, at low temperatures. Only face-centred cubic metals are commonly ductile at the lowest temperatures, and even here exceptions are known.&apos;," Expensive are-melting processes. under inert gases or vacuum, have been developed to overcome brittleness in titanium, zirconium, columbium. and molybdenum. Polycrystal-line zinc, magnesium, and uranium have little ductility at room temperature. Beryllium, chromium, and tungsten have even less; similarly for antimony, bismuth, germanium, silicon, intermetallic compounds, and metallic carbides, nitrides, silicides, and borides. Oxides and other ceramics would be ideal creep-resistant materials but for their extreme brittleness when cold, and great efforts have been made to overcome this problem by mixing ceramics with metals. In fact, the traditional use of the name metallurgy for what is really the science of engineering materials is a recognition that most non-metallic solids have so far been precluded, by their extreme brittleness, from use as major structural materials in mechanical engineering. Most of what we know about brittleness in metals has come from studies of structural steel, and it is this material that shall mainly be considered. The things we have learned from it have a wider application, at least to other body-centred cubic transition metals, although the extent to which similar ideas can be applied to hexagonal metals and other materials is not yet clear. Fracture and Plastic Deformation The theoretical breaking strength of an ideal solid, about E/10 where E is Young&apos;s modulus, has been approached reasonably closely in experiments on fibres. But large specimens break at much lower stresses. For example, brittle cracks in large structural steel assemblies have been observed to spread catastrophically at speeds of 6000 ft per sec under stresses of about 10,000 psi, i.e. about E/3000. There are two sources of weakness; stress concentrations, and chemical agents in grain boundaries or on crack faces that lower the surface energy y of the material. Although we shall deal mainly only with the first of these, much of the discussion is also applicable to the second when different values of y are used. Griffith&apos;s well-known formula p = [ 2Ey/p(1 - v2)c]1/2 [1] gives the smallest tensile stress p able to propagate an atomically sharp surface crack of length c or interior crack of length 2c through a thick plate (compared with c) of elastically isotropic material of

Jan 1, 1959

By F. D. Rosenthal, F. J. Dunkerley, G. J. Mills

Activities, free energies, and heats and entropies of mixing of liquid Pb-Zn alloys have been obtained by the electrode-potential method between 400° and 650°C. The large positive deviations observed from Raoult&apos;s law are in agreement with the phase diagram, which indicates a wide immiscibility field. A vapor-pressure method was used to extend the activity measurements to 900°C, allowing the maximum of the immiscibility gap to be estimated by thermodynamic calculation. Data on the mono-tectic and eutectic points compare favorably with previously existing work. SEVERAL long-standing methods have been in use for the study of phase diagrams from measurement of the activities of the component metals.&apos; The use of thermodynamic analysis for interpreting equilibria data is comparatively recent, however. Such analysis is usually undertaken by first evaluating the principal thermodynamic functions as, for example, the enthalpy, entropy, and free energy of the alloy constituents. These, in turn, quite often can be correlated with the interatomic potential energies and atomistics of the system, from which a clearer understanding of the causes leading to deviations from ideal behavior is gained. The present study of liquid Pb-Zn alloys is concerned with a determination of these quantities by electrode-potential and vapor-pressure measurements, using these values in calculations involving phase equilibria and to obtain a theoretical insight into an alloy system exhibiting strong positive deviations from ideal metallic solution. A considerable portion of the previously reported work is based on thermal analysis. Supplemented by optical studies of solid alloys, these techniques have revealed the essential nature of the immiscible mixtures that are formed. It is difficult, however, using the phase-

Jan 1, 1959

By J. C. M. Li

This exploratory survey was undertaken to repeat some experiments- in which anomalous results were reported1 for bismuth and to measure the thermoelectric power of some bismuth alloys and inter-metallic compounds. sato1 reported that the thermoelectric power of bismuth depends on the temperature gradient. This seems rather unreasonable especially when the Benedicks effect&apos; has not been detected. Even if the material is not homogeneous, the observed thermoelectric power can be represented by

Jan 1, 1959

By D. H. Turner, F. A. Crossley

The titanium-rich corner of the system Ti-Al-Si has been studied to determine the phase relationships in the temperature interval 600° to 1200°C. Metallographic examination of long time isothermally annealed specimens was the means of investigation. PART of a program on phase relations and transformation processes of titanium alloy systems included the study of the titanium-rich corner of the Ti-Al-Si system. The investigation covered ternary compositions in the range 2 to 8 pet A1 and 0.1 to 2 pet Si and binary compositions in the range 0.2 to 2 pet Si. Temperatures were in the range of 600" to 1200°C. Alloys containing 6 pet A1-0.1 to 0.5 pet Si were investigated down to 400°C. Partial vertical sections are presented for 2, 4, 6, and 8 pet Al. The Ti-Si system has been reported by Hansen et al.&apos; It is characterized by a eutectoid decomposition, ß = ± a + Ti3Si3, at 860°C. The maximum solubility of silicon in a is reported to be about 0.5 pet at the eutectoid temperature. The solubility of silicon in 0 increases from 0.9 pet at the eutectoid temperature to approximately 3 pet at the eutectic temperature, 1330°C. Several investigations in the composition range of interest have been reported for the Ti-A1 system."&apos; These investigations are in agreement on the phase fields, but differ to small extents on boundary positions. However, very recent, and as yet unpublished, findings" " indicate that there are perhaps two phases which occur at lower aluminum contents than the ? (TiA1) phase, and that the solubility of aluminum in a titanium is less than 6 pet. In the present investigation phase relations found are in agreement with the published literature exemplified by the work of Bumps et al.3 Therefore, it is probable that the partial system reported herein is metastable and does not represent true equilibrium. Experimental Procedure High purity Bureau of Mines titanium sponge of 103 Bhn hardness, granulated aluminum shot of 99.7 pet purity, and silicon powder of 99.8 pet purity were used in making the alloys. For the work in the range from 600" to 1200°C, 100 g ingots were prepared by arc melting. Melting losses were negligible and spot checks by chemical analysis showed good agreement between nominal and analyzed results. Nominal compositions are used throughout this paper. Ingots were forged to 3/8 in. rounds and cut into specimens for heat treatment. Isothermal anneals in the range from 600" to 900°C were preceded by solution treatment at 1000°C for 1 hr, followed by furnace cooling to the annealing temperature. Samples were sealed in evacuated Vycor bulbs for heat treatments up to 1000°C. Higher temperature anneals were done with the samples sealed in quartz bulbs under a partial pressure of argon.

Jan 1, 1959

By W. Rostoker, S. A. Spachner

FOLLOWING the discovery of the w transition phase in certain titanium-chromium alloys by Frost, Parris, Doig, and Schwartz, much interest has centered on the alloys in which this phase is found and its mode of precipitation. The w phase has been found in alloys of Ti-Cr, Ti-Fe, Ti-Mn, Ti-MO,2 and Ti-v.3 The temperature-time-transformation characteristics have, as yet, not been determined for most of these. In this study, such transformation characteristics have been investigated for two heat-treatable titanium alloys known to exhibit transition phase phenomena. The alloys chosen, Ti-8Cr and Ti-13M0, are representative of two classes of binary equilibrium systems. In the

Jan 1, 1959

By R. Bakish, C. S. Barnett

IN experiments on tantalum strained in tension, Bechtold did not observe deformation-twinning even at a temperature as low as that of liquid air.&apos; This is an unexpected behavior for a metal of body-centered-cubic structure. Therefore, it is desirable to determine whether the lack of twinning is an inherent characteristic of this particular metal, or whether the reluctance to twin can be overcome under suitable conditions. The following experiments were performed under conditions favorable to twinning and cleavage in their competition with slip, namely, with impact loading on large-grained sheet at low temperatures. The crystallography of cleavage in tantalum sheet was also investigated carefully because of the remarkable ductility of tantalum at low temperatures and because recent tests on oxygen-embrittled tantalum had disclosed unusual cleavage behavior for a metal of this structure: cleavage primarily on (110) planes and only occasionally on {100}.2 The tantalum, supplied by Fansteel, was of 99.9 pet purity, with the chief impurities being iron (0.03 pet) and carbon (0.03 pet). Coarse grains were produced by the strain-anneal method, the anneal being 4 hr at 2000°C in a vacuum of 10-3 mm Hg, followed by furnace cooling. Impact deformation was applied in various ways: a) by hammer blows on an anvil, the specimen and anvil being immersed in liquid nitrogen ( —196°C), b) by driving a precooled center-punch into the sheet, and c) by bending around a crystallographically determined axis with a hammer blow. The impact-deformation produced bands and slip lines on the surface, Fig. 1. The bands have every appearance of being deformation twins, a) They are tilted with respect to the untwinned surface. b) They have the appearance of Neumann bands in iron, thin lens shape, some having serrated edges. c) The orientation in each is different from that of the surrounding matrix and uniform within a given band, see slip lines within them in Fig. 1. d) Upon repolishing and etching, the difference in orientation and the resemblance to Neumann bands is again evident, Fig. 2. (In this micrograph the slight bend in the bands as they cross grain boundaries was noted frequently and results from the high degree of preferred orientation in the sheet.) e) The bands persist after annealing treatments that would have removed them had they been a low-temperature martensitic phase, e.g., after an anneal of 1/2 hr at 900°C. When back-reflection Laue data were plotted for single-surface analysis of several grains, every trace of the bands in each grain could be explained by (112) planes. In addition, two of the bands were located in space by traces on two surfaces, and these also were found to lie on (112) planes within the error of the stereographic plot. Since (1 12) is the anticipated composition plane for deformation twins in body-centered-cubic metals it is felt that the observations listed above are conclusive evidence for the identification of the bands as twins. Similar tests with impact at —77° and at 25°C produced no twinning. It is concluded that the critical shear stress for slip at the rates of straining used was always low enough to prevent the applied stress from reaching the value required for twinning at these temperatures. It was noted that the serrations along the edges of the twin bands exhibited parallel crystal facets. Several similarly oriented notches are visible in Fig. 1, and a remarkable set is shown in Fig. 3. It appears from Fig. 1 and similar areas that notches are frequently associated with the intersection of a slip line with a twin, although not all such intersections are at notches. In some instances a slip line appears to enter the twin, cross it, reflect from the opposite side and recross it, producing a pattern resembling a notch but without producing the notch itself, see Fig. 1. It is suggested that the stress concentration at the end of a slip line is responsible for these details. The strain energy associated with the pile-up of dislocations at a twin boundary may be lessened by untwin-ning or failing to twin a portion of the twin band, or

Jan 1, 1959

By D. F. Atkins, B. A. Rogers, E. J. Manthos, M. E. Kirkpatrick

A phase diagram of the uranium-columbium alloys is presented. The apparatus and the procedures used in obtaining the data are described. Data from which the diagram was drawn are given in tabular and graphic form. THE use of uranium in the production of energy from nuclear fission has given considerable im- petus to the investigation of the metal and its alloys. Accordingly, information concerning the phase diagrams of binary alloys of uranium with other elements is of interest to metallurgists engaged in nuclear-engineering activities. As a contribution to the knowledge of the binary alloys, the authors have attempted to establish the diagram of the uranium-columbium system. The reports of laboratories engaged in work for the Manhattan Engineering District and the U. S. Atomic Energy Commission contain a number of references to work on uranium-columbium alloys.

Jan 1, 1959

By J. H. Scaff, J. E. Kunzler

The measurement of the electrical, thermal, and magnetic properties of metals at low temperatures, primarily in the range of liquid helium below 4.2°K, is a powerful tool for investigating many of the fundamental properties of the metallic state. Such measurements also have many practical applications, particularly as an analytical tool. One example of the practical utility of such measurements is illustrated by a short study we have made of the low-temperature resistance of copper used in preparing varistors. Copper-oxide varistors are prepared by the thermal oxidation of copper. This results in the

Jan 1, 1959

By T. J. Bosworth

The effect of hydrogen pretreatment of alumina, magnesia, and zirconia crucibles on reduced oxygen levels in iron charges has been studied. Hydrogen treatment of commercial high-purity magnesia crucibles was observed to produce as high as 70 pct reduction in oxygen content in iron melts. Hydrogen treatment of the commercial high-purity grade zirconia crucibles produced a 25 pct reduction in oxygen levels in iron melts. An average reduction of Knoop hardness of 47 pct was recorded on the iron charges melted in hydrogen-treated crucibles. On the basis of the experiments and the free-energy diagram, it appears that the major source of reducible oxygen to the iron charge is the suboxides and impurity oxides rather than the major oxide of the crucible. Suitable pretreatment of the crucibles to reduce and remove these oxides yields low oxygen levels in iron melted in the crucibles. DURING the last decade, attempts to produce more pure and uniform alloyed metals have brought about the development of many new melting techniques. Notable among these are vacuum-induction melting, inert and consumable-electrode melting, the cold-mold technique, and numerous techniques for removal of impurities by chemical reaction. However great the achievements in this field, metals must still be melted in contact with media of varying reactivity; i.e., gas, ceramic, and slag. Studies have been made to attain an understanding of the reactions that take place during melting, including slag-metal reactions and equilibria, equilibrium of hydrogen and water vapor, and carbon dioxide and carbon monoxide with oxygen in molten iron. These reactions have been treated quite thoroughly. There is one condition, however, that has been widely overlooked, and, to the author&apos;s knowledge, only cursive investigation has been made of it. This is the reaction between the ceramic crucible material and the iron charge. In recent years, Hadley and Bianchi&apos; made a series of studies on hydrogen deoxidation of iron in magnesia crucibles. Bianchi2 studied crucible-FeO equilibria in the temperature range 1525°to 1650°C in high vacuum with, however, inconsistent results. Richardson and Jeffes3 in their series of articles on thermodynamic reactions in the making of iron and steel refer to Wentrup and Hieber&apos;s4 work on iron and aluminum deoxidation. Their pork included melting iron in alumina crucibles and measuring the aluminum and oxygen content in the iron. Because of the low values obtained, question has arisen of their analytical accuracy.3 Dastur and chipman5 obtained values on hydrogen-oxygen equilibrium in molten iron contained in alumina crucibles similar to those obtained in experiments in the present program. Hochmann6 studied removal of impurities in chromium irons in high vacuum. His results with respect to oxygen level in chromium-iron melted in magnesia crucibles are consistent with results we have obtained.

Jan 1, 1959

By W. D. Robertson, W. L. Phillips Jr.

Stress-strain curves were obtained for single crystals of alpha brass in tension and in direct shear. Specimens were strained various amounts in a given slip direction, unloaded, and immediately strained in a second slip direction 60°, 120°, or 180&apos; from the original slip direction. Crystals strained in tension and direct shear had comparable critical resolved shear stresses and stress-strain curves. The density of slip lines in direct shear and in tension was essentially the same. The stress-strain curves obtained in shear were independent of initial orientation, choice of {111 } slip plane, choice of <110> slip direction, prior annealing temperature, and rate of cooling after annealing. There was no recovery after annealing for 4 hr at room temperature or 200°C; recovery was observed after 4 hr at 400°C. The crystals showed no asterism and mechanical properties were completely recoverable up to 20 pct strain. It was found that there is a barrier to slip in all latent close-packed directions, and that the magnitude of these barriers, evaluated at 3 pct strain, is proportional to prior strain and independent of the choice of latent direction in the {111} plane. The formation of Cottrell-Lomer barriers is discussed as a possible explanation for the hardening of the latent systems. AN idealized concept of plastic deformation indicates that a single crystal should yield at some stress that is dependent on crystal perfection and it should then continue to deform plastically by the process of "easy glide," which is characterized by a linear stress-strain curve and a low coefficient, ds/dE, of work-hardening. Hexagonal metal crystals generally conform to this ideal concept of laminar flow. In face-centered cubic metals the range of easy glide is always restricted in magnitude and it is strongly dependent on orientation, composition, crystal size, shape, surface preparation, and temperature. Since one of the principal differences between the two crystal systems, both of which deform by slip on close-packed planes, is the existence of secondary (latent) slip planes in the face-centered cubic crystals, it has been proposed that the transition from easy glide to turbulent flow, characterized by rapid linear hardening, is due to slip on secondary planes intersecting the primary plane.&apos;-.; However, the characteristic differences between individual face-centered cubic metals remain to be explained; in particular, it is not clear why the range of easy glide should vary so greatly in different metals and alloys similarly oriented for single slip. An investigation and comparison of different metals with respect to latent hardening on the primary slip plane should provide some of the information required to specify the necessary and sufficient conditions governing the transition from easy glide to turbulent flow. But, in order to accomplish this purpose, plastic strain must be produced by simple shear in a chosen plane and in a predetermined direction by some form of directed shear apparatus, the results of which must be correlated with the corresponding tension experiments. Two such experiments have been performed previously with zinc and with aluminum. Edwards, Washburn, and Parker" and Edwards and Washburn7 found that the strain-hardening coefficients in two latent directions in the basal plane of zinc were the same as in the primary direction. However, to initiate and propagate slip in either the [2110] or the [1210] direction, following primary slip in the [1l20] direction, it was necessary to increase the stress above that required to continue slip in the primary direction; when the direction of shear was reversed 180 deg plastic strain began at a much lower stress than that required to initiate slip in the original direction and the stress to propagate slip in the reverse direction was lower than the stress to continue slip in the forward direction, indicating a permanent loss of strain-hardening. Rohm and Kochendorfer observed softening in aluminum for all latent close-packed planes and directions. They also found that the critical resolved shear stress obtained from their direct shear apparatus was 50 pct lower than the value obtained from conventional tension tests, that the stress-strain curve was linear at 50 pct plastic strain, and that slip lines were not visible at strains less than 30 pct. At present it is uncertain whether these diverse results correspond to real differences in work-hardening characteristics of the close-packed planes of aluminum and zinc or to differences in experimental technique. In view of Read&apos;s analysis &apos;" of the stress distribution in the experimental arrangement of Rohm and Kochendorfer, there is some reason to question the significance of the latter results. In order to resolve this problem it is necessary to re-valuate the direct-shear technique and either repeat the previous measurements or investigate a third system. The latter choice seemed most likely to produce significant results with respect to work-hardening, and accordingly, it was decided to examine the hardening characteristics of the latent slip directions in alpha-brass. The choice of alpha-brass was dictated by the fact that easy glide is more extensive in this alloy than in any other face-centered cubic metal or alloy and, presumably, more nearly like the idealized hexagonal system. Experimental Procedure Crystals were made in graphite by the Bridge-man method in the form of cylinders, 11/2 in. diam and 8 to 9 in. long. Material for the crystals was 70/30 brass containing the following impurities:

Jan 1, 1959