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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

By C. Kolm, E. P. Warekois, S. A. Kulin

MUCH insight has been gained into the nature of the cold-worked state of metals in recent years through the use of modern X-ray techniques. These methods have revealed the existence of stacking faults together with regions of high internal strain and have provided means of measuring the atomic perturbations in plastically deformed metals. In view of the recent increased interest in the solid state, it is desirable to extend these techniques to the study of lattice imperfections introduced into semiconductors during plastic deformation. It is of particular interest to compare the state of imperfection sustained by metallic bonding with that sustained by the covalent bonding found in semiconductors. A knowledge of the imperfections which can exist in semiconductors is important from both a theoretical and a practical point of view since they can greatly influence many of the physical properties. In order to determine the possible existence of stacking faults in covalently bonded structures, precise measurements were made of the diffracted peak positions of plastically deformed germanium, gallium antimonide, and indium antimonide. These measurements were based on the theoretical treatment of Paterson1 and are similar to those employed by Warren and warekois2 in their studies of deformed a brass. In addition, diffraction peak profiles were measured on the annealed and plastically deformed materials in order to obtain information concerning the distribution of internal strains through the use of the Fourier methods developed by Warren and Averbach.3 EXPERIMENTAL PROCEDURES AND TECHNIQUES Because of the room-temperature brittleness of the semiconductors studied, it was necessary to plastically deform the materials at elevated temperatures. The brittle-ductile transition temperature ranges of GaSb and InSb are sufficiently low to permit hot-filing operations. Therefore, high-purity, polycrystalline GaSb and InSb were filed in an argon atmosphere at 400&apos; and 300°C, respec-

Jan 1, 1959

By P. A. Beck, M. N. Parthasarathi

In high purity aluminum single crystals grown by the strain-anneal method (primary re crystallization after a small deformation) Lacombel observed sub-boundaries with disorientations of 1 to 3 deg. In commercial and high purity aluminum crystals grown by the same method Tiedema observed sub-boundaries with disorientations of about 20 min of arc, radiating from a =nuclear spot," centrally lo-

Jan 1, 1959

By F. W. von Batchelder

The principles of microradiography and their application practically coincided with the discovery of X-rays. These principles were first used in the metallurgy field by Heycock and Neville1 in a study of the dendrite structure of alloys of Au-Na, Au-A1, Cu-A1, and Ag-A1. The method was introduced in the USA by clark2 after a visit to France. Scores of papers have been written, and a very complete bibliography on this subject was compiled by the Eastman Kodak company. Although a number of papers have discussed X-ray

Jan 1, 1959

By L. H. Schwartz, M. V. Nevitt

THE phase Ti2Ni has been described by Laves and Wallbaum,1 who found the phase to be face-centered cubic with 96 atoms per cell, by Duwez and Taylor,2 who confirmed these observations and reported a lattice parameter of 11.333A, and by Rostoker,&apos; who reported the structure to be isomorphous with the double carbide Fe,W,C, type E93, and to have a lattice parameter of 11.29A. In this study a group of isostructural phases has been found among alloys of certain second and third long-period transition elements. The systems investigated included all the combinations of zirconium and hafnium with the Group VIII elements rhodium, palladium, iridium, and platinum. There is evidence that many of these new Ti2Ni-type phases require oxygen for their stability in the temperature ranges in which they were studied. EXPERIMENTAL PROCEDURE Alloy samples weighing 5 g were prepared by arc-melting metals whose purity is indicated in Table I in a helium-argon atmosphere. Samples of the as-cast buttons, wrapped in molybdenum foil and sealed in evacuated quartz tubes, were

Jan 1, 1959

By O. F. Kammerer, W. E. Miller, D. H. Gurinsky, J. Sadofsky, J. R. Weeks

Zirconium and titanium inhibit solution mass transfer of steels by liquid bismuth, mercury, and lead. It is shown that in bismuth and mercury, these adsorb on the surface of the steels and subsequently react with nitrogen and possibly carbon from the steels to form inert, adherent surface layers of ZrN, TiN, or TiN + Tic. Data are presented which describe the condition under which thase deposits form. These inhibitors decrease the solution rate of iron into bismuth, and require a higher supersaturation for precipitation of iron from bismuth. USE of the low-melting heavy metals (bismuth, lead, mercury, and their alloys) as coolants has been limited because solution mass transfer of steels occurs in these liquids; i. e., iron dissolves in the hot sections of the heat transfer circuit and deposits in the colder sections. The rate of solution of iron and the temperature coefficient of solubility are sufficiently great to cause complete or partial stoppage by the deposition in the coldest section of a closed circuit in finite time, even though the actual solubilities are extremely low. In the development of the mercury vapor turbine by the General Electric Co., Nerad and his associates1 discovered that the addition of as little as 1 ppm Ti or Zr to magnesium-deoxidized mercury reduced the mass transfer of ferrous alloys by mercury to a negligible amount. Reid2 reported that titanium was detected chemically on the surface of steels contacted with this mercury alloy in amounts varying from 2.0 to 2.6 mg per sq in., the greatest amount being found in the hottest portion of the circuit. Reid stated that the titanium forms the intermetallic compound Fe2Ti by reaction with iron on the surface of the steels. This compound was presumed to be highly insoluble in mercury. More recently, El-gert and Egan3 have reported a greater than 100-fold reduction in the rate of mass transfer of a 5 pet Cr steel by liquid bismuth upon the addition of titanium (in excess of 50 ppm) and magnesium (350 ppm) in the liquid metal, during experiments performed in thermal convection loops* over the temperature differential 700° to 615° C. Also, Shep-ard and his associates&apos; have reported that the addition of titanium to liquid bismuth and Pb-Bi eutec-tic produced a marked decrease in the rates of solution of both iron and chromium from type 410 steel capsules under static conditions. This inhibiting effect increased with repeated reuse of the capsules. Tests performed in this laboratory under carefully controlled conditions have shown that the addition of zirconium and magnesium, or titanium and magnesium, to liquid bismuth or lead greatly reduces the rate of mass transfer of chromium alloy steels and carbon steels in thermal convection loops with a maximum temperature of 550°C.5-9 The present paper will review the data obtained to date at this laboratory on the behavior of iron and steels in contact with liquid bismuth alloys containing titanium or zirconium, and will attempt to explain the role of the above additives in reducing solution mass transfer. Reaction between the Zirconium or Titanium Dissolved In Liquid Bismuth and an Iron or Steel Surface Reaction between Zirconium Dissolved in Bismuth and the Surface of Pure Iron-—A small pure iron crucible (analyzed by the supplier to contain 0.8 ppm N was contacted with bismuth containing approximately 0.1 pet Mg and varying amounts of a radioactive zirconium tracer. The crucible was then inverted at the temperature of contact. The thin residual layer of adherent bismuth was dissolved in cold, concentrated nitric acid. The crucible surface and the solidified bismuth were then analyzed for radioactive zirconium. An analysis of the activity loss on the crucible surface and the weight loss of the crucible during the nitric acid treatment showed that the acid treatment removed the zirconium that had originally been dissolved in the adherent bismuth, but not any zirconium that may have reacted with the crucible surface. The crucible was then pickled in warm aqua regia to remove all surface activity, hydrogen-fired at 600°C, and recontacted with a new liquid alloy. The results of the experiments contacted 1 hr at 450°C show, Fig. 1, a Langmuir-type adsorption with an adsorption free energy of approximately 17 keal per g atom Zr.5 This deposit was estimated to contain 1 atom of zirconium for each 7 to 8 iron atoms on the crucible surface, assuming a surface roughness factor of the pickled crucibles to be five. Increasing the temperature to 520°C caused consi-

Jan 1, 1959

By J. B. Clark, A. S. Yue

IN recent years, zone melting1 has been applied extensively to the purification of metals having a very low vapor pressure.2-4 This note describes the zone melting of a high vapor-pressure metal, magnesium, where the melting takes place inside a refractory surface skin. The effects of zone speed and the number of passes of the molten zone on the purification have been determined and the effective distribution coefficients for the principal impurity elements were calculated. A schematic diagram of the zone-melting apparatus is given in Fig. 1. The Vycor tube containing the graphite boat with its magnesium charge (an extruded rod—3/8 in. in diam, 10 in. long) is pulled through the stationary furnaces. A molten zone approximately one-fourth the length of the charge is produced under each of the two central furnaces. Two grades of magnesium were studied—electrolytic magnesium and magnesium with a very low alloy content. The spectrographic analyses of these materials, within * 5 pct of the values stated, are given in Table I. Molten magnesium will vaporize severely if protected only by an inert atmosphere such as argon. Consequently an enveloping container is required. In zone melting, a rigid opaque container surrounding the charge is inconvenient because visual control of the zone length is prevented. A more satisfactory container is a strong flexible skin on the surface of the metal charge which is capable of supporting the molten zone. SO2 reacts with magnesium to form a thin coherent surface film of MgSO, and MgO. An atmosphere of SO, of commercial purity was maintained during the zone melting. Enough oxygen was present within the system and the commercial SO, for the satisfactory formation of the protective skin, so that any rupture of the skin during the zone refining was healed immediately.

Jan 1, 1959

By L. R. Shoenberger

Boron has been used to produce nonaging low-carbon sheet steel. Retention of the necessary minimum amount of about 0.006 pet partially killed the steel. Amounts exceeding about 0.012 pet increased the degree of deoxidotion, piping tendencies, and possibility of hot tearing in primary rolling. Semikilled practice resulted in good ingot yields and satisfactory surface quality. Aluminum added with the boron provided a protective de-oxidizer. Good drawobility was indicated by performances of the steel in a limited number of deep-drawing trials. Some problems with hot-tearing and boron-analysis procedures were overcome. Metal lographically, the boron semikilled steels revealed some structures not usually found in plain low-carbon steels. IN 1943 Low and Gensamer1 reported that strain aging, which hardens and embrittles ordinary low-carbon rimmed steel, was due to nitrogen and carbon, and that oxygen played a relatively unimportant role. Since then, many investigators have substantiated their findings and indicated that nitrogen is particularly potent. Commercially, today&apos;s most widely produced non-aging sheet steels for deep drawing are either aluminum killed or vanadium rimmed types. The difference in deoxidation practice, alone, is evidence that oxygen is apparently not an important consideration in control of strain aging. The fact that nitrogen is important is apparent in the consideration that has been given, knowingly or unknowingly, to the amount combined with aluminum and vanadium. Patents were granted to Hayes and Griffis2 for the processing of aluminum-killed steel, and to Epstein" for the manufacture of vanadium rimmed material. Certain prescribed steps in producing these steels can be correlated with the formation of the respective nitrides within certain temperature ranges below the usual hot-finishing temperatures. The potential nonaging properties of either type can be reduced or suppressed by cooling too rapidly to permit the aluminum or vanadium to combine with nitrogen. Subsequent suberitical annealing of the cold-rolled strip, however, normally forms the nitrides and produces the resistance to strain aging. Titanium-killed nonaging steel, described by Comstock,1 forms a nitride in the molten state and is essentially nonaging throughout its processing. Zirconium-killed steel, which was investigated briefly by the author,* appeared to have similar nitride- forming characteristics. It is known" that chromium can produce nonaging rimmed steel, but relatively little is known of the potentialities of some of the other nitride-forming elements such as boron, silicon, columbium, and cerium. In attempting to develop a new nonaging cold-rolled sheet steel with good drawability, the following factors were considered pertinent. Such a steel would necessarily have a low carbon content and therefore have a relatively high degree of oxidation when made in a basic open-hearth furnace. If the denitriding element were also a deoxidizer, a part of the addition would be lost as oxide. The degree of deoxidation would determine whether the steel is rimmed, semikilled or killed, and also could be expected to have an important bearing on ingot yields and ultimate surface quality. Assuming that the pattern for the production of cold-rolled sheets would not be changed to any great extent, the nitride must form in the molten steel, in hot rolling, in subsequent cooling, or in annealing. The nitride, once formed, should resist dissociation and be stable in the final product. Usually an excess of the nitride-forming element is required to combine with sufficient nitrogen. If the element used is a strong ferrite strengthener, a small excess may markedly decrease drawability. With aluminum and vanadium, about 0.03 to 0.05 pct in the steel is preferred. Epstein has said" that about 0.30 pct chromium is required. Titanium nonaging steels are hard unless a sufficient amount (about 0.30 pct) is added also to combine with the carbon. The cost of the necessary amounts of these latter two elements discourages commercial acceptance. Silicon was considered as a possible nitride former, but since amounts up to 0.10 pct in rimmed and semikilled steels do not induce marked resistance to strain aging, larger amounts are apparently required, which would tend to harden and strengthen the ferrite. Of the other elements mentioned, all but boron are expensive heavy-metal elements. Stoichi-ometrically, almost an equal weight of boron would be required to combine with the nitrogen—-ordinarily about 0.003 to 0.006 pct in scrap-practice open-hearth steels. Boron is a slightly stronger deoxidizer than carbon but is less powerful than zirconium, aluminum, or titanium. Thus a rimmed-steel practice might be possible. There is much in the technical literature concerning the hardenability effects of minute amounts of boron in killed steels but very little about its behavior in low-carbon material—particularly as a ferrite strengthener. The available data indicated a need for better information concerning the effects of boron in low-carbon strip steels. Experimental Work Development of a Boron-Treated Nonaging Strip Steel—Initial attempts to produce a boron-rimmed strip steel employed 3-ton basic open-hearth heats which could be teemed into molds large enough to sustain a normal rimming action. Boron as ferro-boron was added to the ladle in small amounts because of the reported hot-short character of aluminum-killed heat-treating grades containing more than about 0.005 pct boron. Actually, the amounts used, i.e., 1/8 and 1/4 lb per ton, would be large for

Jan 1, 1959