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By H. K. Najarian

This paper describes recent development work on the Wheaton-Najarian Vacuum Condenser for Zinc at Josephtown Zinc Smelter, wherein, to dissipate the heat of condensation, the "airlift" action of gases bubbling through the molten zinc in the condenser is utilized to circulate the zinc through an outside "cooling well" and cooling it continuously. AN earlier paper1 gave an account of initial development of the Wheaton-Najarian Vacuum Zinc Condenser at the Josephtown Zinc Smelter of the author's company. This paper is a progress report of further development work over the years directed toward improving the efficiency and increasing the capacity of the condenser. In this type of zinc condenser, zinc vapor with accompanying noncondensable gases from electro-thermic zinc smelting furnaces is passed upwardly through a mass of molten zinc confined in a refractory-lined U-tube. The zinc vapor condenses in the molten zinc and the noncondensable gases are drawn out of the condenser by suction applied over the surface of the molten zinc. The heat of condensation of zinc, amounting roughly to 1000 Btu per lb of zinc condensed, is absorbed by the molten zinc and, in turn, is dissipated continuously to keep the temperature of molten zinc in a range to permit effective condensation. At the time of publication of our first paper, we had at Josephtown Smelter five units of 69-in.-bore metal furnaces and one larger metal furnace having 96-in. bore. Each 69-in. metal furnace had a condenser with 22-ft overall length. The 96-in.-bore furnace had a condenser with overall length of 31 ft. Condensers were of circular cross section, with corrugated steel outer shell and carborundum lining. Diameter of these condensers was 32 in. inside the refractory lining. Molten metal in the con- denser was kept cool by spraying cold water on the outside of the condenser shell. Under good operating conditions, 22-ft condensers produced some 12 tons of metal per day; and the 31-ft condenser, about 22 tons. When the furnaces produced zinc vapor at higher rates, invariably the condenser temperature would rise to levels where excessive blue powder would form and accumulation of accretions in the condenser would be accelerated. We found that, with the system of cooling in use, we had to provide heat-exchange surface of some 150 sq ft to condense 1000 lb of metal per hr with reasonable efficiency. The wall of the condensers was made up of 5/8-in.-thick corrugated-steel shell having next to it several layers of mica and inner refractory lining of special carborundum shapes to fit the corrugation in the steel shell, and having a minimum thickness of about 2 in. Relatively low rate of heat transfer through the thick condenser wall and slow internal circulation of the molten zinc limited the rate of heat exchange between hot metal within the condenser and the cold water flowing over the outer steel shell. The thickness of the condenser wall was about minimum that we considered suitable for continuous operation. As we learned to operate the electrothermic furnaces with higher power input, producing zinc vapor at higher rates, it became apparent that we needed condensers having larger heat-exchange surfaces. Our 96-in.-bore furnace had 6 single-phase power circuits with transformers rated at 500 kva each and normally good for power input of 3000 kw.

Jan 1, 1959

By K. A. Semlak, F. N. Rhines

NFILTRATION is a term used to designate that i- process by which the pores of a metal powder are filled with a relatively low-melting liquid metal through the action of capillary forces. This is accomplished in practice either by heating the porous body in contact with the solid infiltrant metal above the melting point of the latter, or by preheating the porous body separately and then dipping it into the liquid metal. The liquid, as it sweeps through the porous body, replaces the gases progressively, thus yielding a relatively dense product in a short time.' Liquid-phase sintering, which is related to infiltration, is a process by which a mixture of two or more metal powders is sintered at a temperature between the liquidus and solidus of the ultimate alloy.' According to Cannon" liquid-phase sintering can be divided into three stages which he calls liquid flow, accommodation, and solid sintering. The largest density increase occurs during the first stage, where the lower melting component melts and, driven by capillary forces, flows among the particles of the higher melting component, where, after dissolution of the bonds between the solid particles, it moves them into close packing. This happens so quickly that little has yet been learned of its mechanism. A study of the rate of capillary rise of a liquid metal in a higher melting metal-powder compact may be expected, therefore, to contribute not only to a firmer understanding of the process of infiltration as such but also to a more extensive knowledge of what occurs during the initial stage of liquid-phase sintering. Theoretical Basis In order to derive a mathematical expression of the rate of infiltration, it has been assumed that a powder compact consists of a great many parallel capillary tubes and that the rate of rise of a liquid in an average capillary channel represents the rise in the entire compact. For a straight capillary, assuming that Poiseuille's law obtains for the non-stationary state and that wetting is very rapid, Ligenza and Bernstein' have derived the following differential eauation of motion where h is the height of rise of the column of liquid at time t, R, is the radius and 1 the length of the capillary, t) and 7, the viscosities of liquid and air, respectively, p and p, the density of the liquid and air, respectively, y the liquid-gas surface tension, 0 the liquid-solid contact angle, and g the acceleration due to gravity. The term on the left of Equation [I] represents the rate of change of momentum of the contents of the capillary tube. On the right the terms represent, respectively, the forces due to a) surface tension, b) viscous resistance, c) gravity, and d) end-drag effect. Equation [I] is not amenable to explicit solution, but for a tube of sufficiently small radius, the rate of rise may be slow enough so that the rate of change of momentum and end-drag terms may be neglected. The validity of this simplification was established by Ligenza and Bernstein' by graphical differentiation of observed data obtained from organic liquids rising in glass tubes. The solution of this simplified case is:

Jan 1, 1959

By E. R. Macgregor, J. Halpern

The kinetics of the reduction of cupric salts in aqueous solution by molecular hydrogen to metallic copper are described. The rate of reduction appears to be homogeneously determined and shows a marked inverse dependence on the hydrogen-ion concentration. Precipitation of copper is more rapid and complete in sulfate than in per-chlorate solution. A mechanism is proposed which accounts for this behavior. IN recent years a number of important hydro-metallurgical processes have been developed in which metallic salts in aqueous solution are reduced by gaseous hydrogen, usually at elevated temperatures and pressures, and thereby precipitated either in metallic form (e.g. Ni, Co, Cu) or as an oxide or salt of lower valence (e.g. VO, and VA).1 ; In connection with applications such as these, most of which involve heterogeneously catalyzed reactions, recent demonstrations"-" that salts of certain metals, e.g., Cu", Ag' , Hg" , and Hg,+ can activate molecular hydrogen homogeneously and thus catalyze hydrogenation reactions in aqueous solution, are of considerable interest. For example, cupric salts catalyze the otherwise slow homogeneous reduction of dichromate and ceric salts by hydrogen, i.e. Cr,O; + 3HL. + 8H1 ? 2Cr'- -- 7H,O [1] 2Ce ' ! H.. ? 2Ce" | 2H . [2] In perchloric-acid solution, where Cu" is not appreciably complexed, the kinetics have been found" " to be of the form -d [H,] _- k,[HJ [CU"]' dt -LCu+' l+ (k ,/k,) [H] [3] where, K = 1x10"' exp [—26,600/RT] 1, mole-' min-' ... [4] and (k ,/k,) - 0.25 at 110°C. This kinetic behavior suggests that the reaction proceeds by a mechanism involving the following sequence of steps kt Cu" +H1CuH' 4-HA [51 k., CUH + CU" ? + 2Cu f H' [GI 6Cu'+ Cr,07 + 14H'+ 2Cr- (¦ 7H,O + 6Cu" ['i] fast The catalytic activities of the undissociated cupric-sulphate and cupric-acetate complexes are somewhat greater (by factors of 6.5 and 120, respectively) than that of the simple hydrated Cu" ion.'" These considerations suggest that, in contrast to the other hydrometallurgical hydrogenation reactions, referred to previously, reduction of cupric salts in aqueous solutions by molecular hydrogen, should proceed homogeneously, and in the absence of an extraneous catalyst. This has already been demonstrated" for acetate-buffered solutions where the product of the reaction is a precipitate of cuprous oxide (Cu,O). In the present paper, an investigation of the reduction of cupric salts in perchloric-acid and sulphuric-acid solutions, leading to the precipitation of metallic copper, is described. Some results for the sulphate system, which is of considerable hydrometallurgical interest, have been reported previously by Ipatieff",' " and by Schaufel-berger' but these do not give a quantitative account, of the kinetics and mechanism of the reaction. Experimental The reduction experiments were conducted in the 1-gal, titanium-lined autoclave described in connection with earlier related investigations," " and using a similar procedure. The solutions were made up by dissolving known amounts of CP grade Cu(ClO,), and HC10, (or CuSO, and HISO,) in dis-tilled water. While in the autoclave, the solution was stirred and maintained at a constant temperature (±loc) and under a constant partial pressure of hydrogen gas. It was ascertained that the agitation (provided by two 3-in., four-bladed stirrers, rotating at 900 rpm) was adequate so that at no time was the rate of reaction limited by solution of hydrogen. During each experiment, samples of the solution were withdrawn periodically, allowed to cool, and the concentration of copper remaining in solution was then determined electrolytically. Some Cu' is formed during the reaction, but undergoes disproportionation when the solution is cooled to room temperature. For purposes of kinetic calcula-

Jan 1, 1959

By A. P. Young, L. I. Marsh

HE relationship between microstructure and *- fracture is of interest in many metals and alloys. This relationship is sometimes established by examining the fracture surfaces and the flat surfaces near the fracture path in tensile samples. However, it is often difficult to tell from examining the fractured sample whether the fracture is intergranular, intra-granular, or a mixture of both. Also, it is often of interest to follow the progress of slip, twinning, or crack formation along the fracture path before fracture occurs. The ambiguity concerning the type of fracture generally can be resolved if the area along the path of ultimate fracture can be photographed at inter-

Jan 1, 1959

By R. H. Atkinson, R. N. Rhoda

An improved technique has been developed for the deoxidation of palladium with aluminum which is especially suitable for use in making small castings with an induction-melting and casting machine. The effect of various crucible linings on the efficiency of the residual deoxidizer and accompanying oxide film in protecting palladium against oxidation during remelting also has been examined; the preferred crucible lining consists of zirconia cement. THE objective of this work was to develop a simple method of deoxidizing induction-melted palladium which would be suitable for use by manufacturers of jewelry and other small castings. In a common method of deoxidizing torch-melted palladium a piece of aluminum foil is dropped on the surface of the molten metal. If a film is present, which is usually the case, it must first be removed by oxidizing the molten metal thoroughly because it would interfere with the entry of the aluminum into the melt. Removal of the film is probably facilitated by a mild fluxing action of the silica crucibles which are used for torch-melting. However, removal of an alumina film from molten palladium in the crucibles normally used for induction melting is a much slower process and it became necessary to modify the de-oxidation procedure. In the modified procedure the charge is simply melted and the desired amount of aluminum, crimped to one end of a tungsten wire, is plunged through the film into the palladium and the wire immediately withdrawn. The trace of tungsten which dissolves along with the aluminum can be avoided, if considered objectionable, by using a palladium wire. In view of the persistence of the alumina film under the conditions of induction-melting it also was decided to ascertain the efficiency of this film in protecting palladium against oxidation during repeated remelting and casting. Melting Equipment and Materials The equipment used for melting and casting consisted of an Ecco GC:6, 6 to 8-kva high-frequency converter and an Ecco M34B centrifugal casting machine. This unit is being increasingly used for making jewelry and dental castings and it also has been found useful in making exploratory melts of a variety of nickel alloys, for which purpose it is well suited on account of its speed of melting and economy of material. A description of the machine and its operation will be published elsewhere.' A common palladium jewelry alloy, 95.5 palladi-um-4.5 ruthenium (referred to as "palladium" in the trade), was selected for the deoxidation tests. It was available as melting stock which had been melted in air to free it from oxidizable impurities, and also as clean scrap from previous melts which had been deoxidized with aluminum. The latter was thought to be typical of clean "palladium" scrap to be found in a manufacturing jeweler's establishment and it is also similar to one brand of "casting palladium." By the same token, the oxidized melting stock corresponds to "casting palladium" after the latter has been melted and thoroughly oxidized: Pure aluminum wire (99.9 pet), 0.032 in. diam; 1 in. = 0.036 g. Scrap tungsten wire, 0.014 to 0.020 in. diam. Argon, commercial water-pumped; 99.9 pet pure Experimental Procedure Samples of about 50 to 75 g of the palladium alloy were melted in a crucible lined with a proprietary refractory alumina cement. Some charges were melted in air, others in argon. The oxidized melting stock was melted and solidified a number of times in order to remove as much oxygen as possible before deoxidizing, but this treatment was unnecessary in the case of scrap. In either case the metal was deoxidized with aluminum (0.01 to 0.05 pet) by the

Jan 1, 1959

By R. B. Roof, J. J. Lombardo

DURING the course of investigations on U-Cb alloys by X-ray diffraction techniques, an impurity or an additional phase was observed in severa1 alloys of various compositions. The X-ray dif-

Jan 1, 1959

By R. G. Hudson, H. W. Paxton

The activities of iron and chromium in their binary system have been measured by the Knudsen orifice technique. The system is close to ideal at 1200- 1250 C with slight positive deviations. The effect of this on the liquidus and solidus is discussed and these are calculated for two limiting assumptions. The vapor pressure of pure iron, pure chromium, and one alloy is compared with that obtained by the Langmuir free-evaporation technique. The results agree, indicating a vaporization coefficient close to 1. HERE are no reported data on the thermody-A namic activity of iron and chromium in the solid portions of the phase diagram. It is generally assumed'.' that the liquid solutions of iron and chromium obey Raoult's law. Chen and Chipman" have inferred that the liquid solution obeys Raoult's law. The minimum' in the solidus-liquidus curves for the iron-chromium system shows that there are deviations from ideality in either the solid or liquid or both. Because of the importance of developing reliable techniques for obtaining activity data in alloy systems at high temperatures and of the data so obtained, an investigation of the activity of iron and chromium in the binary at 1200-1250 C was undertaken using the Knudsen cell. Experimental The apparatus and experimental procedures used in this investigation were described in a previous paper." The various materials used for the construction of the Knudsen cell are listed in Table I. The metal used for the determination of the vapor pressure of chromium was 99.9 pet pure, obtained from A. D. Mackay, Inc. The iron was obtained as electrolytic grade from Fisher Scientific Company. The Fe-Cr alloys used are shown in Table 11. The largest error and controlling factor in the accuracy in the experiments reported here are introduced because of temperature uncertainty, which is estimated to be ±3 deg C. This introduces an uncertainty of 26 pet in the measured pressure. Experimental Results and Calculations The vapor pressures of pure iron and pure chromium were calculated from the measurements by the Knudsen equation3 on the assumption that only Cr or Fe atoms were present in the gas phase. For metal vapors, at the high temperatures and low pressures involved in these measurements this should be a reasonable assumption. Whitman" corrections for the cells were made. The data and results of pressure calculations are presented in Table I, and are plotted in Fig. 1. In addition the heat of vaporization at the absolute zero, ?E°°, has been calculated for chromium. These calculations are summarized in Table 111. The data used in these calculations are as follows kelley13 (F° - E°°/T ) Speiser, et al H (F° - E°°/T ) 010 where F" — standard free energy at temperature T It was necessary to calculate the total pressure above the alloys from the total weight loss W of the cell during a run, because of the fact that all attempts to collect and analyze the chromium and iron vapor effusing from the cell in the apparatus available failed. The failure resulted from the re-

Jan 1, 1959

By R. Haynes

ON the basis of compositional changes of a phase observed in a eutectoid Cu-Al alloy1 it has been suggested that mechanisms for the decomposition of the ß phase proposed by earlier workers2-5 were incorrect. These data are reinterpreted in conjunction with lattice parameter data obtained on an alloy containing 12.2 pet Al, whose isothermal transformations have been reported elsewhere.5 The a Lattice Parameters of a 12.2 Pet A1-Cu Alloy—~iffraction patterns of completely transformed specimens were obtained in a back reflection camera using copper Ka radiation. Lattice parameters of

Jan 1, 1959

By C. Chiou, M. E. Fine

While Gunier-Preston zones are growing in Al-4.2 pct Cu at room temperature, Young's modulus, measured dynamically, increases about 0.4 pct. From the change in modulus with time the exponent of time in the rate equation for growth of the zones was deduced to be %. From a comparison of the rates of increase of modulus at 1, 28, and 42°C an activation energy of 12 to 14 Kcal per mole is computed. These findings support the idea that copper atoms are supplied along dislocation channels to growing zones. In alloys the elastic constants will be functions of the distributions of the atoms. If the degree of ordering or clustering is changed, one expects a corresponding change in the elastic constants. During age-hardening of aluminum-copper alloys at room temperature, the copper atoms cluster on 100-type planes in the aluminum lattice forming

Jan 1, 1959

By A. S. Nowick, W. A. Goering

INspite of considerable interest in the kinetics of ordering of the alloy Cu3Au there is no direct information available on the activation energy for atom movements in this alloy, such as that obtainable by radioactive tracer-diffusion studies or by internal friction measurements. Accordingly, this alloy was examined to find out whether it displays an internal friction peak resulting from stress-induced ordering, similar to that studied extensively in other alloy systems.1-3 Measurements of the internal friction as a function of temperature were made in a torsion pendulum similar to that described by Ké.8 Wire specimens 0.032 in. diam and 11 in. long were used. The wire, obtained in the cold-drawn condition,* was annealed at 900C in a quartz tube to obtain a large grained sample, and then mounted in the torsion pendulum furnace. Internal friction is reported here as the lag angle, 4, which is equal to the logarithmic decrement divided by .ir. Fig. 1 shows the internal friction at three frequencies (the frequency given for each curve is the value measured at the peak). The data for these curves were obtained on cooling one specimen from 460C to just above the critical temperature for long-range ordering, which is about 390C for this alloy. In this way, the internal friction is measured under conditions where the alloy is in the disordered condition throughout the run. The curves obtained at frequencies of 2.15 and 1.29 cps show peaks in the range of measurement. The corresponding peak for the 0.78-cps curve is estimated, from the shift of this curve relative to the others, to be located slightly below the critical temperature (at 385C). The fact that the peak can be observed above the critical temperature is good evidence for the belief that it is a stress-induced ordering phenomenon similar to that which is observed in other disordered alloys. The fact that the peaks in Fig. 1 are not the same

Jan 1, 1959

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

IT has been shown1,3 that many observed phenomena related to annealing textures in f.c.c. metals can be adequately accounted for, at least in a qualitative way, by considering the orientation dependence of the boundary mobility, without any hypotheses concerning preferred orientation of nuclei. It was noted1 that this approach is particularly successful in the common cases of primary recrystallization in highly cold-worked polycrys-talline metals, where nuclei occur in great abundance, and that in the other extreme case, where the number of nuclei is very limited, or even only a single crystal is grown, the orientation dependence of boundary mobility has only a small effect, or none at all, on the orientations resulting from annealing. Recently Dunn described examples3-6 where observed secondary recrystallization textures apparently cannot be accounted for on the basis of oriented growth alone, but also require oriented nuclei, or at least the absence of nuclei in certain orientation ranges. In general, the great difficulty in correlating the preferred orientation of recrystallized grains with that of nuclei is inherent in the fact that nuclei are by nature very small, and that they are usually identifiable as "nuclei" only after growth, i.e., after they have already been subject to growth selectivity. An investigation was carried out by Liebmann and Lücke,' and also a very similar one by Graham and Cahn,' to obtain quantitative information on the orientation depend- ence of boundary migration rates in the recrystallization of slightly deformed aluminum single-crystal rods or plates, in which artificially nucleated recrystallized grains of predetermined orientation were grown. Liebmann and Lücke foupd maximum boundary mobility for boundaries across which the misorientation corresponded to a rotation of 40 deg around a common [Ill] axis, in accordance with earlier conclusions.9,1 Also, they confirmed that such an orientation relationship predominates among crystals growing into slightly extended single crystals from presumably random artificial nuclei. On the other hand, Graham and Cahn found no preferred orientation among crystals grown in a similar manner. It is not as yet known how these observations may be reconciled with each other. The view has been expressed in various papers5'10,21 that selective growth based on the orientation dependence of boundary mobility is not in itself sufficient to account for the formation of sharp re-crystallization textures, such as those often observed in highly deformed polycrystalline metals after annealing. The present work was undertaken to ascertain whether or not it is possible to obtain a sharp re-crystallization texture in a case where random nuclei are assuredly present in large numbers. It was previously found1' that high-purity aluminum crystals rolled 80 pct on the (110) plane in the [1T2] direction, when suitable precautions are taken, may be annealed for periods of about 1000 sec at 350°C without recrystallization. It was also found that the reluctance to recrystallize in this case is due to the scarcity of material in sufficiently deviating orientations to serve as nuclei. By using such a matrix,

Jan 1, 1959

By J. C. McDonald

A DDITIONAL experimental data are presented in this note on a phenomenon which has been touched on but lightly in the literature. The common magnesium base rolling alloy (AZ31B) contains about 3 pet A1 and 1 pet Zn. When cold rolled, it hardens until it starts to break up in the rolls at 30 to 50 pet reduction. When it is heated after rolling to full hardness, it softens. However, other magnesium alloys have shown themselves capable of being cold rolled indefinitely, provided the ratio of roll diameter to starting gage is sufficiently high. As measured by the tensile test, these alloys actually soften when the reduction becomes large (60 to 90 pct). A subsequent heating at 300' to 500°F can produce hardening of this metal. Heating at higher temperatures (600' to 800°F) causes recrystalliza-tion and softening. Menzen' has shown that a magnesium base alloy can be cold rolled without intermediate anneals as much as 90 pet. The alloy studied, Mg-1.5 pet Mn, softened considerably between 20 and 90 pet reduction, as measured by tensile properties; a decrease in yield strength of 30 pet, and an increase in elongation from 3.2 to 16.7 pet (longitudinal direction of the sheet). However, Menzen gives no data on the reaction of this metal. to heating. Ansel and Betterton2 and Hurst and Hatch3 report a similar effect in Mg-1.5 pet Mn-0.1 pet Ca. Their data show an initial hardening, followed by softening. The former authors also show that the alloy softened by cold rolling will harden when heated at low temperatures, and that these effects are absent in Mg-3 pet Al-1 pet Zn. In the course of work4, 5 some years ago, the author observed similar effects with alloys containing cerium, thorium, or zirconium; but not with elements like aluminum, silver, or zinc. Table IA contains the results of an experiment which shows these effects rather well. A binary alloy with 0.3 pet total rare earths (Mischmetal* added) was rolled hot to 1/16 in. and then annealed to full softness by heating 30 min at 800°F. Rolling was continued at 1.5 pet per pass to 80 pet total reduction on 8 in. diam rolls. The metal was harder after 20 pet work than initially but, at 80 pet reduction, properties were back to their original values. Heating for 1 hr at 450°F produced about the same hardness whether the reduction was 20 or 80 pet. At intermediate reductions, the metal hardened, but not to as high values. Extensive cold rolling may also be carried out on metal hot rolled at temperatures sufficiently low to produce a semihard temper. Mg-0.6 pet Zr was rolled to 0.1 in. at 700° to 800°F, 30 pet per pass. As shown in Table IB, a further cold reduction of 85 pet, at 1.5 pet per pass, definitely softened the metal.

Jan 1, 1959

By M. V. Nevitt

THE Cr,O-type, or P-tungsten, structure having the space group (Oh2— Pm,n) is one of the most widely occurring structures found among the intermediate phases involving transition metals. Including the phases reported here for the first time, the total number of these A,B phases now known is 39. Greenfield and Beck' have correlated the lattice parameters of these phases with the Goldschmidt radius of the close-packed chains of A atoms. Laves' discussed the apparent size of the A and B atoms in this structure. Gel1er" proposed a scheme for reproducing the lattice constants of the phases by the use of a list of effective C.N. 12 radii for the component elements. Reported here is a survey of the A,B combinations which appeared favorable for the stability of the Cr,O-type phase but which, at the time the investigation was begun, either had not been reported upon or had conflicting reports as to the existence of the structure. Seventy systems were investigated, and 8 Cr,,O-type structures were found. Six of these also were reported by other investigators in the interval between the start of this investigation and its completion. This survey yielded information as to the influence of the relative sizes of the A and B atoms on the stability of the phase and, for the various families of Cr,O-type phases, the effects of the sizes of the A and B atoms on the lattice constant. Likewise, a somewhat clearer picture of the connection between the position of the A and B elements in the Periodic Table and their Cr,O-type phase-forming tendencies has become apparent. Experimental Procedure Alloys were prepared in the form of arc-melted 3-gram buttons in all cases where the vapor pressure of neither component was high enough to cause

Jan 1, 1959

By M. Stern, I. S. Servi, W. W. Webb

ZINC has been considered an ideal material for investigations of the behavior of dislocation walls in metals. It has appeared particularly useful for studies of the mechanisms of plastic deformation and the motion of low-angle boundaries under stress, because orientated crystals are easily grown and cleaved. Moreover, the hexagonal structure makes the introduction of controlled tilt boundaries relatively simple. Apparently, another of the many reasons for selecting zinc as a working material is its commercial availability at the 99.999' pct purity level. However, most elements are only slightly sol-

Jan 1, 1959

By M. H. Mueller, P. A. Beck, W. P. Chernock

HARRIS introduced the term inverse pole figure for the diagrams previously used by Barrett' to represent the volume fraction p(a,ß) of material in various orientations with respect to the fiber axis in a specimen with fiber texture. The direction of the fiber axis with respect to the crystal lattice is specified by the two independent angle variables a and ß. In such a diagram p gives the fiber axis density distribution over the various crystallographic directions. The p(a,ß) may be given in a two-dimensional diagram by means of contour lines (p=con-stant) in a stereographic projection. The inverse pole figure incorporates in a single contour line diagram all the information given conventionally in pole charts for various (hkl) reflections and, therefore, it represents a considerable degree of condensation. Also, it gives this information directly in terms of the volume fraction of the specimen in various orientations, and it obviates the necessity of referring back and forth between the various pole charts in an attempt to interpret them in terms of orientations. Inverse pole figures undoubtedly represent the most adequate method for describing a texture in a quantitative manner and, at least in the case of fiber textures, this method is certainly a practicable one. Harris described1 a simple procedure for determining at least the rough outlines of a quantitative inverse pole figure. This method depends on the measurement of the intensity of X-ray reflections from various (hkl) planes lying parallel to the same specimen surface. In the case of a rod, reflections from a plane specimen surface perpendicular to the rod axis (fiber texture axis) are to be used. Harris has shown that the measured intensities I,,, reflected by crystal planes (hkl), aligned perpendicularly to the fiber axis of a specimen with unknown fiber texture, and the corresponding intensity Iu nkl from a random specimen are related to the p(a,ß) value for the unknown texture by the following equation IAkl/I°Aklw=c/c°.p(a, ß) [1] where C and C° re parameters depending on the crystal imperfections (extinction), surface preparation (e.g., thickness of oxide layer), the absorption coefficient in the specimen, effective line breadth, and instrumental factors. The values of the variables a and ß1 defining the crystal orientation, depend only on the indices hkl of the reflecting plane perpendicular to the fiber axis. Since p, as described by Harris1, is normalized in such a way that upon integration over the total orientation range its mean value is 1, the parameter C/C may be calculated approximately by the summation of Eq. l over all available X-ray reflections hkl, corresponding to a set of discrete orientations (rather than by integration over the complete range of orientations represented by the continuous variables a and ß). From the summation of Eq. 1 1/n SI AKL/I° Akl = C/C. SP(a,ß)/n is obtained where, as stated above 2p(a,ß) =1. n Therefore

Jan 1, 1959

By W. F. Carew, F. A. Crossley

The stress for rupture in 500 hr at 1000° F has been reported to be about 13,000 psi higher for Widmanstitten than for equiaxed microstructures for the Ti-7A1-3Mo alloy.1,2 Also, limited data indicated Widmanstatten and equiaxed micro-structures to have approximately the same creep resistance at 1000°F.' Recently, data have been obtained which show Widmanstatten structures to be significantly more creep resistant than equiaxed structures at 1000°F, see Fig. 1. These data represent several ingots and several heat treatments of the solution treat and age type. The thermal history and tensile properties corresponding to the creep data are given in Table I. The creep data were taken from creep-rupture tests. The associ- ated rupture data are given in Table 11. It may be noted that total creep deformations are considerably greater for equiaxed structures. Previous evaluations of stability indicated that all of the structures tested are stable with respect to exposure to stress at elevated temperature.1,2 For a minimum creep rate of 10-4 in. per in. per hr the difference in stress levels is indicated to be about 17,000 psi. Holden,et found an irreversible contraction upon heating three a-ß titanium alloys in the equiaxed condition above their ß-transus temperatures. The alloys were: Ti-6Al-4V, Ti-155 A (5Al-1.3Cr-1.5Fe-1.2Mo), and C-130 AM (44-4Mn). The net contractions in length between the original equiaxed and the final Widmanstatten structures measured at room temperature were: 0.4, 0.4, and 0.7 pct, respectively. The greater creep and rupture resistance of the WidmanstStten structure of the Ti-7Al-3Mo alloy may be associated with the phenomenon

Jan 1, 1959

By S. A. Spachner

An analysis of the powder patterns of the omega transition phase in three binary titanium alloys containing 8 pct Cr, 13 pet Mo, and 15 pet V, respectively, showed that all could be indexed on an orthorhombic unit cell. The unit-cell dimensions were all quite similar. There is evidence for the occurrence of more than one transition phase in Ti-Cr and Ti-V alloys. FOLLOWING the discovery of a new brittle phase in certain titanium-chromium alloys by Frost, Parris, Hirsch, Doig, and Schwartz,' named ? by these investigators, much interest has developed concerning the identification of alloy systems in which this phase exists, kinetics of the transformation in such systems, and the crystal structure of the ? phases appearing. Omega has been found in alloys of titanium-manganese, titanium-molybdenum, titanium-iron,' and titanium-vanadium.' In the present work, a study was made of the powder patterns of the ? phase occurring in alloys of Ti-8Cr, Ti-13Mo and Ti-15V in an effort to obtain a basis of comparison for ? phases appearing in these different alloys. Comparison of Alloys for ?-Phases Two hundred mesh powders of Ti-8Cr, Ti-13Mo and Ti-15V were prepared. A portion of powder sufficient for three x-ray powder specimens was placed in a Vycor tube, evacuated to less than 0.1 µ pressure, filled with argon, and sealed. The tubes were then heated to 900°C, held at this temperature for 30 min, and water-quenched. Following this transformation to the ß phase, the specimens were quenched in lead or solder pots, held at the desired temperature for varying lengths of time and water-quenched. The heat-treatments used and the phases identified are listed in Table I. The intermediate water quench was used in lieu of direct downquenching from 900°C to the bath temperature desired to circumvent the possibility of transformation of the powder specimen from ß to (ß + a) while it was being moved from the homog-enization furnace to the lead bath. To check the possibility that upquenching to the bath temperature might bring into play a different mechanism than downquenching to this temperature, resistivity measurements were compared on Ti-8Cr rod specimens which were transformed isothermally at 400°C by downquenching from the solution-treatment temperature and those which were transformed at 400" C by upquenching ß specimens from room temperature. The results are shown in Fig. 1. No difference in transformation mechanism was noted. It soon became apparent that sufficiently detailed Debye-Scherrer photograms of the ? phase in the alloys which were to be used could not be obtained by the use of copper radiation. Although satisfactory photograms of ß and ß + a phases were obtained with this radiation, the ? phase appeared to exhibit mild fluorescence, making interplanar spacing computation virtually impossible. Molybdenum radiation appeared to offer promise in cutting down this fluorescent effect, the mass absorption of titanium for molybdenum radiation being 23.7 in contrast to 204 for copper radiation. The reduction in the accuracy in determining the location of the photo-gram lines caused by the shorter wave length of molybdenum characteristic radiation did not appear to be a significant factor. Utilizing a camera of 57.3 mm radius, best results were obtained for exposure times ranging between 30 and 40 hr. Tube potential

Jan 1, 1959

By H. R. Peiffer

Recently artin has indicated that the recovery of resistivity at 145°C following elongation of molybdenum at room temperature was the result of the annihilation of vacancies. The activation energy for this process was, according to Martin, 1.26 ev. This energy seems to be a reasonable one for the activation energy for the diffusion of vacancies in molybdenum. However, impurity atoms such as carbon, nitrogen, and oxygen4 have an activation energy for diffusion in molybdenum of the same order of magnitude (i.e., 1.45, 1.15, and 2.09 ev, respectively). Cottrell and Churchman have already correlated the return of impurity atoms to dislocations in cold-worked iron with the return of the upper and lower yield point. According to cottrel16 the diffusion of carbon atoms to dislocations results in the return of the yield point. As the carbon atoms become trapped by dislocations, Bhatia has shown that a decrease in the electrical resistivity is to be expected. Cottrell and Churchman were able to correlate experimentally the decrease in electrical resistivity with the return of the yield point. Since one would expect strain aging to occur in molybdenum, an experiment was performed to determine whether the resistivity recovery at 150°C for molybdenum cold-worked at room temperature can be correlated with the return of an upper and lower yield point. For this experiment 3/16-in. tensile bars of Climax molybdenum, 99.961 pct pure, were used. The specimens were annealed at 1000° C for 1 hr in an argon atmosphere and then were elongated up to 10 pct on a Baldwin-Lima-Hamilton FGT

Jan 1, 1959

By J. S. Kirkaldy, W. V. Youdelis

THE occurrence of concentration distributions in rapidly cooled castings with gradients of opposite sign to those expected on the basis of the constitution diagram and diffusion controlled kinetics, has long interested metallurgists. The work on inverse segregation to 1937 has been adequately reviewed by Vaughan, and to 1949 by ell-walpole. The general conclusion for unidirectional solidification, that the enrichment of the initially solidifying regions with lower melting point compositions is due to the flow-back along interdendritic channels of normally segregated residual liquid, has a very sound experimental basis. Perhaps the best experimental work and the most complete qualitative description of the process has been given by Adams.3 The authors accordingly assume the reader's understanding of the content of this paper. It appears that one of the principal deterrents to the complete understanding of the process has been the lack of an analytical description. Although a number of workers including Masing,4-6 Sauerwald,7 and Adams3 have attempted quantitative predictions,

Jan 1, 1959

By M. W. Burkart, B. Lustman

Uranium-base alloys exposed to high temperature water fail either by uniform oxidation or by sudden cracking and disintegration of the metal. The disintegration results from the oxidation of a second phase which is precipitated during the corrosion process. The precipitate has been identified as a metastable hydride of uranium. URANIUM-BASE alloys consisting of the body-centered-cubic ? phase are susceptible to two different modes of corrosion failure when exposed to high temperature water. In the first process, a smooth oxide film is formed on the metal surface which continually flakes off during exposure and results in a uniform weight loss of the specimen. The oxide is present as a thin, adherent layer whose thickness remains approximately constant. As the metal oxidizes during corrosion, a nonadherent layer is built up on this film and continually sloughs off. Coincident with the uniform corrosion just mentioned, another process occurs which eventually leads to failure of the metal by cracking and general disintegration. The failure takes place during a relatively short time compared to the total exposure. To distinguish this type of failure from the uniform corrosion, the cracking or disintegration of the metal will be referred to as discontinuous failure. For the ? phase uranium alloys it is discontinuous failure rather than uniform corrosion that limits the useful corrosion life of the alloy. This paper will be concerned primarily with the mechanism of discontinuous failure. Physical Changes During Corrosion—The alloys used in this investigation were ? phase uranium alloys containing 7 to 12 wt pet Mo or Cb. The preparation of the alloys, the method of corrosion testing, and the actual corrosion results are presented in another paper.' The ? quenching treatment consists of annealing the alloy for 24 hr at 900°C in a sealed Vycor glass tube filled with helium and then water quenching to room temperature without breaking the tube. The corrosion behavior typical of a ? phase uranium alloy is shown in Fig. 1. This specimen was a U-12 wt pet Mo alloy tested in pressurized, degassed water at 650°F. The corrosion rate was practically constant at 0.28 mg per sq cm per hr or increased slightly until about 15 to 20 days of exposure, when the onset of discontinuous failure occurred in this particular sample, and the specimen soon began to crack and disintegrate. The simultaneous increase in the observed corrosion rate is a result of the increased area of exposure due to cracking of the specimen. The microstructure of a specimen that failed by cracking is shown in Fig. 2. The presence of a plate-like precipitate can readily be seen. Metallographic examination of corrosion specimens reveals that the onset of discontinuous failure is always preceded by the formation of a plate-like second phase in the ? uranium matrix. Hydrogen analyses of specimens periodically withdrawn from corrosion test reveal that the hydrogen content of the alloy increases on exposure to the high temperature water, as shown in Fig. 3. The hydrogen is available as a corrosion product resulting from the formation of UO2 by the reaction of the alloy with water. Specimens analyzed just prior to discontinuous failure contained as much as 1200 ppm H, whereas the plate-like phase appears to precipitate out at a hydrogen concentration of between 10 and 25 ppm. The observed increase in hydrogen content prior to and during the formation of the plate-like precipitate suggests that this constituent may be a hydride of uranium. Additional evidence linking the identity of this phase to a hydride is that it can be removed by vacuum annealing at temperatures of 100°C and above. Decomposition products of the ? phase would certainly not dissolve at such temperatures, nor could other likely products of corrosion, such as oxides, be dissipated at any of the test temperatures. The precipitation and growth of the second phase during corrosion is accompanied by an increase in hardness of the specimen. The hardness increase results from the dispersion of the harder precipitated

Jan 1, 1959