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By K. G. Gorling, S. J. Wallden, N. B. Lindvall

It is the policy of The Metollurgical Society to provide, in the TRANSACTIONS OF THE METALLURGICAL SOCIETY OF AIME, a prompt and accurate medium for publication of reports of significant new research in both the scientific and engineering aspects of metallurgy. Papers submitted to the Society are judged by competent reviewers according to established criteria for technical merit, accuracy, originality, and presentation. STAFF: Editorial Director, Rixford A. Beals; Associate Editor, James J. Burke; Assistants, L. Capria and R. K. Larkin. PUBLICATIONS COMMITTEE OF THE METALLURGICAL SOCIETY: A. W. Thornton, Choirmon; Dennis Carney, John Chipman, J. C. Fulton, J. H. Hollomon, H. tl. Kellogg, A. E. Lee, R. Maddin, J. D. Sullivan, and O. Swan. Review and selection of manuscripts is under the supervision of the following Publications Committees: Extractive Metallurgy Division T. B. King. Cha~rmon; S. J. Dickenson, R. P. Hermsdorf, R. Schuhmann, Jr.. and P. T. Stroup. Institute of Metals Division: Robert Maddin, Chairman. F. Lincoln Vogel, Jr., Vice-chairman, W. A. Backofen, R. W. Balluffi, J. H. Bechtold, M. B. Bever, R. S. Busk, C. G. Goetzel, Paul Gordon, C. D. Graham. Jr., Robert F. Hehe-mann, R. I. Jaffee, F. E. Jaumot, Jr., lrving R. Kramer, A. J. Leno, Horold Margolin, C. J. McHorgue, Russell A. Meussner, J. 6. Newkirk, H. W. Paxton, G. E. Pell~ssier, I. S. Servi, Alan U. Seybolt, A. J. Sholer, and Sack Wahsburn. Iron and Steel Division: J. C. Fulton, Chairman; T. B King, F. C. Langenberg, W. O. Philbrook, and T. B. Winkler. Published bimonthly by the American Institute of Mining Metallurgical and Petroleum Engineers Inc., 29 West 39th Street, New York 18, N. Y. Telephonne pennsylvania 6-9220.Petroleum Subscription Engineers$20 per year for non-AIME members in United States and North South and Central 6-9220.SubscriptionAmerica $25 toreign; $5 for AIME members. Single copies, $4.00, iinalo copies Southfpr;ign,andCentral $5 00. The AIME 'is $25not responsible for any statement made or opinion expressed in its publications Copyright 1958 1958 by the American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc. . Registered coble address, AIME New York . . . Indexed in Engineering Index, Industrial Arts Index, ...and Chemical Abstracts . . . Application for second class mail privileges IS pending at New Yark, N. Y. Volume 212, Number 2.

Jan 1, 1959

By N. F. Neumann, A. W. Schlechten

Metal chlorides were formed by reacting metal oxides and calcium chloride; the effect of additions to the reaction mixture was studied. It was found that by use of proper additions, metal chlorides could be prepared from mixtures that were not reactive under ordinary conditions. ManY recent metallurgical developments involve the use of chlorine or chlorides as primary reagents; good examples are found in the production of ductile zirconium and titanium by reduction of their chlorides with magnesium. Various methods of preparing metal chlorides are used and many others have been proposed. Some chlorides are formed by the direct combination of a metal or alloy with chlorine. Other processes react chlorine and metallic oxides; carbon or other reducing agents are usually employed to reduce the metal oxides and so promote chlorination. Metallic chlorides have also been produced by the exchange of chlorine between metal oxides and a chloride, such as sodium chloride. This type of reaction was the basis for the old process of chloride roasting in which metal ores were roasted in the presence of salt. Soluble chlorides thus formed

Jan 1, 1959

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 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. 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 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 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 J. B. Newkirk, W. G. Martin

Oxidized cobalt powder is known to have a magnetic hysteresis loop which is asymmetric with respect to the magnetization axis. The experiment described herein shows that the orientation relationship between the basal plane of hexagonal cobalt and the oxide which forms upon it at 400°C is {111}ux//{100.1 }co <110>ux//<11.O> This orientation relationship allows a magnetic interaction between the antiferromagnetic oxide and the ferromagnetic substrate which could account for the offset hysteresis loop. Oxidized nickel powder has a symmetrical hysteresis loop and so is apparently not influenced by any magnetic interaction between metal and oxide. The orientation of the oxide (cubic) was found to be identical with that of the nickel substrate when the oxide forms on a polished surface parallel with {111} Ni. IN 1956 W. H. Meiklejohn and C. P. Bean discovered that fine particles of cobalt which had been prepared in a certain way have a magnetic hysteresis loop which in a strong field is asymmetric relative to the magnetization axis.&apos; The cobalt powder exhibited this unusual magnetic property only after it had been oxidized in air or oxygen; it lost the shifted hysteresis loop when the oxide was reduced in hydrogen. X-ray and neutron diffraction&apos; experiments showed the presence of cobaltous oxide (COO) and hexagonal cobalt in samples exhibiting the biased hysteresis loop and specifically showed no indication of any other compound with the exception of mercuric oxide.* The magnetic hysteresis loop becomes symmetrical above the Nee1 temperature (paramagnetic state) of COO. Therefore, it was concluded that the anomalous magnetic behavior is associated with the influence of cobaltous oxide upon the metallic cobalt. It has been proposed that crystallographic coherency may exist between the cobalt and a plane of some antiferromagnetic material which has unbalanced spin distribution and sufficient magnetic anisotropy to hold its spin in the direction which existed when the specimen was cooled. COO has these properties. Therefore, Roth&apos; has suggested that cobaltous oxide may form with a {111} plane parallel and coherent with the basal plane of the hexagonal cobalt metal and proposed that, as consequence of the antiferromagnetic interaction between COO and the underlying cobalt, the magnetization direction in oxidized fine Co particles may be ro-lated from the easy c-direction.2 Such a relationship, he proposed, would explain the observed magnetic effect in oxidized cobalt powder. The main purpose of this study was to determine the orientation relationship, if any, between the basal plane of cobalt and the oxide which forms upon it. Attempts to produce a film of COO which was strong enough to be handled were not successful. However we did succeed in making a film of CoCo2O, which was strong enough to be removed from the cobalt substrate and mounted on an electron-microscope grid. Because of the close structural similarity of COO and CoCo2O, we believe the orientation relation found for CoCo2O, on cobalt probably also holds for COO on cobalt. The epitaxial relationship of NiO and Ni also was investigated. To date no shifted hysteresis loop has been observed with nickel powder. However, the similarity of atomic array in cobalt and nickel leads to the prediction that a {111} of NiO may be parallel with a (111} of nickel. Experimental Method Cobalt-Cobalt Oxide—A coarse-grained specimen of a (hexagonal) cobalt was prepared by allowing a large crystal of fee cobalt to transform slowly at 400°C. The crystal was then cut to expose a surface parallel with the basal plane. A back reflection Laue X-ray photograph showed that the 00.1 plane was within 2" of the cut surface. The surface was mechanically polished and then electro polished in 85 pet orthophosphoric acid after which the crystal was held for 30 min at 400°C in air. During this heat-treatment the surface darkened slightly due to the oxide film which formed. The film was not thick enough to give an X-ray diffraction pattern, even by a glancing-angle technique. Glancing-angle electron diffraction was not possible either, owing to the interference of the electron beam with the high magnetic fields which exist at the 00.1 surface of the cobalt. However, it was possible to make an electron-diffraction photograph of the oxide film by stripping it from the cobalt substrate using the method described later. By maintaining reference marks carefully, it was possible to preserve the orientation relationship between the stripped film and the substrate on which it was formed. The oxidized surface of the crystal was first covered with a 1 pet solution of collodion (cellulose nitrate) in amyl acetate. When the film was dry, small rectangles were scored on the surface with a needle point. The specimen was then repolished

Jan 1, 1959

By C. A. Bruch, J. F. Duffey

On the basis of metallographic and cooling-rate studies of 15 U-Zr alloys, a new version of the 6 phase region of the U-Zr phase diagram is proposed. IN several published diagrams of U-Zr alloy system:&apos; there is good agreement that at elevated temperatures complete solid solubility exists between y uranium and ß zirconium. Similarly, there is reasonably good agreement concerning the uranium-rich and zirconium-rich ends of the diagram. However, there is no agreement concerning the nature of the diagram at intermediate compositions and at temperatures below about 650°C. The early work of Saller et al.8 hows an intermediate phase, 6. In a later diagram by Saller and Rough&apos; shown in Fig. 1, the d phase field is drawn with dotted lines, indicating doubt that this phase exists. The diagram of Summers-Smith2 does not show the d phase. More recently Holden and Seymour&apos; have shown that in the composition range 40 to 60 wt pet Zr, the high-temperature ? phase, which is body-cen-tered-cubic, transforms to an ordered structure, 8. They found that the order-disorder transformation occurs between 595° and 610°C, and presented a diagram based on the study of four different alloy compositions. Most recently Saller et a1.5 presented a new diagram which differs with respect to the composition limits of the 8 field from the others proposed by these authors. The purpose of the present investigation was to determine the boundaries of the d phase field. Experimental Procedures and Results Alloys—Buttons, weighing 80 g of 15 different alloy compositions were prepared by arc melting Mal-linckrodt uranium and iodide-process zirconium in a water-cooled crucible. A controlled atmosphere of argon and helium was maintained in the furnace. Prior to making each button, a sacrificial button of zirconium was melted to increase the purity of the furnace atmosphere. Each alloy was then melted six times to improve its homogeneity. Subsequently the alloy buttons were jacketed in copper and hot rolled to slabs at 775°C. From these slabs, specimens were machined for chemical, thermal, and metallographic analyses, Table I gives both the estimated chemical composition of the alloys, and the values which were obtained by analysis. The oxygen contents varied from 0.013 to 0.032 pet, nitrogen from 0.0014 to 0.014 pet, and carbon from 0.0013 to 0.011 pet. The purity of the alloys ranged from 99.947 to 99.975 pet. Thermal Analysis—The specimens for thermal analysis were blocks 11/4 x 1/4 x % in. The bead of a calibrated thermocouple was placed between two of these blocks and molybdenum wire was wrapped around the assembly. Each assembly was sealed in a quartz capsule having an argon atmosphere. The capsule was placed inside a refractory crucible which was heated in a furnace. Using a method described by Smith,&apos; the emf of a differential thermocouple, with junctions inside and outside of the refractory crucible, was used to activate the

Jan 1, 1959

By L. M. Pidgeon, W. Curlock

FREE energies of formation of zinc sulfide and magnesium sulfide had previously been estimated to an accuracy of ± 5.0 kcal per g mol. In the present work, these values were determined experimentally. As the determinations of the free energies of formation of zinc sulfide and magnesium sulfide presented different problems, separate experimental procedures were employed for each. ZINC SULFIDE It is difficult to measure the free energy of formation of either zinc sulfide or magnesium sulfide by measuring their decomposition pressures directly, as they are very stable compounds. An attempt was made by Jellinek and zakowski3 to study the equilibrium. zns(s) + H2(g) = Zn(g) + H2S(g) [I] They passed hydrogen over zinc sulfide and analyzed the gases leaving the reaction zone for H2S. They were unable to determine the true partial pressures of the H2S by this method, as some of the H2S on being cooled from the reaction temperature, reacted with the zinc in the gas to produce ZnS. Consequently, they were unable to establish any true equilibrium data for reaction [I]. More recently,&apos; the equilibria ZnS(sphaledte) + Fe (s) — FeS(s) + Zn(g) [2] and ZnS(sphalerite) + 2Cu(s) — Cu2S(S) + Zn (g) [3] were studied. As the standard free energy of formation of Cu2S is known to * 3.0 kcal, and of FeS to ± 1.0 kcal, it should be possible upon performing equilibrium studies on reactions [2] and [3] to deduce the standard free energy of formation of ZnS (sphalerite). However, as both of these equilibria involve 2 solid sulfides, and as it is possible for these sulfides to dissolve in one another, it is necessary first to ascertain the activities of the various sulfides in these solid phases.

Jan 1, 1959

By D. W. Lillie

It has been demonstrated that considerable bend ductility exists in bulk specimens of polycrystalline high-purity silicon. The possibility of hot-forming at 1200°C is suggested. EXCELLENT corrosion resistance in many media and low cross section for absorption of thermal neutrons (0.13 barn) would make silicon of interest to nuclear engineers were it not for extreme brittle-ness and the difficulty of fabrication by any reasonable means. The use of silicon for structural purposes also has been considered in view of its light weight and oxidation resistance. Johnson and Han-sen&apos; have investigated the properties of silicon-base alloys and concluded that there was no way of making pure silicon or silicon-rich alloys ductile at room temperature. In view of reports of appreciable ductility in germanium single crystals above 550°C&apos;." and some plastic deformation in single-crystal silicon above 900oC,&apos; the present investigation was undertaken to define more precisely the limits of high-temperature ductility in pure silicon. After this investigation was begun torsion ductility in both germanium and silicon was reported by Greiner." Through the courtesy of F. H. Horn, a small bar of cast extra high-purity silicon was obtained and small bend specimens were made from it by careful machining and grinding. All of the reported tests results were obtained from samples from this bar (bar No. 1) and one other of similar source (bar No. 2). No complete analysis was obtained but, based on analysis of similar semi-conductor grade material, metallic impurities were under 0.01 pct total. Vacuum-fusion analysis for oxygen showed a value of 0.0018 2 0.0003 pct for the first bar tested and metallographic analysis showed no evidence of a second phase. Bend tests were carried out on an Instron tensile machine using a bend fixture with a 1 -in. span loaded at the center. Supporting and loading bars were 0.250 in. round and the load was applied by downward motion of the pulling crosshead of the machine. Specimen thickness and width were approximately 0.10 in. and % in. respectively. Loading rate was controlled by holding crosshead motion constant at 0.02 ipm. In some cases a smaller specimen was used on a 5/8-in. span with a 0.129-in.-diam loading bar. The entire bend fixture was surrounded by a hinged furnace and all heating was done in air atmosphere. Temperature measurement was made with thermocouples fastened directly to the bend fixture within less than 1 in. from the specimen. Autographic stress-strain curves were recorded during each test, and breaking load, total deflection, and plastic strain could be obtained from these curves. Stress was calculated from the beam formula S = 3PL/2bh2, where P is the load in pounds, L the span in inches, b the specimen width in inches, and h the specimen thickness in inches. This formula is strictly correct only in the elastic range but has been used to calculate a nominal stress for convenience in the plastic range. The stress given is the maximum stress in the specimen. Results The results of the complete series of tests are shown in Table I. The first group of tests (specimens Nos. 1-6) showed the beginning of plastic flow at a test temperature of 900°C, so two additional tests (Nos. 8 and 9) were made at 950°C on small-size specimens from bar No. 2. Specimen No. 8 was tested in the as-machined condition, and No. 9 was heat-treated in hydrogen at 1300°C for 2 hr, cooled to 1200°C and held 1 hr, cooled to 1000°C and held 1 hr, cooled to 900°C and held 1 hr, and finally cooled to a low temperature before removal from the hydrogen. It is apparent that the heat-treatment had a significant effect on yield strength and ductility. In addition, the magnitude of the yield point was conslderably reduced in the heat-treated specimen as is shown m Fig. 1 by tracings of the stress-strain curves. After obtaining a furnace capable of reaching higher temperatures specimens Nos. 10 to 13 were tested at 1100 and 1200°C. Strain rate was increased by up to a factor of 10 to see whether the ductility observed was excessively strain sensitive. Specimen NO. 10, strained at 0.02 ipm and 1100oC, was still bending at a deflection of 0.322 in. when the load rate was increased to 0.2 ipm, resulting in immediate

Jan 1, 1959

By A. J. Griest, P. D. Frost, H. A. Robinson

The flow characteristics and uniform elongation of alpha-beta titanium alloys in the solution-treated condition were shown to be markedly affected by the solution temperature. Two classes of alpha-beta alloys were distinguished, based on the effect of solution temperature on the uniform elongation. Martensitic alpha-beta alloys, which are relatively weakly beta-stabilized, showed decreasing values of uniform elongation as the solution temperature was initially increased. However, after solution-treatment at still higher temperatures in the alpha-beta field, the uniform elongation of these alloys was again high, and often attained its maximum value. Nonmartensitic alpha-beta alloys, which are more heavily beta-stabilized, showed a continuous decrease of uniform elongation with increasing solution temperature. The behavior was rationalized in terms of the alpha-beta ratio and the alloy content of the beta existing at the solution temperature. The data indicate that in commercial practice close temperature control may be required to get maximum uniform elongotion, and hence, maximum potential formability, in solution-treated sheet. Bend-test data also were obtained for the solution-treated conditions. A MOST important objective of current titanium research is the development of age-hardenable alloys with superior formability in the solution -treated condition. Alpha-beta titanium alloys have been shown to be amenable to high-strength aging treatments after solution-treatment in the alpha-beta field.&apos; However, heat-treatment data on the properties of solution-treated sheet, such as uniform elongation, minimum bend radius, and flow properties, which have a bearing on the potential formability, have not been widely available. This paper presents only the most significant results of a research program conducted at Battelle for the Air Force in an effort to develop sheet alloys that can be formed readily as solution-treated and subsequently aged to very high strengths. Data for 10 compositions representative of the more than 25 alloys studied in this program are presented. A primary objective of the paper is to demonstrate the pronounced dependence of the flow characteristics and uniform elongation on solution-treatment temperature. This effect is believed to be vitally important in the commercial heat-treatment of age-hardenable titanium sheet alloys. Experimental Procedures Melting and Fabrication—The nominal and actual compositions, beta transi temperatures, and rolling temperatures of 10 of the 30 alloys studied are presented in Table I. Stock :€or two of the alloys, E (Ti- 8Mn) and J (Ti-6A1-4V) was obtained from commercial heats. The remaining heats, except D and I, were double melted as 10-lb heats in a consumable-electrode furnace. Melting stock was 120 Brine11 hardness sponge. The oxygen and hydrogen analyses spotted throughout the heats indicate the range of interstitial levels resulting from the melting practice used. Heats D and I were melted as 20-lb ingots with the same grade of sponge. These ingots were cut in half and one portion used in the present evaluation. The ingots, which were about 4 in. diam and 4 in. in height, were upset forged and drawn at 1750°F to sheet bar 5/8 in. thick by 2 1/2 in. wide in such a manner that the top of the ingot corresponded to the top of the sheet bar. Slabs of the sheet bar, 5 1/2 in. in length were scalped to 1/2 in. thickness and rolled at the temperatures indicated in Table I to approximately 0.055 in. sheet. Elongation during rolling took place at 90" to the original forged length. The fabrication procedure used is described in some detail since the experimental heats showed considerable directionality in mechanical properties. The rolling procedures for the commercial heats were unknown, but were such as to produce essentially isotropic properties. All heats, as rolled, showed microstructures typical of alpha-beta alloys worked in the alpha-beta field; that is, the structures consisted of equiaxed alpha particles in a beta matrix. Heat Treatment— The effects of solution and aging heat-treatments on the properties of the alloys were evaluated uSing longitudinal and transverse tensile and bend coupons sheared from the sheet. Two or three solution-treated conditions were evaluated for each alloy. In addition, the alloys were also tested after annealing at 1200°F for 4 hr and furnace cooling. The solution-treated and annealed conditions were those in which the alloys might be expected to

Jan 1, 1959

By C. Feng, C. Elbaum

Knoop hardness measurements were carried out on large grains of iodide titanium containing different amounts of oxygen. For each oxygen content the hardness is recorded ainingas a function of the crystal orientation and of the angle 4 between the indenter diagonal and the projection of the C (hexad) axis in the surface. The results can be expressed by the following relation; hardness = n-k cos 2ø, where n and k are constants for a given oxygen content and crystal surface orientation. A NISOTROPY of hardness is a well-known phe-nomenon and has been reported for many metals.1-3 At the present time, however, such information is not available in the literature for titanium. Consequently, a systematic study of the simultaneous effects of oxygen content and crystallographic orientation on the hardness of titanium was undertaken in this laboratory. Evaluations of oxygen content in titanium are frequently carried out through hardness tests. Although such procedures may be justified in small grain specimens, the results of the present investigation indicate that the anisotropy of hardness should be taken into account in the case of coarsegrained specimens as well as in the case of pronounced preferred orientation. Materials and Experimental Procedures Iodide titanium, 99.99 pet pure and containing of the order of 0.002 wt pet O, was used throughout this investigation. The metal was arc melted in an argon atmosphere and cold rolled into strips 1/16 in. thick. These strips were subsequently recrystal-lized and strain annealed in vacuum (10" mm Hg or better) at 850°C in order to produce crystals varying in diameter from 10 to 25 mm. Oxygen was introduced into selected large crystals by heating at 700°C in an atmosphere of pure oxygen under an observed pressure of approximately 50 mm Hg. Each sample was subsequently annealed in vacuum at 850°C for 100 hr, in order to homogenize the oxygen content throughout the specimen. It was found that longer annealing was not necessary, for no change of surface hardness in a given direction was detected after prolonged annealing. The oxygen content was determined by the difference in weight of the specimens before and after the oxidation-annealing cycle. The accuracy of oxygen determination is within ±0.1 mg in samples weighing 0.5 to 1 g. A vacuum fusion analysis of oxygen was performed on several samples and gave results in good agreement with the ones obtained by the weight change. It should be emphasized that expected weight losses through evaporation of the metal in vacuum at 850°C&apos; are many orders of magnitude lower than the precision of these measurements. Following the annealing treatment, both oxidized and unoxidized crystals were carefully polished. All detectable traces of surface cold working were removed by repeated polishing and etching. Laue back reflection X-ray patterns were taken for each crystal for the purpose of determining the orientation and ascertaining the absence of substructures detectable by this method. Hardness measurements, using a 1 kg load, were subsequently carried out on a Tukon hardness tester equipped with a Knoop indenter. The Knoop indenter was used throughout this work because indentations obtained by means of a Vickers indenter are considerably distorted due to the anisotropy of the elastic constants in titanium. Such distortions are much less pronounced in the case of Knoop indentations, although for some orientations a cer-

Jan 1, 1959

By W. M. Parris, P. D. Frost, H. A. Robinson

The effects of hydrogen content and strain rate on the static tensile and notch-rupture properties of the Ti-3Mn-complex alloy heat-treated to differed strength levels were investigated. The extent of embriulement was found to be proportional to the amount of hydrogen present and the strength to which the specimens were heat-treated. The research suggests the possible necessity of specifying lower hydrogen limits than are now allowed when titanium alloys are heat-treated to higher strengths than are presently used. The research also supports a hypothesis advanced earlier for a mechanism of hydrogen embrittlement. MUCH attention has been focused on the effects of hydrogen in in Most of the published in- formation has dealt with the effects of hydrogen on alloys in the annealed or lowest-strength condition. The work of Kotfila and Erbin3 is one of the few exceptions. In view of the fact that heat-treatments are now being used to produce high strength in titanium alloys,&apos; it is necessary that more attention be given to the effects of hydrogen on these alloys in the heat-treated condition. Research was initiated to establish the effects of hydrogen on the properties of the Ti-3Mn-complex alloy at various strength levels. This research, which supplemented that of Kotfila and Erbin, was started because it was found that high-strength tensile specimens of this alloy were strain-rate sensitive. The essential results of the research are summarized in this paper. MATERIALS AND EXPERIMENTAL PROCEDURES Material for this investigation was a 41/2-in.-diam bar forged from a single commercial heat of the Ti-3Mn-complex alloy having the composition given in Table I. The as-received forging was reduced further by forging at 1750°F to 3/4-in. square bars. About one fourth of this material was vacuum annealed at 1400°F for 24 hr to obtain a base hydrogen content of 25 ppm. The remaining bars were hydrogenated to levels of 90, 140, and 260 ppm in a large Sievert&apos;s apparatus in the following manner: Four 3/4-in. square bars, 5 in. long, were placed in the reaction chambzr. The chamber was evacuated, heated to 1400°F, and a measured amount of hydrogen was introduced. When absorbtion was complete, as indicated by the drop in pressure, the reaction tube was cooled and the bars removed. Each batch of bars was then sealed in individual evacuated Vycor containers and heated for 24 hr at 1400°F in order to distribute the hydrogen homogeneously. After vacuum-annealing or hydroge nation, the bars were rolled at a temperature (1400°F) below the ß-transus to 1/2 - in. - diam rounds. Groups of the rolled specimens representing each of the hydrogen levels were given the following heat-treatments: 1) One hr at 1300°F, water-quenched. 2) One hr at 1300°F, water-quenched, and aged 8 hr at 1100°F. 3) One hr at 1300°F, water-quenched, and aged 4 hr at 1000°F. 4) One hr at 1300°F, water-quenched, and aged 48hr at 800°F. Heat-treated bars were machined into standard 0.250-in.-diam tensile specimens having 1-in. gage lengths. Throughout the processing and testing of this material, hydrogen analyses were made by vacuum-fusion methods to check for accuracy of hydrogen additions, homogeneity, and possible losses during processing. A summary of these analyses is given in Table II It may be seen that the actual hydrogen contents were reasonably close to the desired levels. In addition, it was noted that the variation in hydrogen content within any one bar did not exceed

Jan 1, 1959

By W. S. Hyler, L. W. Berger, R. I. Jaffee

Hydrogen additions of 390 ppm to A-55 titanium and 368 ppm to Ti-8 pet Mn have no deleterious Hydrogenadditionseffect on the unnotched and notched rotating-beam fatigue properties of these materials. &apos;These amounts of hydrogen, however, are sufficient to cause severe notch-impact thesematerials.embrittlement in A-55 titanium and pronounced loss of tensile ductility in Ti-8 pet Mn. The lack of embrittling effect in fatigue in the latter alloy is consistent with the postulated strain-aging mechanism of hydrogen embrittlement in a-ß alloys. There is a significant strain-agingincrease in the unnotched endurance limit of A-55 titanium with the addition of hydrogen. This increase may be explained as the result of internal heating effects which would dissolve the hydride and cause solid-solution strengthening. TITANIUM and its alloys may be seriously embrittled by relatively small amounts of hydrogen. The form which this embrittlement takes has been shown to vary with alloy type. The a alloys, for example, suffer most strongly from loss of notch-bend impact toughness&apos; when sufficient hydrogen is added, and this effect has generally been associated with the presence of hydride phase in the micro-structure. In a-ß alloys, on the other hand, hydrogen is most detrimental to tensile ductility in slow-speed tests,2-1 and the embrittlement may be detected in a most convincing manner by means of rupture tests at room temperature. This particular kind of embrittlement has not been associated with a change in microstructure, but has been classified rather generally as associated with a strain-aging type of mechanism.&apos; In the present paper, the effect of an embrittling amount of hydrogen on the rotating-beam fatigue properties of both an a and an a-ß titanium alloy is covered. For this study, annealed commercially pure (A-55) titanium was chosen as an a alloy, and equilibrated and stabilized Ti-8 pet Mn as representative of a typical a-ß alloy. Nominal hydrogen levels of 20 and 400 ppm were evaluated, the latter amount having been shown previously to be severely detrimental to the impact toughness of commercially pure titanium and to cause pronounced strain-aging embrittlement in the Ti-8 pet Mn alloy. The only report of the effect of hydrogen on the fatigue properties of titanium is given by Anderson et al.,° in which a push-pull type of fatigue test was conducted on as-received commercial-purity titanium sheet. Much scatter was found in the results, but generally the presence of hydrides slightly decreased the fatigue strength of unnotched specimens in the longitudinal direction. The results of notched tests were masked too greatly by scatter to be significant. Experimental Procedure Preparation of Materials—Analyses of the A-55 titanium and the Ti-8 pet Mn alloy used in this investigation are given in Table I, which indicates the 8 pet Mn alloy to be more nearly a 6 pet Mn alloy. This alloy will be referred to as Ti-8 pet Mn, however, since this is the commercially designated composition. Both alloys were received in the form of5/8-in. diam rod and, after suitable surface preparation, 5-in. lengths were vacuum annealed at 820°C. Half of the rods for each material were then hydrogenated at 820°C to a nominal hydrogen content of 400 ppm. The hydrogenated and vacuum-annealed A-55 rods were hot swaged at 700°C from 5/8-in. diam to 1/4-in. diam, and then annealed 1 hr at 800°C and air cooled prior to preparation into test specimens. Fabrication of the Ti-8 pet Mn alloy was by hot swaging to 3/8-in. diam at 760" and then 1/4-in. diam at 704°C. This material was then annealed 1 hr at 704", followed by furnace cooling to 593"C, and finally air cooling to room temperature. Evaluation—In order to examine more completely the effects of hydrogen on the particular materials studied, slow-speed tensile and notch-bend impact properties were determined in addition to fatigue data. Tensile specimens were of the standard ASTM type with a reduced section of 1/8-in. diam and a gage length of 1/2 in. A subsize cylindrical Izod specimen was used for impact tests. These specimens had a 45" notch with a 0.005-in. radius and a 0.150-in. root diam, and the stress concentration factor of this notch in bending was Kr = 3. Both the ten-

Jan 1, 1959