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By R. D. Nelson, S. D. Dahlgren

The conditions of temperature, strain rate, and total strain favoring deformation by grain boundary sliding, slip, or deformation with concurrent recrystallization were evaluated for alpha plutonium. Grain boundary sliding and slip were studied by examining structures formed on polished surfaces with 4.5 pct compressive deformation. The conditions required for recrystallization were determined from compressive deformation us time curves. At 110" C and at a strain rate of 10&apos;per min, deformation was almost exclusively by grain boundary sliding whereas slip was the predominant deformation mode at -10°C and lo-&apos; per min. Defarmation at intermediate tenzperatures and strain rates produced structures showing mixtures of grain boundary sliding and slip. Recrystallization occurred concurrently with deformation only after a critical strain was reached. About 14, 6, and 3 pct strain was required at 105", llO°, and lZO°C, respectively, before recrystallization started, irrespective of the strain rate in the range of lo-&apos;1 to 10&apos;4 per nzin. L HE temperature and strain-rate dependency of the modes of plastic deformation were evaluated for high-purity as-cast alpha plutonium. The techniques used to study slip and grain boundary sliding were similar to those employed previously for alpha plutonium by Bronisz and Gorum,&apos; and spriet.&apos; Recrystallization was investigated using the methods reported by Nelson.3 Bronisz and Gorum&apos; found that slip occurred on more than one slip system at room temperature, and suggested that grain boundary sliding also contributed to the deformation. spriet2 found that deformation was predominantly by slip at room temperature, and observed one to three orientations of slip traces in individual grains. In addition, he deformed polished samples at 10O° C, but concluded that the deformation character of alpha plutonium at 100° C and at room temperature were not essentially different. Several investigators reported that twinning was only occasionally observed.1&apos;2&apos;4 Nelson3 recently found in creep tests that high-purity alpha plutonium would recrystallize concurrently with compressive deformation at temperatures between 25" and 115°C. EXPERIMENTAL PROCEDURE Electrorefined plutonium having less than 300 ppm total impurities was received from Los Alamos Scientific Laboratory in the form of +-in. diarn cast rods. Major impurities were americium, <I00 ppm, and tungsten, (60 ppm. Less than 25 ppm each of other impurities were present. The rods were cut into right half-cylinders 0.35 in. long and 0.25 in. in diam, and the flat faces along the cylinder axes were metal-lographically polished. To avoid loss of the metallo-graphic polish by oxidation, the polished samples were deformed in a silicone fluid heat treating medium contained in a chamber evacuated to a pressure of lo-&apos; torr. Deadweight loading was used to compress the samples between 4.5 and 20 pct at strain rates between 10"4 and lo- &apos; min-&apos;. Strain rates were determined by dividing the total deformation by the elapsed time of the test, even though the strain rate was not constant during deformation. Curves of strain vs time for samples deformed with a constant compressive stress3 show that the strain rate changes by less than a factor of four during the testing of a given sample, which is small compared to the three orders of magnitude change in strain rate investigated. Two samples were loaded into an ordinary metallographic mounting mold and impacted by striking the mold piston with one blow of a 2-lb hammer. Deformation temperatures for the two impact samples were 25" and 90°C. The samples, following deformation, were washed in carbon tetrachloride and their polished and deformed surfaces were immediately inspected metallographi-cally. Subsequently, the deformation structures were replicated with acetate replicating tape for later electron microscope examination, and the samples were then repolished and etched to reveal the microstruc-tures of the deformed metal. Second-stage carbon replicas were prepared from decontaminated acetate replicas using the procedure developed by Miller, Bierlein, and astel.&apos; Additional samples, which were 0.35 in. long by 0.25 in. in diam, were used to obtain constant load deformation vs time curves. These samples were deformed 10 to 20 pct with loads of 15 and 20,000 psi at 120°C; 30, 45, and 55,000 psi at 110°C; and 20 and 30,000 psi at 105°C. Samples were polished and etched to determine whether or not recrystallization or twinning had occurred during deformation. RESULTS AND DISCUSSION The experiments showed that alpha plutonium deforms by grain boundary sliding, slip, and deformation with concurrent recrystallization. Deformation by twinning was insignificant. Metallographic examination of polished and deformed surfaces revealed grain boundary sliding and slip. The start of recrystallization was ascertained from constant load deformation vs time curves. Deformed surface structures of samples compressed 4.5 pct under four different conditions of temperature and strain rate, Fig. 1, show how the deformation mode changes from predominantly grain boundary sliding to predominantly slip with increasing strain rate and decreasing temperature. Deformation at 110°C and 10" 4 min-&apos;, Fig. l(a), was predominantly by grain boundary sliding. Only a few slip traces can be seen in Fig. l(a).

Jan 1, 1969

By Luc Delaey, Horace Pops

The structure and morphology of thermoelastic and burst type martensitic phases that form upon cooling in Cu-Zn-Si p phase alloys have been studied by transmission electron microscopy. The martensitic phases are composed of a lamellar mixture of two close-packed structures with different stacking sequence, namely ABCBCACAB (orthorhombic) and ABC (fcc). Striations within thermoelastic martensite are most likely produced during interaction with impinging burst-type martensite and not as a consequence of secondary shears. In a study of the martensitic transformation in ternary Cu-Zn based 0 phase alloys1 the dependence of the martensitic transformation temperature, M,, with composition shows variations for elements within a constant valence subgroup and between different subgroups. Such variations are not reflected in a change in habit plane, which is approximately the same for each ternary alloy, namely in the vicinity of (2, 11, 12 Ip. The fact that the habit plane remained constant, despite large differences in M, temperature and electron concentration, suggested2 that the crystal structures of the martensitic phases could be nearly the same. Crystal structures of ternary Cu-Zn based martensites have been determined recently for alloys containing the three-valent elements gallium3, 4 and aluminm. The present studies have been made to examine the structures and morphology of the martensitic phase in ternary Cu-Zn based alloys containing a four-valent element, silicon. I) PROCEDURE Two alloys were prepared by melting and casting weighed quantities of the component high-purity metals in sealed quartz tubes under half an atmosphere of argon. They were subsequently remelted by levitation under a protective atmosphere of argon. After allowing for losses of zinc as determined by the difference in weight before and after casting, the compositions in atomic percent of both alloys were established to be Cu-33.5 Zn-1.8 Si and Cu-27 Zn-5.0 Si. These alloys were homogenized in the P-phase field for 2 days at 800" C. Bulk samples consisted of a martensite phase at room temperature, the M, temperature being approximately 30&apos; and 200" for the 1.8 and the 5 pct Si alloys, respectively. Thin disks were cut from the ingots using a spark machine, and they were heated for 5 min at 800&apos; and quenched into water in order to obtain martensite. These slices were thinned chemically at room temperature in a solution consisting of 40 parts HN03, 50 part H3PO4, and 10 parts HC1 and thinned further electrolytically by the Window technique, using a voltage of 15 to 25 v and a mixture of 1 part HN03 and 2 parts methanol, which was kept at a temperature near -30° c. Foils were examined by transmission electron microscopy using a Philips EM 200 electron microscope. 11) RESULTS AND DISCUSSION 1) Structure and Morphology. Fig. 1 shows the martensitic phase in the alloy containing 1.8 at. pct Si. This phase is composed of contiguous platelets, each containing striations. The direction of the striations changes at the boundary between individual platelets. These internal markings resemble the striations that are usually identified as stacking faults, as for example in Cu-A1 martensites6-a or the lamellar mixture of two close-packed phases in Cu-Zn-Ga marten-sites.3p &apos;9 lo In the present alloys, selected-area diffraction experiments have been obtained in order to determine the nature of the striations. Figs. 2(a), (61, and (c) are electron diffraction patterns of an area inside a single martensite plate. Fig. 2(a) contains diffraction spots which correspond to two close-packed structures with different stacking sequences, namely ABCBCACAB (orthorhombic) and ABC (fcc). Spots belonging only to the fcc structure are indicated by arrows. By tilting the foil either the orthorhombic structure, Fig. 2(b), or the cubic structure shown in Fig. 2(c) may be obtained. When the foil is oriented so that only the diffraction spots of the orthorhornbic structure are present, bright-field illumination shows small lamellae, as seen in Fig. 3. In this figure the lamellae that belong to the fcc structure are bright bands inside the dark extinction contours of the orthorhombic structure. The boundaries of the lamellae are parallel to the basal planes of the orthorhombic structure and to the {Ill} planes of the cubic structure, the close-packed directions of both structures being parallel. The 5 pct Si alloy shows similar features as those described for the 1.8 at. pct Si alloy.

Jan 1, 1969

By William D. Klopp, Joseph R. Stephens

A substantial reduction in the 300°F ductile-to-brittle transition temperature for unalloyed chromium was achieved in alloys from systems which resemble the Cr-Re system. These alloy systems include Cr-Ru, Cr-Co, and Cr-Fe. Transition temperatures ranged from -300° F for Cr-35 at. pct Re to -75°F for 0-50 at. pct Fe. The ductile alloys have high grain gvowth rates at elevated temperatures. Also, Cr-24 at. pct Ru exhibited enhanced tensile ductility at elevated temperatures, characteristic of superplas-ticity. It is concluded that phase relations play an importarlt role in the rhenium ductilizing effect. The ductile alloys have compositions near the solubility limit in systems with a high terminal solubility and which contain an intermediate o phase. The importance of enhanced high-temperature ductility to the rhenium ductilizing effect is not well understood although both may have common basic features. CHROMIUM alloys are currently being investigated for advanced air-breathing engine applications, primarily as turbine buckets and/or stator vanes. The inherent advantages of chromium as a high-temperature structural material are well-known1 and include its high melting point relative to superalloys, moderately high modulus of elasticity, low density, good thermal shock resistance, and superior oxidation resistance as compared to the other refractory metals. Additionally, it is capable of being strengthened by conventional alloying techniques. The major disadvantage of chromium is its poor ductility at ambient temperatures, a problem which it shares with the other two Group VI-A metals, molybdenum and tungsten. For chromium, the problem is further amplified by its susceptibility to nitrogen em-brittlement during high-temperature air exposure. In cases of severe nitrogen embrittlement, the ductile-to-brittle transition temperature might exceed the steady-state operating temperature of the component. The low ductility of chromium would make stator vanes and turbine buckets prone to foreign object damage. The present work was directed towards improvement of the ductility of chromium through alloying, with the anticipation that any improvements so obtained might be additive to strengthening improvements achieved through different types of alloying. The alloying additions for ductility were selected on the basis of the similarity of their phase relations with chromium to that of Cr-Re. The reduction in the ductile-to-brittle transition temperatures of the Group VI-A metals as a result of alloying with 25 to 35 pct Re is well established.a4 the temperature range -300" to 750° F. This phenomenon is commonly referred to as the &apos;<rhenium ductilizing effect"; this term is also used to describe systems in which the ductilizing element is not rhenium. Other alloy systems which have recently been shown to exhibit the rhenium ductilizing effect include Cr-Co and c-Ru.= In order to explore the generality of this effect, alloys were selected from systems having phase relations similar to that of Cr-Re, primarily a high solubility in chromium and an intermediate o phase. The following compositions were prepared: Cr-35 and -40Re; Cr-10, -15, -18, -21, -24, and -27 pct Ru; Cr-25 and -30 pct Co; Cr-30, -40, and -50 pct Fe; Cr-45, -55, and -65 pct Mn. Seven other systems were also studied which partially resemble Cr-Re. These systems have extensive chromium solid solutions or a complex intermediate phase, not necessarily o. The compositions evaluated include the following: Cr-20 pct Ti; Cr-15, -30, and -45 pct V; Cr-2.5 pct Cb; Cr-2.5 pct Ta; Cr-20 pct Ni; Cr-6, -9, -12, and -15 pct 0s; Cr-10 pct Ir. The compositions of alloys in these systems were chosen near the solubility limit for the chromium-base solid solutions, since in the Group VI-A Re systems, the saturated alloys are the most ductile. These alloys were evaluated on the basis of hardness, fabricability, and ductile-to-brittle transition temperatures. In addition to the studies of alloying effects on ductility, an exploratory investigation was conducted on mechanical properties at high temperatures in Cr-Ru alloys EXPERIMENTAL PROCEDURE High-purity chromium prepared by the iodide deposition process was employed for all studies. An analysis of this chromium is given in Table I. Alloying elements were obtained in the following forms: Commercially pure powder — iridium, osmium, rhenium, and ruthenium. Arc-melted ingot — titanium and vanadium. Electrolytic flake — iron, manganese, and nickel. Sheet rolled from electron-bearn-melted ingot — columbium and tantalum. Electron-beam-melted ingot — cobalt. Sheet rolled from arc-melted ingot — rhenium. All alloys were initially consolidated by triple arc melting into 60-g button ingots on a water-cooled hearth using a nonconsumable tungsten electrode. The melting atmosphere was Ti-gettered Ar at a pressure of 20 torr. The ingots were drop cast into rectangular slabs and fabricated by heating at 1470" to 2800° F in argon followed by rolling in air. Bend specimens measuring 0.3 by 0.9 in. were cut from the 0.035-in. sheet parallel to the rolling direction. The specimens were annealed for 1 hr in argon, furnace cooled or water quenched, and electropolished prior to testing. Three-point loading bend tests were conducted at a crosshead speed of l-in. per min over

Jan 1, 1969

By S. G. Epstein

Electromigration has been measured in dilute liquid alloys of lead in antimony and antimony in lead. In these alloys antimony migrates with the electron current; lead migrates in the opposite direction. These results, which contradict the mass criterion, were predicted by the electron drag model for electromigration in liquid alloys. The existing experimental data are shown to correlate with the difference in electrical resistivities of the alloy components. FOR many years investigators have attempted to relate observed electromigration phenomena in liquid alloys to the physical properties of the alloy components. The most successful correlation was found by Angus et&apos; al.,1 who in 1959 proposed an empirical criterion for predicting the relative direction of motion of the components of a liquid alloy in an electric field: the component with the smallest atomic mass concentrates at the cathode. While this criterion is obeyed in nearly all the alloy systems which had been investigated, the physical basis for such an effect was not understood. It was also disturbing that the mass criterion predicted the wrong sign for the Haeffner effect; observations with pure liquid metals revealed that in every instance the lighter isotope was transported to the anode.2 Klemm3 explained these isotopic separations by suggesting that the lighter isotopes were more mobile and more easily carried to the anode with the electron stream. Additionally, several deviations from the mass criterion have been found in liquid alloys, notably involving transition metals such as chromium, nickel, palladium, and zirconium, which migrate to the anode in liquid bismuth.4&apos;5 Recently, a model has been proposed6 in which electromigration in liquid alloys is attributed primarily to the interaction between the electron stream and the metal ions. In essence, this model predicts that the component with the greater electron-ion scattering cross section will be preferentially transported to the anode, displacing the other component to the cathode. The electrical resistivity of each pure component at its melting point is taken as the measure of its scattering cross section. This model was developed from the results of systematic studies with various solutes in liquid mercury,7&apos;8 bismuth,9 and sodium.10 In every alloy, the component with the greater resistivity has centrates at the anode. Coincidentally, in every instance the component with the greater resistivity has also the greater mass, apparently satisfying the mass criterion. In order to differentiate between electron-ion coupling and atomic mass as the relevant physical prop- erty influencing electromigration, measurements were made with Pb-Sb alloys. Lead has an atomic mass nearly twice that of antimony, but lead has an electrical resistivity of 91 microhm-cm while antimony has a value of 113.5 microhm-cm at their respective melting points. The mass criterion predicts that in an alloy of the two antimony will concentrate at the cathode; the electron drag model predicts that antimony will concentrate at the anode. EXPERIMENTAL To conclusively determine the relative motion of lead and antimony in each other, solute electromigration was measured in dilute liquid alloys of antimony in lead and lead in antimony. Both starting materials were 99.999+ pct pure. The measurements were made with the same capillary-reservoir technique previously used for measuring electromigration in liquid bismuth alloys.11 Several changes in the experimental apparatus were necessary, however, to accommodate liquid antimony, which has a higher melting point than bismuth. The modified apparatus is depicted in Fig. 1. In each experiment four quartz capillaries were filled with the molten alloy. A direct current was passed through two of the capillaries; the electrode in one of these capillaries was made the cathode, and the electrode in the other was made the anode. The remaining two capillaries sampled the alloy in the reser-

Jan 1, 1969

By H. E. Cline, J. L. Walter

Grain boundary sliding and migration were studied in pure aluminum bicrystal and polycrystal samples with two-dimensional grain structure. Scratches, 50 P apart, were used for measurement of sliding and migration distanceso. Samples were deformed at constant rate at 315C and events recorded continuously on wrotion picture film. Electron micrograPhs of boundary-scratch intersections were obtained. Yield and flow stress values were measured. The sequence of sliding and migration events for a three-grain junction is described in detail. Sliding depended only on the resolved shear stress imparted to the boundary. Sliding was accowmodated by formation of shear zones in grains opposite triple points and adjacent to curved boundaries. These shear zones provided the driving force for grain boundary migration. Migration caused rumpling of the boundaries, decreasing the sliding rate. Sliding and migration generally began at the same time, occurred simultaneously and ended at the same time. In the bicrystal, sliding and migration rates were proportional. Initial sliding rules of 5 X joe cm per sec. were measured for the polycrystal and bicrystal samples. These sliding rates agree wilh the internal friction experirnents of K;. The observations seem consistent with a viscous boundary sliding nzechanism. GRAIN boundary sliding is the translation of one grain relative to its neighbor by a shear motion along their common boundary. Sliding is thought to be an important mode of deformation at elevated temperatures and at low strain rates such as prevail in creep,&apos; and perhaps in the area of superplastic behavior.2"4 Although much work has been done to investigate grain boundary sliding, the effort has not led to the identification of a mehanism. KG showed that grain boundaries in aluminum exhibit a viscous nature under very small displacements of internal friction measrements. Various dislocation mechanisms have been proposed but are without conclusive experimental support. Attempts to relate sliding to 6&apos;s viscous boundaries have been unsuccessful in that measured rates of sliding are always several orders of magnitude lower than KG&apos;S results would predict.= In bi crystals7and polycrystalsR of aluminum tested under constant load, the grain boundary sliding was found to be proportional to the total creep elongation which indicated that sliding might be controlled by deformation of the grains. Shear zones were observed to extend beyond grain boundaries at triple points to accommodate the sliding.8 Surface observations brought forth the opinion that sliding and migration occurred alternately, in sequence.&apos; Measurements of sliding at the surface have been criticized because they might not be representative of the interior of the sample. Generally speaking, it seemed that much of the previous work and knowledge was based on observations made at relatively low magnification and examination of samples after deformation had been accomplished. Thus, it was the purpose of the present study to continuously record, at high magnification, the events occurring during the deformation of pure aluminum. Samples with two-dimensional grain structures were used to simplify interpretation of the results. The sliding and migration of small areas of many samples were continuously recorded by time-lapse motion pictures. Replicas of the surface were used to provide high-resolution electron micrographs. These observations, coupled with tmsile strength data, provide sufficient information to arrive at an understanding of the phenomenon. EXPERIMENTAL PROCEDURE An ingot of 99.999 pct A1 was rolled to sheet, 0.127-cm thick. Tensile specimens, with a gage length of 0.85 cm, were machined from the sheet. Bicrystal tensile specimens, of the same dimensions, were spark cut from a large bicrystal ingot. The grain boundary was oriented at 45 deg to the tensile axis. The surfaces of the tensile samples were ground flat on fine metallographic paper and were then electropolished in a solution of 75 parts absolute alcohol and 25 parts of perchloric acid. The solution was cooled in an ice-water bath. Using a weighted sewing needle suspended from a small pivot on a precision milling machine, a grid of fine scratches, 50 p apart, was scribed on one surface of the sample. The polycrystalline samples were then annealed in hydrogen for 15 min at 350" to 400°C to produce a two-dimensional grain structure of about 0.2-cm average grain diameter which would not undergo further growth at the test temperature, 315OC. Examination of both surfaces of the samples showed that the grain boundaries were perpendicular to the surface of the polycrystal and bicrystal samples. A hot-stage tensile machine was constructed for use with an optical microscope as shown in Fig. 1. The specimen is shown mounted in the grips. The grips ride in V-ways so that the sample can be mounted without damage. The rear grip is free to slide so that when the sample expands during heating it is not put under a compressive stress. When the grips and samples are at temperature, the rear grip is locked in place by two set-screws. The other grip is connected to a synchronous drive motor which, through a worm gear and a fine-threaded rod, deforms the

Jan 1, 1969

By Hansheinz Portisch, Harold Margolin

A surface expansion was found to occur sometime after etching in Ti-A1 alloys containing 9.5 to 12.5 wt pct Al. The structure formed, grew, and disappeared with tzrrze. The surface expansion was followed by microscope observations and interferometric and lattice parameter measurements. Activation energy measurements for the growth of the "expansion structure" and chemical analysis indicated that the phenomenon occurred as a result of hydrogen pzckup during etching. It is proposed that hydrogen initially enters octahedral sites of Ti3Al coherent with a Ti and later shifts to the tetrahedral sites. It is postulated that expansion occurs when hydrogen enters the tetrahedral sites. The expansion structure disappeared, it is proposed, because of diffusion of hydrogen from the surface into the body of the alloy and because of loss of coherency of Ti3Al. In examining Ti-A1 alloys, Ence and arolinl observed markings on the surface of specimens. These markings did not appear after electropolishing only, but rather appeared only after etching. The markings appeared to grow as a function of time after etching and later seemed to disappear. Although the markings had some similarity to precipitates, showing, frequently, a Widmanstatten type of arrangement, the observation that other microstructural markings continue to be seen within the new structure suggested that it was actually not a precipitate. The source of this structure was unknown and an attempt was made in the present investigation to develop some understanding of its nature. It has been labeled expansion structure. 1) EXPERIMENTAL PROCEDURE A) Alloys. Alloys in the range 6.5 to 14.5 wt. pct A1 were studied. Bars, 4 in. sq, forged from Bureau of Mines (73 Bhn) titanium consumably arc-melted 4-lb ingots,&apos; as well as 50-g arc-melted buttons of desired aluminum contents were used. The 50-g buttons also used Bureau of Mines titanium (73 Bhn) and aluminum of 99.99 pct purity. Buttons containing up to 8.5 wt pct A1 were hot-rolled from a furnace at 900&apos; . Those with higher aluminum contents were hand-forged on a titanium anvil, and heated with an oxygen-hydrogen torch in the region of 1200" to 1300°c. Frequent reheating kept the samples at the desired temperature range. After a reduction of about 30 pct, the samples were water-quenched. To eliminate any contamination picked up either during hot rolling or forging, at least 1 mil of the surface of the sample was taken off. B) Heat Treatment. Prior to heat treatment all alloys were vacuum-annealed to remove hydrogen. Samples were annealed at 900&apos; until a vacuum of 10&apos;5 mm Hg was established. After this treatment, the samples were wrapped in molybdenum sheet and heat-treated in argon-filled quartz capsules, which were broken under water or iced brine at the conclusion of the heat treatment. All heat treatments under dynamic vacuum were performed in a rapid-quench furnace. This consisted of a molybdenum-lined quartz tube attached to a vacuum system and through a stopcock to a beaker of water. At the completion of the heat treatment the vacuum stopcock was closed, the furnace shut off, and dropped below the quartz tube. Then immediately the inlet stopcock was opened and water admitted until the tube was filled. The steam formed was allowed to escape through the inlet stopcock. This method was used in heat treatments up to llOO°C. C) Metallography. Specimens for metallographic examination were ground, then electropolished using a Disa Electropol machine with a perchloric acid electr01te. Specimens were etched with R-etch.3 A standard etching time of 3 min was used, with the specimen being agitated during immersion. D) Sample Preparation for X-ray Analysis. Samples 0.2 to 0.5 mm in diam were produced from heat-treated rods which were turned to 2 mm diam on a lathe and then rotation-etched. An etchant consisting of 1 pt HF, 7 pt HN03, and 12 pt HzO was satisfactory. With the rod rotating in a vertical position at 50 to 100 rpm, a needle with uniform dimensions could be obtained. Care had to be taken to insure that the rod was at the center of rotation, otherwise cavitation developed. If a small unevenness developed, it was possible to grind it off with a fine emery paper. E) X-ray Diffraction. All X-ray work was done on a North American Phillips X-ray diffraction apparatus and a Jarrell Ash microfocus X-ray unit. The Phillips unit was used with a copper target and nickel filter. The Jarrell Ash unit was fitted with a cobalt target and iron filter. For the Phillips unit 35 kva and 20 ma were used, whereas for the microfocus unit with the 100-p fixed-focus gun 40 kv and 1.5 ma were used. It was found that alignment of cameras on the Jarre11 Ash unit was very critical. The X-ray beam contains an intense area which is not the beam center. The cameras were aligned with the intense region by monitoring the beam coming out of the camera with a Geiger counter. Adjustments were made until a maximum intensity was obtained. A Phillips diffractometer with a Brown chart recorder furnished some of the lattice parameter data. The divergence slit up to 80 deg 28 was I deg; above 80 deg, a 4-deg opening was used, while the scatter slit was1 deg and the receiving slit had a 0.003-in. opening. The general scanning rate was 1 deg per min, while peaks of special interest were rescanned at -j deg per min. For elevated-temperature X-ray diffraction a Uni-cam High Temperature Camera with a film diameter

Jan 1, 1969

By E. S. Machlin

The wzodel of Blandin and Diplunt;, generalized to include a phase factor, is applied to the carbon-carbon interaction in iron. Darken&apos;s "energetic" model is generalized to include not only first neighbor interactions but further neighbor interactions as well. On the bases of these generalized models relations are derived for the activity of carbon in both austenite and ferrite in terms of the carbon-carbon Pair interaction energies. A single function then yields the pair interaction energies consistent with the experimental activities of carbon in both ferrite and austenite. Thus, a simple explanation is given for the observation that the nearest-neighbor interaction between carbon is repulsive in austenite and attractive in ferrite. Certain consequences of this approach are explored. OnE object of the present paper is to attempt to take into account the consequences of electrostatic contributions to the carbon-carbon pair interaction energy for carbon as a solute in iron. Friedel&apos; has shown that oscillations in electrostatic potential are to be expected about a solute atom in a metallic solution. Blandin and 6lant6&apos; have shown that such oscillations yield an interaction energy between pairs of solute atoms that obeys the relation: W{ = A cos(2ftFri + 4>)/(kFri)3 [l] where kF = Fermi wave vector, ri = distance between solute atoms comprising the pair7 <p = phase factor dependent only on electronic nature of solute and solvent, A = coefficient dependent only on electronic nature of solute and solvent. Machlin3 found that Eq. [I] accurately described the pair interaction energy derived from short-range order measurements based on field ion microscope observations of dilute alloys of platinum. He also found that the value of the phase factor $ derived from residual resistivity measurements agreed well with that obtained from the analysis of the short-range order data. Harrison and paskin4 were able to predict the long-range ordering energy of 0 brass using Relation [I] and residual resistivity values to predict the value of the phase factor $. Machlin5 has repeated their analysis and applied it to the prediction of the long-range ordering energy in AgZn and AgCd with excellent agreement between prediction and experiment. Both A and $ are independent of the crystal structure. The Fermi wave vector depends uniquely upon the conduction electron concentration per unit volume in the spherical approximation of the Fermi surface. Thus, Eq. [I] is expected to apply to both fer- rite and austenite with only one set of values of A and $. Mossbauer studies6 yield the result that iron has one 4s electron. We shall make an assumption found to hold previously for platinum3&apos;7 and nikel, which is that only the s electrons are involved in shielding the perturbing potential of carbon. With this assumption, kF = 1.35 A-l. Although A and $ may be obtained from certain mdels&apos;&apos;&apos; we shall take A and $ to be empirical constants in the spirit of Kohn and osko.&apos; Thus, Eq. [I] involves two adjustible parameters. Consequently, two independent relations in A and $I are required in order to evaluate them for carbon as a solute in iron. We may use a recent analysis of Aaronson, Domain, and poundg who showed that Darken&apos;s energetic model,1° as well as others, can be used to describe the activity-temperature data for carbon in iron in both the aus-tenitic and ferritic phases. Darken&apos;s model takes into account only first neighbor pair interactions. For our needs, all neighbor pairs need to be taken into account. It is convenient to generalize Darken&apos;s model. The result for the partition function for austenite is: over the temperature range 800" to 1200°C and where the uncertainty corresponds to one standard deviation. Eq. [4] effectively yields only one relation. Another relation is required to obtain unique values for A and $. One property of Eq. [4] is that it is independent of crystal structure. Hence, data for a iron can be used to obtain another relation. To arrive at this relation we must generalize Eqs. [2] and [3] so that they may be applied to the bcc a iron. The result is that:

Jan 1, 1969

By B. W. Christ, P. M. Giles

Mossbauer effect measurewents have been made on I-mil-thick foils of commercial 1 wt pct C steel and Fe-2 wt pct C alloy. The experimental method required about 3 to 5 vol pct of a phase in the nzultiphase steel sample for detection. Room-temperature Md&apos;ssbauer patterns obtained on austenitized atid quenched samples exhibit fifteen, and possibly twenty-one, lines. A sharp parama&tetic singlet and a quadrupole doublet, poorly resolued from the singlet, are attributed to austenite. Remaining lines are due to tnartensite. Accurate evaluation of austenite line paranzeters is not feasible if significant amounts of other phases such as carbides or martensite occur simultaneously with austenite. This is demonstrated by comparison of hyperfine interactions determined for austenite in multiphase high-carbon samples with those reported for Fe-C austenite in a nearly 100 pct austenitic sanple. Lines from carbides are incompletely resolced from austenite lines, as demonstrated by comparison of austenite line positions with carbide line positions calculated frow published values of hyperfine interactions. One martensite line overlaps an austenite line in the pattern for commercial 1 wt pct C steel. Results of this study suggest that the usefulness of e M6ssbauer pectroscopy for quantitatizle analysis of austenite in bulk samples of quenched and tempered high-carbon steels is restricted by poor resolution. Use of Mossbauer spectroscopy for phase identification and for evaluation of atomic and electronic structures appears quite feasible, however, The Mijssbauer effect has been widely discssed,&apos;-and e Mossbauer effect measurements have been reported on materials of metallurgical interest.7"20 In particular, it has been proposed that e Mossbauer patterns of commercial steels and laboratory-made Fe-C alloys, in the quenched condition, are composed of lines originating in two phases, Fe-C austenite and Fe-C martenite.-&apos; Evidence accumulated in this study demonstrates that three absorption lines found in the central region of the e Mossbauer pattern obtained on quenched steels are attributable to retained austenite. This interpretation is supported by parallel decreases in the intensity of these three lines caused by subambient cooling of commercial 1 wt pct C steel samples after water quenching to room temperature. A second result of this study is to clarify effects of line resolution and sensitivity in the Mossbauer patterns of multiphase steels on the accu- rate determination of austenite line parameters. Experimental line widths (full width at half height) are generally 1.5 to 3 times larger than the natural line width of 0.19 mm per sec. At least two lines, and sometimes more, from a single phase such as cementite (Fe3C), other carbides, martensite, and austenite fall in the energy band, i0.85 mm per sec. hhis band width is employed simply for convenient reference. It represents approximately the energy interval between the + 112 to 112 transitions in ferrite and is expressed as the velocity needed to Doppler shift a 14.4kev 7 ray to the aforementioned ferrite energy levels. This energy band is referred to as "the central region of the Mossbauer atttern:: in this paper. Hence, due to the large number of lines from different phases in a multiphase steel falling in a relatively narrow energy band, absorption lines from the different phases may overlap. Analysis of available data, presented below, indicates that this occurs to a significant extent for phases which commonly occur in quenched and quenched and tempered high-carbon steels. One consequence of limited resolution in the Mdssbauer patterns from multiphase steels is difficulty in accurate determination of such line parameters as position, width, and intensity. In fact, it appears that quantitative analysis for retained austenite in quenched and tempered high-carbon steels is not practical with the present experimental method. Line resolution is influenced to some extent by sensitivity. We point out below that atom or volume fractions of less than about 3 to 5 pct are not detected by the present experimental method. Thus, the presence of a multiplicity of phases does not always lead to impaired resolution. Finally, we report in this paper room-temperature MGssbauer parameters determined for austenite in a freshly quenched, commercial 1 wt pct C steel and in a freshly quenched laboratory heat of an Fe-2 wt pct C alloy. These parameters are compared with others reported in the literature. Three types of hyperfine interactions are detectable in a Mossbauer effect measurement: isomer shift, quadrupole interaction, and magnetic dipole interaction. These interactions are evidenced by one, two, and six line patterns, respectively.&apos;-4 More than one type of interaction has been reported in certain metallurgical phases thus far studied by this method. Isomer shift is the experimentally measured displacement of line position from some arbitrarily defined reference position. In the case of a multiline pattern, isomer shift is given by the displacement of the centroid (center of gravity) of that pattern from the reference position. All isomer shifts measured at finite temperatures contain a second-order Doppler effect characteristic of that temperature. The isomer shift is related to the total s electron density at the nucleus, becoming more negative with increasing s electron density. The first-order quadrupole effect arises from the interaction between the nuclear quadrupole moment and any axially symmetric electric field gradient in

Jan 1, 1969

By G. Baralis, P. Gondi, I. Tangerini, G. Scandola

The precipitation behavior of Zn-0.5 pct A1 alloy single crystals was studied by means of electrical resistivity measurements and by optical and electron microscopy. The single crystals for the resistivity measurements were prepared by an original method in - 100-p -thick sheets. The order of the precipitation kinetics ranged between 1 and 1.5. The dislocations play a relevant role in the first-order kinetics. Precipitation always occurs both on dispersed particles and on dislocations. Statistical examinations have shown that the first-order kinetics can have two different activation energies; i.e., the precipitation can have dz;fferent mechanisnrs which could not be identified, however, in the course of the research. During the tnetallographic exanzination of the precipitation structures a specific process of dislocation decoration was obsereed. The main purpose of this work was to study the contribution of dislocations to the precipitation. A number of authors have observed precipitation on dislocations and reference might be made to several monographs on the ubject.&apos;&apos; The possibility that dislocations also accelerate precipitation has been considered by Turn-bull3 and Fischer et al.4 The studies described in the present paper were carried out on zinc, chosen as a base metal owing to the ease with which dislocations can be introduced into it and because of the absence of excess vacancies after quenching in conditions where phenomena of accelerated precipitation still occur. Aluminum was preferred as alloying element because of the accelerated precipitation phenomena that resulted in a preliminary reearch. EXPERIMENTAL METHODS The observations refer to a Zn-0.5 pct A1 alloy. The zinc was 99.995 pct pure; a typical spectroscopical analysis is given in Table I. As a rule the alloy was subjected to homogenization, quenching, or slow cooling and annealing. Homogenization was carried out by heating at 390" to 410°C for 24 hr. From the homogenization temperature, some specimens were quenched and some slowly cooled at a rate of 2°C per sec. At this rate no precipitate was detectable under the optical microscope just after cooling. Quenching was carried out simply by dropping the specimens into water, aqueous ethylene glycol solution at -30" c, or liquid-nitrogen baths placed close to the homogenization oven. Vaseline oil baths were used with a thermal stabilization of 10-20 for both the aging treatments and the measurements; aging was generally carried out at 90" or 130°C. To avoid oxidation phenomena during heating, the vaseline oil baths had to be frequently renewed. The precipitation kinetics were studied by means of electrical resistivity measurements, using ans potentiometric method (reproducibility ± 5 x 10 5 v, that is 0.5 pct of the total voltage decreases on the specimens during precipitation). First, various types of specimens were tested, i.e., polycrystals, single crystals grown in capillary quartz tubes, and thin single-crystal sheets prepared by means of an original method requiring no container except for the natural oxide. Even if fully annealed, the polycrystals and the capillary grown single crystals showed resistivity in -creases, most probably due to dislocations introduced in the course of the measurements. Similar resistivity increases in pure zinc were noticed by another author. Only the single-crystal sheets showed no resistivity change; thus they were chosen for the subsequent tests. As already mentioned, these single crystals were obtained by using, as a container, the natural oxide on the zinc surface; the oxide strength is sufficient to maintain the original shape during melting with sheets up to 500 p thick. An initial zone melting and subsequent zone leveling, which led also to formation of the single crystals, were thus carried out on rolled sheets of the required thicknesses (- 100 p) and shape, lying on a flat silica surface. The resistivities were first evaluated by measurements at the liquid-nitrogen temperature. This method gave poor reproducibility, however, and this was attributed to the thermal cycles which had to be operated. To avoid cycles and handling, it was therefore decided to make measurements directly in the annealing oil baths; this required thermal stabilization at ilo-&apos; "C. In this way only the resistance changes were measured. Specimens of pure zinc and of completely annealed alloy were always examined as controls together with those under consideration; only those measurement runs were taken into account where the reference samples showed no resistance increases. Again, the main inconvenience was due to oxidation and this was avoided by renewing the oil baths; even so data reproducibility was poor and the observations were therefore carried out on a large number (many hundreds) of specimens so as to provide indications of statistical value. For the transmission observations under the elec-

Jan 1, 1969

By Elwood G. Haney, R. N. Parkins

Stress corrosion cracking of two heats of 18 pct Ni maraging steel in rod form immersed in an aqueous solution of 0.6N NaCl at pH 2.2 has been studied on un-notched specimens stressed in a hard tensilf machite. Austenitizing temperature in the range 1830 to 1400 F has been shown to have a marked influence on the propensity to crack, the loulest austenitizing- temperature producing the greatest resistance to failure. In the nzosl susceptible conditions, the cracks followed the original austenile grain boundaries; but when tlze steels zcere heal treated to inproze their resistance to stress corrosion, the cracks becatne appreciably less branched and slzouqed significant tendencies to become trans granular. Electron metallography of the steels indicated the presence of snzall particles, possibly of titanium carbide, along- the prior austenite grain boundaries and these particles u:ere more readily detectable in the structures that were most susceptible to cracking. Crack propagation rates, which appeared to be dependent upon applied stress and structure, were usually in tlze reg-ion of 0.5 mm per hr and may, therefore, be e.xplained on tlze basis of a purely electrochetnical ,nechanism. However, there is some ezliderzce from fractography that crack extension may be assisted by ttlechanical processes. Anodic stit)zulation reduced the tiwe to fracture, although cathodic currents of small magnitudes delayed cracking-; further increase in cathodic current resulted in a sharp drop i,n fracture litne, possibly due to the onset of hydrogen ewbrittlement. THE use of the high strength maraging steels, with their attractive fracture toughness characteristics, is restricted because of their susceptibility to stress corrosion cracking in chloride solutions. Although this limitation has resulted in investigations of the stress corrosion susceptibilities of these steels, there have been few systematic studies aimed at defining the various parameters that determine the level of susceptibility. It is the case that the usual tests have been performed with the object of defining some stress or time limit, on unnotched or precracked specimens, within which failure was not observed,&apos; but while such results may be of some use in design considerations, they are necessarily concerned only with the steels as they currently exist and not with their improvement to render them more resistant to stress corrosion failure. This omission may be considered unfortunate because the indications are that stress corrosion in maraging steels shows dependence on structure in following an intergranular path, and since experience with other systems of intergranular stress corrosion crack- ing is that susceptibility may be varied by modifying heat treatments, a similar effect may be expected with maraging steels. It is sometimes from such observations that a fuller understanding of the mechanism of stress corrosion crack propagation begins to emerge, leading in time to the development of more resistant grades of material. The present work was undertaken to study only one aspect of the influence of heat treatment upon the cracking propensities of the 18 pct Ni maraging steel, namely the effect of austenitizing temperature, although certain ancillary measurements and experiments have been undertaken. EXPERIMENTAL TECHNIQUES Most of the measurements were made on a steel, A, having the analysis shown below, although a few results were obtained on a steel, B, having a slightly different composition. Both steels were supplied in the austenitized condition, A as 3/8-in-diam rod and B as 1/2-in.-diam rod. Cylindrical tensile test pieces were machined from the rods: the overal length was 2 1/2 in., the gage length 1 in. and the diameter 0.128 to 0.136 in. The stress corrosion tests were carried out with the specimens strained in tension in a hard beam testing machine, the necessary total strain being applied to the specimen over a period of about 30 sec, after which the moving crosshead was locked in position and the load allowed to relax as crack propagation proceeded; the load relaxation was recorded. The load was applied after the specimen had been brought into contact with the corrosive solution, the latter being contained in a polyethylene dish having a central hole through which the specimen passed, leakage being prevented by the application of a film of rubber cement. The specimen was in contact with the solution for over half of its gage length and the solution was exposed to the air during testing. The solution was prepared from distilled and deionized water to which NaCl was added, 0.6N, and the pH adjusted to 2.2 by HCl additions. The composition of the solution

Jan 1, 1969

By N. F. Dyson, T. R. Scott

The iilzfluence of catalytic agents on the oxidation of ZnS has been studied under pressure leaching conditions, using a chemically prepared sample of ZnS which was substantially unreactive on heating at 113°C with dilute sulfuric acid and 250 psi oxygen. Nurnerous prospective catalysts were added at the ratio of 0.024 mole per mole ZnS in the above reaction but pvonounced catalytic activity was confined to copper, bismuth, rutheniuwl, molybdenum, and iron in order of. decreasing effectiveness. In the absence of acid, where sulfate was the sole product of oxidation, catalysis was exhibited by copper and ruthenium only. Parameters affecting the oxidation rate were catalyst concentration, temperature, time, oxygen pressure, and a7riount of acid, the first two being most important. The main product of oxidation in the acid reaction was sulfur, with trinor amounts of sulfate. An electrochemical (galvanic) mechanism has been suggested for the sulfuv-forming reaction, whereby the relatively inert ZnS is "activated" by incorporation of catalyst ions in the lattice and the same catalysts subsequently accelerate the reduction of dissolved oxygen at cathodic sites on the ZnS surface. Insufficient data was obtained to Provide a detailed mechanism for sulfate fornzation, which is favored at low acidities and probably proceeds th&apos;rough intermediate transient species not identified in the preseni work. THE oxidation of zinc sulfide at elevated temperatures and pressures takes place according to the following simplified reactions: ZnS + io2 + H2SO4 — ZnSO4 + SG + HsO [i] ZnS + 20,-ZSO [21 In dilute acid both reactions occur but Reaction [I] is usually predominant, whereas in the absence of acid only Reaction [2] can be observed. Both proceed very slowly with chemically pure zinc sulfide but can be greatly accelerated by the addition of suitable catalysts, as suggested by jorling&apos; in 1954. Nevertheless, an initial success in the pressure leaching of zinc concentrates was achieved by Forward and veltman2 without any deliberate addition of catalytic agents and it was only later that the catalytic role of iron, present in concentrates both as (ZnFe)S and as impurities, was recognized and eventually patented.3 It is now apparent that another catalyst, uiz., copper, may have also played a part in the successful extraction of zinc, since copper sulfate is almost universally used as an activator in the flotation of sphalerite and can be adsorbed on the mineral surface in sufficient amount The importance of catalysis in oxidation-reduction reactions such as those cited above has been emphasized by various writers and Halpern4 sums up the situation when he writes that "there is good reason to believe that such ions (e.g., Cu) may exert an important catalytic influence on the various homogeneous and heterogeneous reactions which occur during leaching, particularly of sulfides, thus affecting not only the leaching rates but also the nature of the final products." Nevertheless relatively little work has appeared on this topic, one of the main reasons being that sufficiently pure samples of sulfide minerals are difficult to prepare or obtain. When it is realized that 1 part Cu in 2000 parts of ZnS is sufficient to exert a pronounced catalytic effect, the magnitude of the purity problem is evident. An incentive to undertake the present work was that an adequate supply of "pure" zinc sulfide became available. When preliminary tests established that the material, despite its large surface area, was substantially unreactive under pressure leaching conditions, the inference was made that it was sufficiently free from catalytic impurities to be suitable for studies in which known amounts of potential catalytic agents could be added. The first objective in the following work was to identify those ions or compounds which accelerate the reaction rate and, for practical reasons, to determine the effects of parameters such as amgunt of catalyst, temperature, time, acid concentration, and oxygen pressure. The second and ultimately the more important objective was to make use of the experimental results to further our knowledge of the reaction mechanisms occurring under pressure leaching conditions. The fact that catalysts can dramatically increase the reaction rate suggests that physical factors such as absorption of gaseous oxygen, transport of reactants and products, and so forth, are not of major importance under the experimental conditions employed and an opportunity is thereby provided to concentrate on the heterogeneous reaction on the surface of the sulfide particles. As will appear in the sequel, the first of these objectives has been achieved in a semiquantitative fashion but a great deal still remains to be clarified in the field of reaction mechanisms. EXPERIMENTAL a) Materials. The white zinc sulfide used was a chemically prepared "Laboratory Reagent" material (B.D.H.) and X-ray diffraction tests showed it to contain both sphalerite and wurtzite. The specific surface area, measured by argon absorption at 77"K, varied between 3.9 and 4.6 sq m per g. Analysis gave 65.0 pct Zn (67.1 pct theory) and 31.9 pct S (32.9 pct theory). Other metallic sulfides (CdS, FeS, and so forth) used in the experiments were also chemical preparations of "Laboratory Reagent" grade. Samples of mar ma-

Jan 1, 1969

By C. E. Richards, C. N. Reid

The influence of preferred orientation on the incidence of defbrtnation tuinning has been studied. High-purity iron with almost vandonz grain orientation was cotnpared uitll iron of the sa)ne grain size and composilion lza,ing a strong (110) fiber texture. As expected from published work on single crgslfls, /he ))lean stress for the onset of luitzning-, and the l,olu)nt. fraclion of twinned nzaterial obserlled in lension differed fron the 1-a1ue.s it2 co?nPression for tnolerial with a slrong texlure. The llinning stress of "rctndorrl " )zalerial did not 17ary with the sense of the aPPlied unin.via1 stress, but sirprisinglg the incidence of 1c)i)zning- was about three 1i))zes greater ill conzp?&apos;ession Illon in lension. These results (Ire attributed entirely to ovienbation and may be nderslood in ler?ns of the shear slresses acting on the allowed twinning syster)is. J. HE twins most commonly formed in bcc metals may be described as regions of the crystal in which a particular set of (112) planes is homogeneously sheared by 0.707 in the appropriate ( 111) direction. A similar twin-related crystal could be produced by a shear of 1.414 in the reverse (111) direction but twinning by this large displacement has never been reported. Thus, twinning is unidirectional and a shear stress which produces twinning does not do so when its sense is reversed. The sense of a shear Stress is reversed when the loading is changed from tension to compression, or vice versa. Consequently, for a given orientation of a crystal relative to a uniaxial stress, only a fraction of the twelve (112) twinning systems are geometrically capable of operating in tension, and the remaining systems may operate only in compression. Therefore, when twinning is involved, there are expected to be differences in behavior between crystals tested in uniaxial tension and those tested in compression. This has been verified experimentally by Reid et 01.&apos; and Sherwood el al.,&apos; although a critical stress criterion was not encountered. Furthermore, twinning stresses in colmbium," tungten, tantalum,&apos; irn,&apos; i-Fe,\ nd molybdenum7 single crystals have been shown to depend critically on orientation, although again twinning did not occur at a critical value of the macroscopic shear stress. However, when twinning occurs, it generally does so on the most highly stressed systems, 1--4&apos;6&apos;8&apos;9 implying that the stress level does have some relevance to twin formation. In view of the large orientation dependence of twinning in bee single crystals, it might be expected that such an effect would be present in poly crystalline material which possesses a recrystallisation texture. Indeed, riestner" showed that the twinning stress in tension is very orientation-sensitive it1 <&apos;grain-oriented, silicon-iron;" this material possessed a very strong t c m^ii a nnr x_____k . i-_ii__ ri_______j. _x r»i_._:__i preferred orientation obtained by secondary recrystallisation. Reid et a/.&apos; observed a marked difference in the tensile and compressive yield stresses of polycrys-talline columbium which was rationalised in terms of the effect of a preferred orientation on twinning. No other such illformation is known to the authors. Several investigations of twinning in polycrystalline bcc metals have been reported in which the possible existence of a preferred orientation was not even mentioned. It is the purpose of this paper to show that there is a strong effect of texture on twinning in polycrystalline iron, and to poilt out the difficulty in eliminating preferred orientation in recrystallised metals. 1. EXPERIMENTAL METHOD Material and Specimen Preparation. Low-carbon, high-purity iron was obtained from the National Physical Laboratory in the form of $-in. diam rod which had been cold-swaged from a diam of 1 in. The composition of the material is given in Table I. The as-received bar was cold-swaged directly to 0.185 in. diam from which cylindrical tensile and compression specimens were machined. Specimen geometry is illustrated in Fig. 1. The gage length was 0.30 in. long and 0.10 in. diam; it should be noted that, apart from the extra heads which are necessary for tensile loading, the geometry and dimensions of the two types of specimen are identical. The specimens were heat treated either by sequence A or B outlined in Table 11. The essential difference between these two treatments is that in one case the material was repeatedly cycled through the y- to a-phase change in order to produce grains of almost random orientation ("random" iron)

Jan 1, 1969

By M. Gell, G. R. Leveran

The high- and low-cycle fatigue properties of the nickel-base superalloy, Mar-MBOO, in columnar-grained and single-crystal forms were determined at room temperature. It was found that the fatigue lives of these materials were greatly affected by the size of preexisting cracks in MC-type carbides contained in the micro structure. Most of the data falls on two curves given by: (zN)&apos;/A€= K, where Nf is the number of cycles to failure, Af is the total strain range, and K is a function of carbide size. No difference was observed in the fatigue behavior of the columnar-grained and single-crystal materials for the same MC carbide size. Matrix slip and crack initiation occurred at precracked MC carbides and, to a lesser extent, at micropores. Fatigue crack propagation was mainly in the Stage I mode, i.e., on cry stallo graPhic slip planes. The Stage I fracture in these materials was unusual in that distinct features were observed on the fracture surfaces. In high-cycle fatigue, these features resembled those commonly observed on the cleavage fracture surfaces of bcc and hcp materials. Yet, in this study, the cracks propagated slowly in a cyclic manner. In low-cycle fatigue, the Stage I facets contained equiaxed dimples, similar to those observed on the tensile fracture surfaces of ductile materials. These observations indicate that both local normal and shear stresses are involved in these Stage I fractures. A model is proposed to explain these results based on the weakening of the cohesive energy of the active slip planes by reversed shear deformation and the fracture of the bonds across the weakened planes by the local normal stress. RECENT developments in casting technology have produced cast nickel-base superalloys in columnar -grained and single-crystal forms.1&apos;2 The tensile and creep properties of the nickel-base superalloy, Mar-M200, cast in these forms have been shown to be superior to the corresponding properties of the conventionally cast polycrystalline material.lp2 This improvement in properties results, in part, from the elimination of grain boundaries in the single crystals and the alignment of the grain boundaries parallel to the stress axis in the columnar-grained castings. As part of a program to evaluate the fatigue properties of nickel-base superalloys cast in single-crystal and columnar-grained forms, a study has been made of the cyclic deformation and fracture of Mar-M2OO at room temperature. M. fiFl I .hininr Mpmher AIMF ic ^pninr Rocoarrh Accn^iata anH I) EXPERIMENTAL PROCEDURE The composition range of Mar-Ma00 in weight percent is: 8 to 10 Cr, 9 to 11 Co, 11.5 to 13.5 W, 0.75 to 1.25 Cb, 1.75 to 2.25 Ti, 4.75 to 5.25 Al, 0.01 to 0.02 B, 0.03 to 0.08 Zr, 0.07 to 0.12 C, bal. Ni. All of the castings met the above specifications. The castings were solutionized for 1 to 4 hr at 2250°F followed by aging at 1600°F for 32 hr which resulted in a 0.2 pct offset yield stress of 150,000 psi at room temperature. The microstructure of the material consisted of cuboidal, coherent particles of ordered, fcc Ni3(A1,Ti) (commonly designated y&apos;), approximately 0.3 p on edge, distributed in an fcc y solid-solution matrix. MC carbides together with shrinkage and gas micropores were also distributed throughout the materials. The MC carbides and micropores were located preferentially in the interdendritic interstices, as well as in the grain boundaries in the columnar-grained castings. The (100) direction of all the single crystals and the common (100) axis of the grains in the columnar materials were aligned within about 5 deg of the specimen axis. Fatigue testing was carried out in the high-cycle (HCF) and low-cycle (LCF) fatigue regions, with the major difference being gross yielding of the specimen occurred during the first cycle in the LCF region. This division also corresponded with the more usual one in which the life of a specimen in LCF is less than lo4 cycles and that in HCF is greater than lo4 cycles. The designs of the high-cycle fatigue and low-cycle fatigue specimens are shown in Figs. l(a) and (c), respectively. The gage sections of both HCF and LCF specimens were electropolished prior to testing. The HCF specimens were tested in an MTS, closed-loop, hydraulic fatigue machine at 10 cps in air. The specimens were cycled between a tensile stress of 5000 psi and a maximum tensile stress which ranged from 35,000 to 125,000 psi, Fig. l(b). The LCF specimens were cycled under strain control from zero to a maximum tensile strain, Fig. l(d), in a Wiedemann-Baldwin testing machine. The experimental procedure has been described elsewhere.3&apos;4 Both HCF and LCF tests were interrupted periodically in order to replicate the development of slip and cracking at the specimen surface. This was accomplished by placing plastic replicating tape around the gage section of the specimen while the specimen was in the mahine. The size of the MC carbides for all specimens was measured on a polished longitudinal section through the gage section after fatigue testing. The method of measurement consisted of carefully scanning the entire polished section in order to locate the largest MC carbides. Photographs were then taken of the six longest carbides oriented approximately normal to the

Jan 1, 1969

By G. P. Airey, R. F. Mehl, T. A. Hughes

The coarsening of cementite particles in a ferrite matrix has been studied in a series of steels with 0.15 pct C only and 0.15 pct C plus 1 pct Ni, Mn, and Cr, respectively. Two initial states were employed: quenched nartensite, and quenched and cold-rolled martensite. A series of tempering temperatures between 500&apos; and 700" and tempering times of up to 190 hr were used. The structures were studied by replica and transmission electron microscopy. Particle size distribution curves were determined. From the average size value coarsening curves were obtained. These were plotted in accordance with the Wagner analysis assuming diffusion control. A discussion of the significance of the results is given. L HE reactions occuring upon the tempering of martensite have long engaged the attention of metallurgists. The latter stages, when cementite particles coarsen in a ferrite matrix, have been studied both qualitatively and quantitatively. Studies of such coarsening processes have recently been spurred by the publication of the Lifshitz-Wagner theory1, and the extension of this to the a Fe-Fe3C system by Oriani3 and by Li, Blakely, and einold. Following Wagner the coarsening process is often designated as "Ostwald Ripening". The only quantitative data on the rate of coarsening, except for the work of Hyam and uttin,&apos; in the a Fe-Fe3C system are those of Bannyh, Modin, and odin&apos; for a commercial eutectoid steel and those of Heckel and ereorio" using a pure eutectoid steel. The data of Bannyh, Modin, and Modin have been employed by 0riani3 to derive the a Fe-FeE interface energy. The reaction is one of the most important ones in steel and is worthy of detailed study. This is the purpose of the present study. Laboratory heats were prepared; these were steels with approximately 0.15 pct C, selected so that the num ber of carbide particles would be relatively small and thus so that the overlapping diffusion fluxes would be minimized, presumably a desirable circumstance.&apos;-3 In addition to Fe-C alloys, comparable heats containing 1 pct of Ni, Mn, and Cr, respectively, were included with a view of appraising the effect of alloying elements. This report includes an account of the micro-structures observed, primarily with the electron microscope, and of kinetic data and their interpretation. MATERIALS AND TREATMENT The alloys were prepared from electrolytic iron ("Plastiron") and high-purity graphite; these were melted in a zirconia crucible using a vacuum furnace. The alloy steels were made by adding electrolytic nickel, electrolytic manganese, and "vacuum grade" chromium, respectively, under a partial pressure of argon. Each melt was poured into a mold within the vacuum furnace and cooled in the mold. The ingots were 2 in. in diam. and 8 to 10 in. long. The analysis of the alloys is given in Table I. These ingots were hot-rolled to strip 0.1 in. thick, then cold-rolled to 0.05 in. and each alloy split into two batches. One batch was austenitized at 1200 for 1 min, quenched in cold brine, then cold-rolled to 0.02 in.; samples given this treatment are hereinafter designated as "worked". The other batch was cold-rolled to 0.025 in., austenitized at 1200" for 1 min, and quenched in cold brine; such samples are hereinafter designated as "quenched". These two batches were then tempered, as below. The purpose of the treatment given the first batch was to provide an initial structure of cold-worked martensite, with the expectation that the additional defect structure created by cold work would encourage a higher rate of nucleation of cementite on tempering and hence a more uniform distribution of cementite particles. Individual specimens were sealed in evacuated quartz or Pyrex tubes, then tempered in a muffle furnace. The temperature control was better than 3&apos;C at 700. Tempering treatments wer: performed at 400°, 500°, 550°, 600°, 65o°, and 700C for time periods between 15 min and 190 hr. PREPARATION OF SPECIMENS Specimens for optical and replicalelectron microscopy were mounted, polished conventionally, and etched with 2 pct nital. For electron microscopy, single-stage "formvar" replicas were made, dry-stripped and rotary-shadowed with chromium at an angle of 30 deg. Carbide extraction replicas were prepared from electropolished specimens usirig the method described by Smith and uttin.&apos; Thin foils for electron transmission microscopy were prepared by chemical thinning in an H202-HF bath prior to electropolishing in a chromium trioxide-acetic acid solution. The most

Jan 1, 1969

By A. J. Mortlock

Cobalt and nickel have been diffused at tracer concentrations in gold at several temperatures in the range from approximately 700° to 950°C. The diffusion penetration profiles were determined by a serial sectioning technique in which the gold is first anodized and then the anodic layer is dissolved in acid. In this ulay sections as thin as 250A could be removed reproduci-bly. In all cases, the region close to the specimen surface was characterized by irregular behavior in the sense that the logarithm of concentration was not linear in the square of the penetration distance. In sotne cases, there zuas an indication of the operation of very slow dijfusion in this region, while in others the apparent diffusion coejj&apos;icient was negative. Possible reasons for this anomalous behavior are briefly discussed. In recent years it has been found that the region close to the surface of a metal can sometimes exhibit anomalously slow diffusion characteristics relative to the interior of the metal. One of the best examples of this fact is the work of Styris and omizuka,&apos; who showed that the apparent diffusion coefficient for zinc in the region withi: about 1 p of the free surface of copper was about ,,,, that at deeper penetrations. This result is particularly interesting, because it is free from the possibly complicating effects of low solubility of the diffusing tracer in the solvent metal. In the case of diffusion under conditions of low solubilitjr, interpretaticn of the results in terms of lattice diffusion is difficult because of the enhanced short-circuiting produced by segregation to dislocations.2&apos;3 Measurements by Duhl et 1. suggest that cobalt diffusing in gold may also show a near-surface effect of this type. Once again the solubility is high, so that this result could be of great interest. However, the technique used for analyzing the diffusion penetration zones by Duhl, viz. the counting of residual gamma activity in the specimen following sectioning, appears to have indicated a near-surface effect in a parallel experiment on the self-diffusion of gold reported at the same time. The latter result is known to be spurious, since Kidson5 has demonstrated that self-diffusion in gold does not show this effect. Duhl et 01. also reported some measurements on the diffusion of nickel in gold, but failed to give any data for the near-surface region. As the solubility of nickel in gold is high, such data would also be of special interest. We, therefore, decided to conduct another set of experiments on the diffusion of nickel and cobalt in gold, using a sectioning technique that allows the individual sections to be assayed for solute content and thus gives direct determinations of penetration profiles. Also, by sectioning with an anodizing/stripping tech- nique, very thin layers can be removed and the region close to the surface studied in detail. MATERIALS The gold specimens were supplied as single crystal disks $ in. in diam by a in. high by Monocrystals Co. of Cleveland, Ohio. The gold itself was of spectro-scopic purity, i.e., better than 99.99 pct pure. METHOD Specimen Preparation. One flat end face of each gold crystal was spark planed with a Servomet spark erosion machine set for minimum spark energy. Following this treatment the crystals were preannealed for 2 to 4 days at temperatures of either 400" or 700°C. The three crystals preannealed at 700°C showed signs of recrystallization. The spark-planed end face of each crystal was then coated with the appropriate amount of 63i or 60 radioactive tracer. This deposit was laid down in a simple plating bath containing the as-supplied solution of the radioactive isotope as well as sufficient ammonium oxalate to saturate the solution. Some ammonium oxalate remained undissolved on the floor of the bath for this purpose. During plating further additions of ammonium oxalate were sometimes required to allow the plating to continue satisfactorily, perhaps due to passivation of the undissolved oxalate already present. The thickness of the deposited layer was determined by comparison of the apparent surface activity of the plated specimen with that of a similar specimen having a weighable deposit of the isotope on its end face. Correction for self-absorption of the radiation was made in this calculation. Annealing. The deposited crystals were annealed in a hydrogen atmosphere in sealed silica tubes. During this heat treatment they were supported, active face down, on optically flat silica plates. The temperature was measured with calibrated Pt vs Pt-10 pct Rh thermocouples, and the tabulated values can be taken to be correct to Z°C. All the crystals showed evidence of recrystallization following these heat treatments, suggesting that initially they may not have been good single crystals or had suffered strain during delivery. Concentration Profile Analysis. After annealing, the crystals were sectioned by the anodizing-stripping technique.6 The anodizing involved suspension of the specimen with its cylindrical axis horiz6ntal by a gold wire in a 200-ml beaker containing 1 M Hg304. A cathode in the form of a strip of gold sheet, 2 in. wide and positioned to be in contact with the curved side of the beaker, completely encircled the specimen. An anodizing current of 30 ma, corresponding to a current density of 5 ma per sq cm on the surface of the specimen, was passed for times ranging from 5 to 150 min depending on the thickness of gold to be removed; the solution was stirred continuously during this process. Following this treatment, the specimen

Jan 1, 1969

By D. Mills, G. B. Craig

The defortnaliotz of zirconicltt single crystals conlaining osygen in the range 740 to 6800 atom parts per nilllion was esanined oc7er the range 77" to 950°K. An anctlsis of the dqfarmaliotz parameters leads to the cotcllsiotr that the rale -cotzfrolling thermally activated dqivr,irrtion process oe-r /he range 77" to 560°K is oc.crco,ling osvgen alotns. A thermally actitaled defor,ilntion process is not found between 600" and 800", but does occur aboz%e 800°K. THE present investigation was undertaken to measure the effects of controlled amounts of oxygen on the deformation parameters of a zirconium single crystals over the temperature range 77" to 950°K and to determine the rate-controlling mechanisms. Although there is no doubt that the mechanical properties of the group IV metals, titanium, zirconium, and hafnium, are strongly influenced by the interstitial impurities oxygen, nitrogen, carbon, and hydrogen, there are many conflicting theories as to the role played by the interstitials during the deformation proess.&apos;- There is general agreement that the mechanisms which control plastic flow in a metal impose characteristic values on such parameters as the flow stress and its temperature dependence, the activation volume, and the activation energies. These parameters will be used to analyze the deformation mechanisms. eltham,&apos; Sargent,16 and ibbs&apos; have shown that the stress relaxation technique allows the activation volume characteristic of the deformation process to be found during the course of a simple tension test. In many cases it is found that the relaxation of stress is logarithmic with time and obeys a relationship of the following form: T-T = AT =S logl0(qt + C) [I] where t, is the shear stress at the start of the relaxation test, t is the shear stress at time t, and S. q, and C are experimental constants, and S is the strain rate sensitivity of the stress t as shown in the appendix. The slope found from a semilogarithmic plot of At vs time is approximately equal to S. The activation volume u, association with the deformation process, is found from the following relationship: The theoretical treatment of thermally activated plastic flow due to schoeck18 shows that the activation volume when combined with the temperature dependence of the flow stress gives the activation energy for the process according to equations: seegerZ3 considers that the flow stress at lower temperatures ld is composed of two parts such that Tapplied = tinternal + Teffective , where Teffective 3 ff , is the stress necessary to overcome the local obstacles to deformation and Tinternal, ri, is the stress necessary to overcome the long-range elastic stress field of dislocations on other planes. ri is considered to be largely elastic in origin and can be estimated from the stress value at the temperature independent portion of the flow stress-temperature curve. EXPERIMENTAL The crystal bar zirconium used in this investigation was supplied by Wah Chang Corp. whose certified analysis gave the following impurity contents in parts per million by weight: oxygen, 150; nitrogen, 10; iron, 180. All others were less than 100 ppm. The oxygen and iron contents were confirmed by neutron activation and chemical analyses, respectively. Single crystals were grown in an electron beam furnace according to the method of Wilson and Pickle-simer&apos;&apos; and ills.&apos;&apos; The orientation of the crystals was such that the specimen axes were located in the lower third of the standard section of the basal plane stereographic projection for zirconium. This orienta-

Jan 1, 1969

By E. Miller, K. L. Komarek, M. Ettenberg

The activity of aluminum in solid Co-A1 alloys has been measured by an isopiestic technique between 850° and 1200°C from 45 to 80 at. pct Al. The activity shows a Precipitous decrease around the stoichzornetric composition of CoAl. Free energies of mixing have been calculated over a limited composition range. Considering an antistructure-vacancy defect mechanism, the degree of intrinsic disorder, a , in CoAl was related to the alunminum activity. Excellent agreement between the calculated and experimental activity curves was obtained for a = 1.25 x 10-4. ThERMODYNAMIC properties of solid aluminum-transition metal alloy are being studied in an investigation of disordering in ordered compounds. In a continuing series of investigations, activities of solid Fe-1,&apos; Ni-A1, kd r-A13 alloys have been measured. From the results for Fe-A1 and Ni-A1, the degree of intrinsic disorder for the equiatomic compounds was calculated2 using equations derived by Wagner and chottk. From the results for Cr-A1 the degree of intrinsic disorder was calculated from equations derived by Orr.&apos; In this paper, the results of the study of Co-A1 alloys are described. Published activity data in the Co-A1 system has been limited to liquid alloys at 1600°C.° A heat capacity study7 of stoichiometric CoAl indicated that a second-order phase transformation occurs at 790° C, attributed to an order-disorder reaction. Oelsen and Middel,&apos; employing the calorimetric mixing of pure liquid metals, obtained heats of formation for compositions from 6 to 90 at. pct Co. Heats of formation for 50 and 78 at. pct Co alloys have also been measured by acid solution calrimetr. The Co-A1 phase diagram, as compiled by Hansen and Anderko,lo is in good agreement with more recent X-ray evidence. The method for measuring activities of aluminum in this study is essentially that employed in the studies of the Fe-1,&apos; i-Al, and r-A13 systems. This isopiestic method entails placing cobalt specimens, in a temperature gradient, in a sealed alumina system containing a pure liquid aluminum source of fixed vapor pressure. The specimens are equilibrated, cooled to room temperature, and their final compositions determined. From the measured temperature of the specimens and the known vapor pressure of pure aluminum the activities of aluminum in the alloy can be calculated. EXPERIMENTAL PROCEDURE The cobalt was 3-mil-thick sheet of 99.9 pct purity (herritt Gordon Mines Ltd., anada). The major impurities were 0.1 pct Ni, 0.014 pct C, 0.018 pct Fe, 0.004 pct S, and 0.005 pct Cu. The aluminum metal had a purity of 99.99 pct (Aluminum Corp. of America) and all alumina parts were 99.7 pct A1,O3 (Triangle RR Grade, Morganite Refractories, Inc.) with major impurities 0.05 pct SiOz, 0.1 pct Fe203, 0.2 pct NazO, and 0.05 pCt K20. Runs 1 to 3 were made with annular cobalt specimens (12 mm ID by 21 mm OD) punched from the sheet. The specimens were deburred and degreased in carbon tetrachloride and in acetone. The samples, each weighing about 150 mg, were then positioned along an alumina rod, a in. OD by 14 in. long, separated by alumina spacers, i in. ID by | in. OD by & in. long. The lower end of the rod was placed in a hole drilled in the center of an 80-g aluminum cylinder. This assembly was put into an alumina crucible, 1+ in. ID by 13 in. OD by 3+ in. high, and the position of each sample was measured to within 50.5 mm relative to the bottom of the crucible. An alumina tube, 28.5 mm ID by 35.5 mm OD by 14 in. long, closed at the top, was slipped over the whole assembly, so that it fitted snugly into the bottom crucible. The entire reaction assembly was tied with molybdenum wire and lowered into a mullite tube, closed at the bottom. A quartz thermocouple tube, closed at one end, containing a t/Pt-10 pct Rh thermocouple, calibrated according to the specifications of the National Bureau of standards,&apos;&apos; was placed along the reaction assembly inside the mullite tube. The temperature of each specimen could be determined by gradually raising the thermocouple and measuring the temperature gradient along the reaction assembly. The combined error in temperature measurement and sample position resulted in a total error of Q°C in the recorded temperature of each sample. The mullite tube was sealed at the top by a water-cooled brass head, connected to a conventional glass vacuum system. The aluminum reservoir is heated to its melting point sealing the alumina system containing the samples. During this process the pressure is maintained below 0.01 li Hg. During subsequent heating to establish the proper temperature gradient and throughout the entire run the pressure is maintained below 2 1 Hg by means of a two-stage mechanical pump. Equilibration runs lasted from 4 to 6 weeks and were terminated by air cooling. The temperature of the liquid aluminum reservoir was brought below its melting point in less than 20 min. For runs 4 and 5, alloy buttons with 49 and 69 at. pct A1 were prepared from the initial high-purity metals by arc melting under purified argon. The alloy buttons were comminuted to powder with an alumina mortar and pestle until the powder passed through a 400-mesh screen, particle size 0.0014 in. Portions of this powder weighing between 50 and 200 mg were placed in small alumina trays, 25 by 15 by 5 mm, which were then

Jan 1, 1969

By E. T. Turkdogan, L. S. Darken

Using the quadratic formalism, thermodynamic equations are derived for the composition dependence of the heat and entropy of mixing. The applicability of these equations is confirmed by available experimental data on the activities and heats of mixing for binary metallic systems of Group ZZB elements. In a recent paper arkeen&apos; introduced a quadratic formalism describing the composition dependence of the activity coefficient in the terminal regions of binary metallic solutions. That is, in the terminal region, which may extend to as much as 60 at. pct, the logarithm of the activity coefficient, log y,, of component 2 is a linear function of (1 - N,)&apos; where N2 is the atom fraction of component 2. Similarly, for the other component, log yl is a linear function of (1 - N,)&apos;. A number of iron-base binary liquid alloys were shown to obey this quadratic formalism. arkeen&apos; extended this formalism also to any corner of a ternary system and showed that the activity coefficients of the components 1, 2 and 3 (1 is taken as the solvent) can be represented by quadratic terms involving five parameters, four of the binaries and one for the ternary system. Numerous examples given by arkeen&apos; demonstrated the general applicability of the quadratic formalism to iron-base systems over a wide composition range. In this paper further examples are given of binary liquid systems (Group IIB elements, Zn, Cd, and Hg) and of several solid solutions, again demonstrating the appropriateness of this concept. A further purpose of this paper is to extend the quadratic formalism to the enthalpy and excess entropy of binary metallic solutions and to test the equations so found using available experimental data. QUADRATIC FORMALISM FOR HEATS AND ENTROPIES OF MIXING OF BINARY METALLIC SOLUTIONS The following equations, reproduced from Darken&apos;s paper, are for the two terminal regions of binary systems. at infinite dilution and a&apos;s are temperature dependent parameters to be determined from the experimental data. Although the quadratic formalism is an assumed representation of the data, Eqs. [I] to [4] are thermo-dynamically consistent with the Gibbs-Duhem relation and satisfy Raoult&apos;s and Henry&apos;s laws as limiting cases. As pointed out previously,&apos; the following form of the Gibbs-Duhem equation facilitates the integration in general but particularly in regions I and 11, where each of the derivatives is constant. The partial molar enthalpy of solution i, (and i; the value of i, at infinite dilution) are related to the activity coefficients y, and y," by the thermodynamic relation Differentiating Eq. [l ] with respect to 1/T and substituting the above thermodynamic relation gives for region (I) It is reasonable to assume that over a temperature range of experimental interest, the enthalpy of mixing is essentially independent of temperature, implying from Eq. [7] that the derivative da,,/d(l/) is also independent of temperature. On the basis of this argument, the temperature dependence of a has the form where £ and S have the units of enthalpy and entropy respectively; they are characteristic parameters for a terminal region of a binary system, e.g. for region (I), C12, S12 and for region (II), d:,,, S2,. Using this equation gives for dff ,/ d(l/), From Eqs. [7] and [9] an expre_ssion is obtained for the composition dependence of L,. Similar calculations are made for El and the results are summarized below for the two terminal regions. For region (I), The corresponding expressions for the molar heat of solution, AHM, are readily obtained from the above equations for the two terminal regions: For region (I),

Jan 1, 1969

By R. F. Ashton, D. S. Thompson

In reporting results of precipitation hardening experiments, it is customary to include such conditions as solution heat-treatment temperature, specimen size, and quench medium as well as the aging time and temperature. One portion of thermal history that is often overlooked is the effect of the heating rate employed to achieve the aging temperature. It is the intent of this note to demonstrate the importance of the rate of heating to aging temperatures. This work was carried out on the aluminum alloy 7075 aged at 162oC, a temperature commonly used to obtain stress corrosion resistant tempers. A 2 in. thick plate of 7075 was quenched into 24°C water after solution heat-treatment for 2 hr at 470°C. Approximately 13 in. around the periphery of the plate was discarded to minimize quench rate variations, and the remainder was divided into 0.5 by 1.8 by 2.0 in. blocks which were held at room temperature, 24oC, for 4 days. This aging, or incubation period, at room temperature allowed a copious supply of GP-zones to form. Blocks were then heated at various rates to 162oC using the practices shown in Table I. Both single- and two-step aging practices were employed for each heating rate. The single step consisted of heating directly to temperature at the indicated rate while the two-stage practice included an interruption of heating for 7 hr at 107°C. In the case of the two-stage 100°C per min heating rate experiment, the specimens were returned to room temperature after 7 hr at 107°C where they were held for 16 hr be-fore finally heating at this rate to 162°C. This devia-tion in practice is not considered to be significant. Blocks were removed after various times at 162oC, and aging curves were determined from duplicate R. F. ASHTON and D. S. THOMPSON,Member AIME, are Senior Scientists, Metallurgical Research Division, Reynolds Metals Company, Richmond. Va. Manuscript submitted December 2. 1968. IMD Table I. Aging Practices Two-step Single-Step Heating Rate* Aging Aging Heating Method oC per Min A B Programmed Air Oven 0.23 * 0.01 C D Programmed Air Oven 0.93 ? 0.03 E F Air Oven at Temp -10 G H Oil Bath at Temp ˜100 *Heating rate was measured with a thermocouple at the center of a specimen. An average value between the starting temperature and 3°C below the aging temperature is reported for practices E-H. PRACTICES 70 — A B C E and G 50 - 2 4 6 810 20 40 60 HRS.AT 162°C Fig. 1—The influence of processing variables on 7075 aging curves. Fig. 2—7075 aged according to practice H (single-step aged, fast heating rate) for 3 hr. Magnification 100,000 times.

Jan 1, 1970

By M. J. Stewart, F. Weinberg

PREVIOUS investigations into convective flow in molten metals have examined systems in which the length-to-height ratio of the enclosure is large, usually using long graphite boats.&apos;&apos;2 In normal castings this ratio is generally small and it is not possible to extrapolate the results of previous work to casting configurations. The present investigation was undertaken to examine liquid flow in systems of low length to height ratio. The apparatus used for the experiments is shown in Fig. 1. The molten zone of tin is contained in an aluminum mold of inside dimensions 6.4 by 6.4 by 0.31 cm. A heating block containing a resistance coil is attached to one end of the mold and a cooling block is attached to the other end. These are used to produce a wide range of temperature differences across the mold. The mold is contained in a stainless steel tank which is heated from the outside by resistance heaters to give the required operating temperature during the experiment. Temperature measurements in the molten tin are made with an iron-constantan thermocouple PT equal to 5 atm. The phase diagram derived by us was the same as that found by Krivsky and Schuhmann, except for a similar discrepancy in one boundary line representing the gas composition in equilibrium with SO a. The vapor pressures of the pure components can be neglected at 1700°K, 1 atm and 2500°K, 5 atm. There-fore, in these cases PT is essentially the total pres-sure in the system. This is valid for all the diagrams presented by Krivsky and Schuhmann except for the one at 2500°K and 0.01 atm, where the vapor pressure of silicon is comparable to PT.6 This work was supported in part by the American Iron and Steel Institute. &apos;C. E. Wicks and F. E. Block: Thermodynamic Properties of 65 Elements, U S. Bur Mines, Bull. No. 605, 1963. R. P. Elliott: Constitution of Binary Alloys, 1st supplementary, McGraw-Hill Book Co., New York, 1965. 3W. A. Krivsky and R. Schuhmann, Jr.: Trans. TMS-AIME, 1961, vol. 221, pp. 898-904. 4M. F. Ancey-Moret, M. Olette, and F. D. Richardson: Mem. Sci. Rev. Met., 1964, vol. 61, pp. 169-76. 5J . F. Elliott and M. Gleiser: Thermochemistry for Steelmaking, vol. 1. Addison-Wesley, Reading, Mass. 1960. 6 J.Drowart, G. De Maria, and M. G. Ingraham: J. Chem. Phys., 1958, vol. 29, p. 1015. probe of 0.4 mm diam inserted into the open top of the mold. Radioactive sn113, in the form of a small sphere, was gently lowered into the molten tin at point A in Fig. 1 THERMOCOUPLE> WATER ARGON END HEATER QUENCH ARGON Fig. 1—Apparatus for detecting liquid flow. Point A indicates position the tracer was introduced.

Jan 1, 1970