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By M. Schussler, J. S. Brunhouse

Arc-melted and electron-beam melted tantalum in the cold-worked and the recrystallized conditions showed high strength, good tensile ductility, and excellent notch toughness down to 321°F. Arc-melted material, containing moderate amounts of interstitials, possessed better short-time strength than higher purity electron-beam melted material up to 2000°F. Cold-working substantially strengthened arc-melted tantalum, whereas electron-beam melted material exhibited a low work-hardening rate and possessed better formability characteristics. With identical compositions and microstructures, the mechanical properties of melted tantalum and uacuum-sintered tantalum should be similar. TANTALUM metal usage is increasing rapidly in a number of applications. The outstanding chemical corrosion resistance of tantalum accounts for its applications in chemical processing equipment for severe service conditions and for surgical uses in the medical field. The largest present requirements for tantalum are in the electronics industry, where its special properties are useful in capacitors. The high melting point (5425°F) and inherent ductility of tantalum also suggest that tantalum and tantalum-base alloys might offer an excellent combination of high strength at very high temperatures and good fabri-cability. Pure tantalum has been used in significant amounts in parts requiring high-temperature strength, such as heating elements, reflectors, and heat shields in high-vacuum high-temperature furnaces and in electronic tubes. A few very promising tantalum-base alloys have been developed and are being investigated extensively. The possibilities for tantalum as a high-temperature structural material, either unalloyed or alloyed, will become better defined when more extensive mechanical property data are known. pughl measured the tensile properties of vacuum-sintered tantalum in sheet form for the temperature range of 78" to 1500°K (-321' to 2240°F), and Bechtold reported data obtained at low temperatures.' Drennen3 determined creep and stress-rupture properties of both vacuum-sintered and arc-melted tantalum sheet at 1200 °F. Some additional data on the mechanical properties of tantalum at temperatures up to 5000 °F have been summarized elsewhere.4'5 It is probable that large structural shapes of tantalum, either unalloyed or alloyed, can most readily be produced from ingots prepared by melting. Consequently, the present investigation was undertaken to determine more extensive short-time mechanical properties of tantalum metal consolidated by melting. EXPERIMENTAL PROCEDURE Melting and Fabrication—Two tantalum ingots were utilized in this study to obtain information on the effect of interstitial elements on mechanical properties. Both ingots were melted from Union Carbide Metals Co. tantalum dendrites.

Jan 1, 1961

By T. A. Read, H. K. Birnbaum

STRESS-induced twin boundary motion in the AuCd ß'phase (52.5 at. pct Au 47.5 at. pct Cd having an orthorhombic structure (space group D h)' was discussed for the case of transformation twins.' Mechanical twinning, i.e., introduction of new twin orientations by the applied stress was sometimes observed in the ß' phase which contained two transformation twin orientations. (See Ref. 2 for experimental details.) The transformation twins terminated at the mechanical twin boundary; the two initial orientations having been twinned to the new orientation as shown in Fig. l. In a "hard" tensile instrument, formation of each mechanical twin was accompanied by a sharp drop in load (and an audible click) resulting in a typical serrated load-extension curve. The mechanical twins increased in width and additional twins were nucleated as the load increased until the entire specimen was occupied by the mechanical twin orientation. A restoring force2 caused the mechanical twin and transformation twin boundaries to return towards their initial configuration on releasing the load. In a stabilized specimen* the total strain introduced by mechanical twinning was recovered on releasing the applied stress. Initial and final microstructures were identical. After decreasing gradually to a critical width, mechanical twins suddenly disappeared accompanied by audible clicks and sharp increases in load (measured at a constant rate of crosshead motion in a "hard" machine). Mechanical twins could be stabilized in any position by maintaining the applied load for a sufficient time, indicating a decrease in restoring force with time similar to that observed for transformation twins.' Orientation relationships for mechanical and transformation twins were determined and are shown in Fig. 2. The mechanical twin, T3, was twin related to transformation twin, T,, by reflection in (1ll), and twin related to transformation twin, T2, by reflection in (111)T, . T, was related to T, by reflection in(ll1)T1 . The "average" mechanical twin composition plane lay several degrees from (1ll), . In every specimen which mechanically twinned, orientation T3 was most highly favored by the applied stress, i.e., it was the twin orientation which provided the greatest change in length compatible with the direction of applied stress

Jan 1, 1961

By J. D. Mote, A. Rosen, J. E. Dorn

The effect of strain rate and temperature on the critical resolved shear stress for (1100) [1120] prismatic slip was determined for the intermediate hexagonal phase containing about 67 at. pct Ag and 33 at. pct Al. Whereas the flow stress increased only slightly as the test temperature was first decreased below room temperature, a rapid increase inflow stress was obtained with yet greater decreases in temperature from about 240" to 4°K. The effect of both temperature and strain rate on the flow stress over the low-temperature range could be completely rationalized in terms of the Peierls mechanism when the deformation is controlled by the rate of nucleation of pairs of kinks. A few years ago Mote, Tanaka, and Dorn1 observed that the critical resolved shear stress for prismatic slip of a 67 at. pct Ag plus 33 at. pct A1 hexagonal intermediate phase by the (1100)[1120] mode decreased precipitously as the test temperature was increased from 4" to about 160°K. Their results for both basal and prismatic slip are given in Fig. 1. It is obvious that only the flow stress for prismatic slip is strongly temperature-dependent, whereas the flow stress for basal slip is independent of temperature. If the temperature dependence of the flow stress were primarily due to interstitial impurities, it might be expected that they would influence the flow stress for basal slip as well. Since the activation volume at 115°K for prismatic slip was determined to be about 15b3, where b is the Burgers' vector, this thermally activated deformation process was tentatively ascribed as being due to the Peierls mechanism. But the various analyses of the Peierls mechanism then available as formulated by Seeger2 and also by Lothe and Hirth3 did not agree well with the experimental data. Since that time a more realistic theory for the operation of the Peierls mechanism under conditions where the strain rate is determined by the rate of nucleation of pairs of kinks has been presented by Dorn and Rajnak.4 The present investigation was, therefore, undertaken in order to provide the essential data for a careful check on the agreement between this theory and the low-temperature deformation by prismatid slip of the above-mentioned Ag2A1 intermediate phase. EXPERIMENTAL TECHNIQUE Single-crystal specimens so oriented that the [1120] direction and the normal to the (1100) plane were at 45 * 2 deg to the tensile axis were grown from the congruent melting composition of about Ag2Al for the intermediate hexagonal phase by the

Jan 1, 1964

By Nicholas J. Grant, H. C. Chang

Microscopic observations during creep tests were made on AI-20 pet Zn, 80 pet Ni-20 pet Cr, and 25 and 3S aluminum specimens. All these materials failed in an inter-crystalline manner under certain stress and temperature conditions. Particular atten-tion was given to the initiation and propagation of intercrystalline cracks in coarsegrained AI-20 pct Zn specimens. The geometry of the grains and grain boundaries in these specimens was known before the tests. On the basis of the observations and a knowledge of the interaction between grains and grain boundaries, a mechanism of intercrystalline fracture and propagation of the fracture has been proposed. METAL, and alloy fracture occurs essentially in two ways: transcrystalline and intemrystalline. In the past most of the work done in this field was centered on the determination of stress criteria for fracture. The specimens used for these studies were tested under varying conditions of stress state, temperature, and strain rate. Unfortunately, very little attention was given to the initiation and propagation of the fracture, whereas the nature of fracture was examined closely only after failure. Several extensive reviews of these studies have been published by Orowan, Smith, Barrett, and Petch.1, 4 It is well known that a material which exhibits a ductile and transcrystalline fracture can be made to exhibit a brittle and intercrystalline fracture by modifying its composition and by heat treatment. This modification may or may not result in microscopically observable precipitation in the grain boundaries." In the creep of any one alloy the transition of transcrystalline to intercrystalline fracture is a function of stress, strain rate, and temperature." The tendency for intercrystalline fracture to occur increases as the strain rate decreases and the testing temperature increases. Extensive work on high purity aluminum (99.995 pet) under creep conditions showed the importance of the interaction between grains and grain boundaries, and the different responses of grain and grain boundaries to the variables: stress, strain rate, and temperature.7, 8 It was also shown that grain boundary deformation necessarily has to be accommodated in the grains by various deformation means as. for example, fold formation. The type of fracture resulting from the creep of high purity aluminum was invariably found to be transcrystalline. On the other hand, 2S and 3s aluminum were, under certain conditions, found to fracture in an intercrystalline manner." One reason given for this was that the grains could accommodate to a lesser extent the deformation of the grain boundaries.19 It was decided to examine this line of reasoning in greater detail and to investigate the particular interactions between grains and grain boundaries that result in the incidence and progression of inter-ct,ystalline fracture. It is also the purpose of this paper to show where and how intercrystalline cracks start and how they propagate to result in fracture. Several alloys—Al-20 pct Zn, 80 pet Ni-20 pet Cr, 2S and 3s aluminum-— were used for this study, but attention was paid mainly to the behavior of an A1-20 pet Zn alloy, since its general creep behavior has been established." From the results of this study a mechanism of intercrystalline fracture is proposed. Experimental Procedure The experimental procedure was similar to that used in previous work and has been detailed elsewhere.' Two parallel flat surfaces were milled from an originally round specimen, giving a gage portion which was 1x0.09X0.17 in. Some round specimens, 1/4 in. round by 1 in., were also tested. The A1-20 pet Zn specimens. which were annealed at 1030°F for 24 hr, showed two to four grains across the width of the test bar, and most of the grains occupied the whole thickness of the specimenu. Before some of the specimens were subjected to creep, the grain arrangement was mapped out in a development drawing, Fig. 1. The initiation and

Jan 1, 1957

By J. J. Gilman

The dependence of ortho kink-band formation on crystal orientation, on temperature, and on the conditions at the ends of a specimen is described. Load-compression curves for crystals that kink are presented. The reversibility of ortho kinking is demonstrated, and motion of kink planes through crystals is shown. Finally, a phenomenological explanation of ortho kink-band formation is given. ORTHO compressive kink bands (Fig. la) were discovered for the case of metals by Orowan,1 and they have been discussed by Jillson2 and in some detail by Hess and Barrett." However, their history in nonmetallic crystals is considerably older. It is not known when they were first observed in mineral crystals, but descriptions of them may be found as early as 1885.* They were sometimes mistaken for twins.6 Mügge seems to have been first to realize their true nature and importance. He reviewed the knowledge of them for a wide variety of crystals: anhydrite, antimonite, kyanite, vivianite, gypsum, mica, graphite, molybdenite, barium bromide, cal-cite, sodium nitrate, and barite. Also, the "twins" observed by Bridgman7 in sapphire crystals resemble kink bands more than twins. The terms ortho and para kink bands have been coined in order to distinguish between two types of kink bands which seem to represent the same geometrical configurations, but which have different origins and sizes. Ortho kink bands are the usual type that form at low loads when zinc crystals are compressed parallel to the basal plane. Para kink bands form at much higher loads in highly deformed crystals. These terms refer to compression phenomena and are not to be confused with analogous tension phenomena such as tensile kink bands and deformation bands. Mügge described the geometry of ortho kink bands quite completely for kyanite crystals, Fig. lc. The geometry observed for cadmium by Orowan1 and for zinc by Hess and Barrett3 is very similar to that described by Mügge. (See Hess and Barrett for a complete discussion.) Mügge associated kinking with bending combined with basal slip. He pointed out that the kink angles

Jan 1, 1955

By F. D. Rosi

The slip and twinning behavior in extended titanium crystals were studied in some detail. The formation and appearance of coarse kink bands are discussed. Their crystallographic geometry was determined by X-ray analysis. A phenomenological interpretation of the complexities in kink band development is also presented. The critical resolved shear stress, coefficient of shear hardening, and plane of fracture were determined for several crystals extended at room temperature. THE slip and twinning elements observed in the room-temperature deformation of titanium were enumerated in a previous paper1 in which considerations were advanced regarding the nature and selection of these elements and their effect on the known mechanical properties of this metal. The present study concerns the crystallographic, microscopic, and mechanical aspects of flow in relation to the slip and twinning elements, and includes a prediction of slip systems, nature of slip and twin markings, inhomogeneities of plastic flow, and stress-strain characteristics. Unless otherwise noted, arc-melted titanium sponge (99.77 pct) was used in these experiments. The method of production of crystals, their dimensions, and the surface preparation for micrographic examination have been reported.&apos; For obtaining stress-strain characteristics, only those crystals which traversed the entire width of the specimen and were at least 8 mm in length were used. Tensile deformation of the crystals was performed with conventional grips for sheet specimens and a constant-stress loading beam, designed after the method of Andrade and Chalmers.&apos; The specimens were loaded by allowing sand to flow from a reservoir into a bucket suspended from the longer end of a balanced 6:1 lever arm at a rate controlled to load the specimen approximately 2 kg per min. Strain measurements were made using the Baldwin SR-4, bonded, resistance-wire strain gage, Type A-8, which permitted a reading accuracy of 2 microinches per inch. The formulas used in the evaluation of shear stress and shear strain, as in deriving the coefficient of shear hardening, are given by Schmid and Boasv n terms of the original orientation and change in length of the crystal. For calculating the critical resolved shear stress, the standard equation was used. The crystallographic nature of the unpredictable slip observed in a number of specimens was determined by the single-surface X-ray method of analysis as described in ref. 1. Experimental Results Prediction of Slip System: It was reported&apos; that room temperature slip in titanium takes place predominantly on {10i0} and in a <1120> direction, giving three potential slip systems. Hence, it should be possible to predict the operative primary system in the manner used by Taylor and Elam&apos; for alu- minum (i.e., the one with the greatest component of shear stress in the direction of slip). The stereo-graphic construction in Fig. 1 shows that this is true. In all cases, slip was found to occur initially on the (0110) plane and, in a number of cases, in the [21f0] direction. (The direction of slip was not determined for all orientations.) It follows that duplex slip can be expected when two slip systems are geometrically equally favorable for slip, as demonstrated in Fig. 2. In both crystals slip took place simultaneously on the (1700) and (olio) prismatic planes, as indicated by Fig. 2a and b. In the case of crystal B the movement of the specimen axis with increasing extension was toward the (10i0) direction, which represents the stable end orientation resulting from alternate slip on the [2ii0] and [1120] directions. This is analogous to the duplex slip process in face-centered cubic metals." Unpredictable Slip: In a number of crystals whose orientations were well within the operation of a single slip system, secondary slip occurred on planes not predicted by the criterion of maximum shear stress. Examples are shown in Fig. 3. In addition to

Jan 1, 1955

By G. H. Rowe, A. N. Stroh, D. P. Gregory

The magnitude and variation with strain of the parameters activation volume, V*; activation energy, H; and frequency factor, A, in the Arrhenius equation for strain rate are determined for colunlbium single crystals and polycrgstals. Comparison of dislocation structures in deformed columbium crystals as determined by transmission electron microscopy with the rate IF deformation of a metal crystal is a thermally activated process, rate theory can be used as a powerful tool in the study of dislocation mechanisms. seeger1 develops the following expression for plastic deformation governed by a single thermally-activated theory results suggests thai formation of lattice vacancies at jogs in screw dislocations is responsible for thermally activated deformation of poly crystalline columbium. Single crystals appear to deform by a different mechanism. Work hardening in fully recrystallized fine grain columbium is found to result from simultaneous decrease in activation volume and in the number of mobile dislocations with increasing strain. Work hardening in recovered polycrystals is found to result from decrease in activation volume with strain only. dislocation mechanism. His equation for strain rate is where N is the number of mobile dislocations per unit volume held up at energy barriers, v is the frequency with which the dislocations "try" the energy barriers, b is the Burgers vector, a is the area a dislocation loop sweeps out after overcoming a barrier, V* is the activation volume which will be defined more completely later, and t* is the thermal component of stress equal to (Ta-Ti), where Ta is applied shear stress and Ti is internal stress of the dislocation network17&apos; given by

Jan 1, 1963

By Bernhard Blumenthal

A melting process was developed by which high purity electrolytic uranium crystals can be converted into sound ingots without serious contamination. Careful preparation of the crystals, melting in a high vacuum, and directional solidification led to a metal of better than 99.993 wt pct purity. The metallographic examination showed a substantially clean metal with only residual amounts of a second phase which responded to heat treatment. The density of high purity uranium is 19.05 g per cu cm. FOR the study of the fundamental properties of uranium and its alloys, a base metal of high purity is needed, and an investigation was started at Argonne several years ago to examine various methods of preparing high purity uranium. Early success was achieved by the fused salt electrolysis process in preparing high purity metal in crystal form,&apos; and the problem became that of melting the crystals into ingots without contamination. The electrolytic crystals contained a few ppm of heavy metals, less than 15 ppm C, and large quantities of potassium and lithium in the form of trapped fused salt electrolyte. On melting in vacuo in magnesia or urania crucibles, the metal picked up considerable quantities of carbon and some iron, copper, and silicon but lost most of the potassium and lithium. It was not metallographically clean, and much research work was necessary to determine the optimum melting conditions for minimum contamination. This work has resulted in the development of a melting procedure by which sound ingots can be prepared with only a limited contamination by carbon. In the section entitled "Melting of the Electrolytic Metal," the equipment and processes that have been developed for melting the electrolytic crystals are described in detail. The "Metallography" section is devoted to the metallography of high purity uranium, and the section "Density of High Purity Uranium" contains the first property measurement on high purity uranium—a density determination. Melting of the Electrolytic Metal Apparatus—Melting and Vacuum Equipment: Uranium may be melted in either resistance or induction-type electric furnaces. Resistance heating was found to be preferable to induction heating for melting down the electrolytic crystals, for several reasons: Although induction heating permits fast heating, this advantage cannot be utilized when crucibles with limited thermal shock resistance are used. Temperature control of induction-heated melts is poor, and the stirring effect increases the rate of contamination of the melt from the crucible, slag, or the furnace atmosphere; liquation and controlled solidification are difficult to carry out. Because of these objections, resistance heating was chosen. A 10 kw Globar resistance furnace of low heat capacity permitted uniform heating of a uranium charge to its melting point in 45 min. The furnace was insulated with a removable aluminum shield so that, after melting and removal of the shield, the furnace could be quickly cooled to room temperature. The furnace was equipped with an apparatus for directional solidification; see Fig. la. The crucible was suspended in the center of the furnace; and when the melting was complete, the crucible was slowly lowered into the cold end of the furnace tube. Solidification took place upward from the bottom; and when the rate of lowering was small, a sound ingot free from sink holes and shrinkage cavities was produced. To remove the large quantities of gas contained in the electrolytic crystals, melting in a high vacuum is mandatory. While, from the standpoint of contamination, melting in a highly purified argon atmosphere appeared feasible, lithium and potassium removal proved less efficient under such conditions. Also, a vacuum-melted ingot has a cleaner surface than one melted in an inert atmosphere. The vacuum system must be of very high pumping speed and leak tight so that a vacuum of less than 2x10-7 mm Hg is attainable when the system is pumped down cold. The system must have a high pumping speed, so that the pressure maximum which may rise to 1x10-4 mm during heating can be quickly reduced

Jan 1, 1956

By D. K. Deardorff, Earl T. Hayes

An improved technique is described for the accurate determination of melting points of metals in the temperature range 1500&apos; to 2500°C. The improvements consist of gradient heating and refinements in cavity preparation to obtain true black-body conditions. The melting point of hafnium, as determined by this method, is set at 2222°±30°C. This is over 200°C higher than one of the values reported earlier. Discrepancies in the previously reported values for the melting point of hafnium are explained. The melting points of zirconium and titanium are found to be 1855O±15OC and 1668°±10°C, respectively. Reproducibility of results was ±3OC. PRIMARILY, this report is being made to correct a 1975o±25oC1 value for the melting point of hafnium, and to present an improved method for melting point determination. As a matter of interest, the technique was also applied to determining the melting point of zirconium and titanium. There is a wide difference in the melting point of hafnium as reported by competent investigators. DeBoer and Fast&apos; reported a value of 2230°±500C, and later work of McPherson, as reported by Aden-stedt, placed the melting point at 1975o±25oC. Zwikker" calculated that the melting point was 2430°C. In resolving this discrepancy, improvements were made in the procedure for determining the melting points of refractory metals in the range 1500" to 2500°C. Special techniques are necessary to determine the melting point of these metals accurately. Since the metals oxidize in air above 900oC, the determinations must be carried out in an inert gas or vacuum. Also, every known refractory contaminates them to some extent. In addition, the attainment of true black-body conditions is always difficult. DeBoer and Fast actually determined the melting point of Hf-Zr as-deposited iodide process alloys and extrapolated to 100 pet Hf. McPherson employed a tungsten wire suspension similar to that described by Schramm, Gordon, and Kaufmann,1 and used hafnium metal produced by the iodide process. There was no apparent reason for the wide spread in melting points, since the quality of the metal was very good and the work was under the direction of highly competent investigators. Retracing some of this work revealed one understandable error in the case of hafnium, and led to development of an improved technique for determining melting points of reactive metals in the range 1500" to 2500°C. Material Crystal bar hafnium, zirconium, and titanium were used for this work, with analyses as shown in Table I. The hafnium was of the highest purity that has been prepared, though not as pure as the zirconium and titanium. At the instigation of the Pittsburgh Area Office of the AEC, a special lot of Hfo2 was purified, converted to the tetraflouride, and bomb-reduced with calcium, all at the Iowa State College Laboratories. This crude hafnium metal was then refined by the iodide process at the Foote Mineral Co. All specimens were cut with a Sic wheel, ground, pickled, and dried carefully before use. Procedure General Tungsten Suspension Method—In this method, a small specimen is suspended by a fine tungsten wire in a slender, induction-heated tungsten or tantalum cylinder, all under vacuum. The melting point is determined by heating the specimen slowly while observing it with an optical pyrometer focused upon a portion of the specimen that radiates as a black body. This means that there should be no reflected radiation, either from colder objects near the pyrometer or from hotter surfaces. The induction heater would be the only hotter object and, if it is slender enough, the specimen will attain the same temperature. Often a slender hole is drilled into the specimen as a source of black-body radiation. This was the general method used by McPherson in obtaining his value of 1975°C for the melting point of hafnium. In trying to repeat this work, it was found that the points of contact between the

Jan 1, 1957

By W. Rostoker, H. Nichols

It has been demonstrated in previous work1&apos;2 that wetting of aluminum alloys by liquid mercury can cause fracture to occur with substantial suppression of prior plastic flow. This has been interpreted as the action of a critical liquid species in reducing the cohesive strength of a stressed solid at sites of potential crack nucleation. In this way the critical transverse stress for fracture nucleation is reached at much lower stresses than is normally the case. The stresses for both fracture nucleation and fracture propagation are depressed by the same mechanism. In so doing the plastic-energy component of fracture energy is reduced to a level which is of the same order of magnitude as the surface, interfacial, or cleavage energy. Recent work2 has illustrated the influence of dispersed precipitates, cold work, and combinations of these on brittle fracture associated with plastic strains of the microyield order of magnitude. This has been rationalized in terms of the contribution of internal microstress fields to the stress magnifications at points of obstruction of active slip bands in a stressed metal. The presently reported studies on an Al-4-1/2 pct Mg alloy amplify this subject by introducing thermal-mechanical conditions which can produce strain aging. As amply demonstrated by Phillips, Swain, and borall, the tensile behavior of aluminum alloys containing magnesium reveals a yield-point elongation and successive discontinuous elongations over the whole plastic-strain range. This gives a stepped or serrated character to the stress-strain diagram. The yield-point elongation is not temperature-dependent. On the other hand, the discontinuous extensions in the plastic-strain range are gradually suppressed by lower temperatures of testing. At -78"C, only the yield-point elongation persists. The yield-point elongation itself can be suppressed by rapid quenching to room temperature from an annealing temperature of 500°C. The argument presented by Phillips et 1. and Cottre114 is that the yield-point elongation derives from surmounting at a critical stress the restraint to slip by grain boundaries which have been reinforced by appreciable magnesium-atom segregation. The serrated character of the plastic-strain range is the result of rapid strain aging during the test. This is made possible by the inevitable proximity of magnesium atoms to any dislocation line. In the Al-4-1/2 pct Mg alloy there is one magnesium atom for every twenty-two aluminum atoms and, with a coordination number of 12, a magnesium atom is on the average only about two atomic distances from any given lattice site. Rapid strain aging is therefore a reasonable expectation. A study of mercury embrittlement of the Al-4-1/2 pct Mg alloy (commercial designation 5083) provides an opportunity to relate the interplay of grain size, grain boundary restraint to slip and strain aging in the brittle-fracture process. One lot of commercial sheet material of 0.125-in. thickness was used for all of the tests. The specimen shape and test procedures used were the same as those described in a previous publication.2 A range of grain sizes between 0.0057 and 0.0125 mm was produced by various combinations of plastic prestrain and annealing. The coarsest grain was somewhat elongated in shape. In this case the measurement was taken in the direction transverse to the axis of tension as more meaningful to a brittle-fracture process. In the annealed condition, specimens wetted with mercury failed with zero permanent elongation at stresses slightly below the normal yield point, i.e., stresses at 0.05 to 0.2 pct strain. Since this occurs before yield-point elongation can begin, fracture derives from slip contained within individual grains and restrained from propagating across grain boundaries. No significant difference in wetted fracture stress was observed between specimens which had been water-quenched or furnace-cooled from the annealing temperatures. This signifies that the degree of magnesium segregation at grain boundaries

Jan 1, 1964

By H. P. Leighly

WORNER1 briefly studied the embrittlement of titanium by mercury. He found that mercury will wet the titanium surface at 400°C in vacuo, if the specimen had been heated previously to 700°C to dissolve the oxide coating. Subsequent exposure to the atmosphere causes the mercury film to recede rapidly. Bending of the titanium specimen even after the mercury film has receded results in a brittle fracture. For the study of the embrittling effect of mercury on titanium, specimens 2 by 12 by 0.051 in. were cut from RC-130-A sheet, an alloy having a nominal 8 pct Mn content and a mixed a-ß structure. The specimens were stressed horizontally at a predetermined value after which a plastic ring having a cavity 1/2 in. diam by 1/2 in. deep was placed on the specimen. The cavity was filled with mercury and a hole was drilled in the specimen through the pool of mercury. If the stress level was high enough, fracture occurred instantaneously with the drilling. By repeating the test at different stress levels, the threshold stress can be determined. Mercury embrittlement causes a drastic reduction in the ultimate tensile strength of this alloy from 132,000 psi to about 15,700 psi. The drilling of the hole, in the absence of mercury, does not change the tensile properties. Fig. 1 shows the typical fractures observed as a result of the embrittlement of this alloy by mercury. The central portion of the fracture was brittle represented by the jagged region which appears to have occurred on the shear planes at about 45 deg to the stress axis. Ductile fracture, which is perpendicular to the stress axis, occurred near the specimen edges accompanied by a reduction of the specimen thickness. Examination of the fracture reveals that only in the brittle region does mercury wet the

Jan 1, 1962

By Irving B. Cadoff, Ernest Levine

The crack formation and propagation in the single -phase Cu-4 pct Ag alloys were studied. The alloys were loaded in mercury to various stress levels, the mercury was removed, and the specimen examined for cracks. Cracks were found to develop below the fracture stress; the frequency of such cracks increased with increasing stress level. Some cracks were nmpropagative. Fracture in mercury was found to occur by the link-up of cracks formed at various stress levels rather than by the growth and propagation of a single crack. If the mercury environment is removed prior to a critical amount of crack formation, then continued loading results in ductile fracture. The appearance of the cracks at selected grain boundaries is related to the relative orientation of the boundaries, as are the propaga-tive characteristics of the crack. The mercury interaction appears to be one of lowering the strength of the metal-metal bonds in the high-stress area of the grain boundary. GRIFFITH&apos;S microcrack theory1 proposed a critical crack size above which a crack in an elastic material grows with decreasing energy at a stress of From his theory it was proposed that the presence of a liquid tends to lower the surface energy of the microcrack faces2 leading to a decrease in the critical crack size necessary for spontaneous fracture propagation. stroh3 proposed that the stress concentration at a grain boundary due to pile-up may initiate a microcrack at the grain boundary. petch4 and Stroh5 evaluated the stress distribution at the head of a pile-up in a polycrystal-line material and deduced that the critical crack size and hence of is dependent on the grain size. Experimental verification of this dependence was found by petch6 for hydrogen embrittlement of steel. Studies in stress-corrosion cracking7 have provided a picture of fracture which shows that initial separations occur in a scattered, independent fashion in regions of high tensile stress. A minimum or threshold stress is necessary to produce a sufficient stress concentration to initiate frac- ture. These separations join up to form a crack. The extension of fracture is largely discontinuous and consists of a joining up of cracks. In recent worka evidence of this scattered crack network was found in a Cu-Ag alloy embrittled by mercury. For the Cu alloy-Hg couple, the crack path has also been found to be dependent on the orientation of adjacent grains, and with the addition of zinc to mercury a reduction in embrittlement along with a change in fracture morphology was found.9 In this present study, a mercury-dewetting method was used to observe crack initiation and fracture morphology when a Cu-4 pct Ag alloy is deformed in mercury and Hg-Zn solutions. PROCEDURE Specimens of Cu-4 pct Ag were prepared as in previous crack-path studies.&apos; The specimens were heated at 770°C for 24 hr and water-quenched Tension tests using a table-model Instron were carried out in mercury and in various concentrations of Hg-Zn. Loading was in steps up to the fracture stress, with the load being removed and the specimen examined for surface cracks at each step. The specimens were dewetted after each load to permit examination of the surface structure and rewetted prior to continued loading. The specimens were wetted by electro polish ing in phosphoric acid, rinsing in alcohol, and then immersing in a pool of mercury. Dewetting was accomplished by flame heating the specimen for 30 sec in a vacuum. Some surface contamination was found, but not enough to obscure crack configurations and grain boundaries. RESULTS Fracture Characteristics in Mercury. Fig. 1 is a stress-strain curve showing the progressive step-wise loading of the specimen. As may be seen from the graph, the first position stopped at a is at a stress 5000 psi below the expected fracture stress of 25,000 psi. Examination of the specimen after removal of mercury showed only one crack. The appearance of this crack at a stress far below the fracture stress of this alloy in mercury did not affect the stress-strain curve in any manner. The specimen was then recoated with mercury and deformation was continued (curve b, Fig. 1) raising the stress by 4000 psi, and the same procedure re~eated. The initial crack was located and appeared as in Fig. 2 (crack lb). In this figure the crack is

Jan 1, 1964

By H. D. Mellom

The direction of the optic or "C" axis of a uniaxial metal crystal can be found with the metallurgical polarizing microscope by examining two planes of section on the crystal. Complete orientation of the crystal can be determined if a twin crystal is common to both surfaces of section. Examination of Uniaxial Metals in Polarized Light-Rotation of a uniaxial crystal surface, properly prepared,&apos; shows four extinction positions 90 deg apart, provided that the surface is not close to a basal section. One of these two extinction directions corresponds with the projection of the optic axis on the surface of section. This direction can be found if the &apos;sign of the rotationr2 for the metal is known. To find the direction of the optic axis, the crystal is rotated on the stage 45 deg from an extinction position. With a crystal of negative sign, to produce extinction the analyser must be rotated towards the optic axial direction and vice versa. All sections, other than basal, of a uniaxial crystal have the same sign of rotation and, since there is no change in sign with wave length, white light can be used for these measurements. U the sign of the rotation is not known the presumed direction of the optic axis can be determined assuming a positive sign. A third section cut normal to the presumed optic axis will show basal extinction if the assumption is correct. It is convenient to use the edge between the two planes of section as a fiducial direction common to both surfaces. The optic axis can be related to this direction. If the above measurements are repeated on the other plane of section and the angle between the two section planes measured, stereographic projection can be used to determine the orientation of the crystal optic axis. Determination of Complete Orientation—The complete orientation of a uniaxial crystal can be determined provided that a twin crystal is common to both surfaces of section, and the twin law is known. The orientation of the twin crystal optic axis can be determined in the same way as for the main crystal

Jan 1, 1962

By F. V. Lenel, G. S. Ansell, E. C. Nelson

IRMANN&apos;S&apos; discovery that extrusions of fine alumi-num-flake powders possess remarkable high-temperature strengths has led to the production of a new class of engineering materials whose properties are derived from a fine dispersion of oxide particles in a metallic matrix. A fundamental study of such materials and elucidation of the mechanism whereby the oxide parti-

Jan 1, 1958

By M. C. Lavine, H. C. Gatos, R. S. Mroczkowski

The structure of GaAs-Ge heterojunctions prepared by a back-melting process was studied by X-rav diffraction, melallographic, and electron-micro-analyzer techniques. The boundary region between the GaAs and the germanium was found to consist of a four-layered band. A discontinuity between the two inner bands was brought about by solidification occurring simultaneously from the GaAs and the germanium side. The junction material OH either side of the central discotinuity was found to have grown as a single Crystal with the orientation of the parent substrate. It was found essential to determine the GaAs-Ge phase diagram. This was accomplished by a series of alloys containing 0 to 40 wt pet GaAs. Over this range the diagram is a simple eutectic with the eutectic point at 74 wt pet Ge and 845 C. The limiting- solubility of Coils in germanium was found to bc less than 5 wt pet. The Kossel divergent-beam X-ray technique was used to study orientation relationships across the boundary lager. A great deal of effort has been recently expended on the electrical properties of heterojunctions. Little attention, however, has been given to the metallurgical variables which may be of importance in the formation of the junctions. The present work was undertaken to investigate some of the more pertinent metallurgical aspects of interface-alloyed GaAs-Ge heterojunctions. Such parameters as solidification processes, composition gradients, orientation effects, and the accommodation of crystal structures have been the objects of study in this program. EXPERIMENTAL PROCEDURES Phase Diagram. The phase diagram of the GaAs-Ge pseudobinary system was determined by means of cooling curves. A Bridgeman furnace was employed with the center section maintained at 1200°C and the upper section at 800°C. Melts varying from 0 to 40 at. pct in GaAs content were used. Each charge was incapsulated under a two-thirds atmosphere of argon in a carbon-coated quartz tube. Five min in the furnace hot zone provided rapid melting and homogenization. The capsule was then removed to the cooler portion of the furnace. Cooling times were of the order of 3 min. The resulting homogeneous microstructure indicated that equilibrium conditions were obtained by this procedure. Formation of Heterojunctions. Rectangular parallelepiped single-crystal samples were cut with the large faces of either the (l00), (110), or (111) orientation. The remaining four surfaces were also cut to specific orientations to permit accurate relative orientation of the GaAs-Ge pairs. The

Jan 1, 1965

By W. D. Robertson

SINCE the comprehensive paper of Moore, Beckin-sale, and Mallinson,&apos; little consideration has been given to the mechanism of mercury stress cracking of copper-base alloys, apart from extensive work on metallurgical and fabrication variables employing mercurous nitrate as an evaluation test. However, with the phase diagrams now available and the recent considerations of interfacial tension at grain boundaries, developed by Smith,2 it appears that the elements of a detailed solution to the problem are available. The facts that require explanation are: 1—Pure copper is not embrittled by mercury, with or without an applied or residual stress. 2—Cu-Zn and other copper-base alloys, in excess of some undefined solute concentration, are embrittled provided an external or residual stress is acting; cracking is not observed in the absence of stress. 3—The path of fracture is invariably intergranu-lar. 4—Copper and copper-base alloys do not dissolve readily in mercury at room temperature.&apos; Consideration of the Cu-Hg phase diagram% hows that, at room temperature, solution of copper in mercury is probably limited by the formation on the surface of a microscopically thin layer of inter-metallic compound, CuHg, having a very limited range of solubility which effectively restricts diffusion of copper and mercury. But, above 150°C (the highest peritectic temperature) copper solid solution is in equilibrium with a liquid Hg-Cu solution and, consequently, copper should dissolve freely in a large volume of mercury with the formation of an equilibrium dihedral angle at grain boundaries in contact with the liquid phase. Depending on the magnitude of this angle, mercury will or will not penetrate the solid phase along grain boundaries and spread over grain faces. Thus the measurement of the dihedral angle of grain boundaries in equilibrium with the liquid phase above 150°C should indicate whether copper is intrinsically resistant to embrittlement by mercury. In view of the fact that mercury is appreciably soluble in copper, it may also be anticipated that diffusion of mercury will take place at higher temperatures in the absence of the intermetallic compound and possibly at a more rapid rate along grain boundaries than through the grains, resulting in a Cu-Hg alloy of unknown properties. In the case of brass, the ternary system Cu-Zn-Hg is involved and, from the resistance of brass to general solution in mercury at room temperature, it is probable that a compound of limited solubility range also exists, similar to the binary Cu-Hg sys- tem. Also, compared with copper, a change in the dihedral angle at grain boundaries in contact with mercury may be expected to result from the addition of zinc to copper. The preceding generalizations appear to be confirmed by the following experiments. Experimental Results Oxygen-free copper wire, annealed at 700°C for 3 hr in copper foil, was immersed in mercury at 170°C, with and without an applied stress. After 24 hr immersion, specimens which were spring loaded to a nominal stress of 10,000 psi had not failed, and there was no apparent embrittlement as indicated by a 180" bend around a diameter approximately equal to the diameter of the wire (0.125 in.) : General solution of the surface had taken place, indicated by a change in diameter of the wire, and the resulting structure of the surface is shown in Fig. 1. It is apparent that angles have developed at grain boundaries and examination at a high magnification indicates that the angle is in excess of 120°, completely excluding penetration of mercury. In view of the measurements made by Smith n the

Jan 1, 1952

By E. E. Schumacher

IN a laboratory devoted to the furtherance of the science of communication, the breadth and variety of the problems encountered are challenging to a metallurgist. In my own long association with the Bell Telephone Laboratories, our metallurgical group has dealt with a vast number of alloys, both ferrous and nonferrous, and with many materials in the border range of metallic properties., The objectives of our design engineers embrace every phase of telephony, and the properties they desire in metals are generally unusual, frequently unique, and often conflicting. Commercial alloys have not always been available with properties to meet a special requirement in the telephone plant, and many alloys have had, therefore, to be custom-made. Anyone who has had the opportunity to observe the results of tests of all types on numerous such alloys, both commercially and specially produced, or who has taken part in the development of an alloy of some necessary, but new or unusual combination of properties, could not fail to be impressed by the frequency with which a desired goal has been reached or adequately approached through the presence of decimal quantities of alloying elements. Nor could One fail to be struck by the occasions when, conversely, of a minute amount Of impurity element has rendered an alloy useful. It is no exaggeration to state that the content be- hind the decimal point often spells success or fail-ure, and the critical content is sometimes far to the right of the decimal point as I shall later illustrate. The great effects of small additions have long been recognized and have, in fact, been described by many investigators. The importance of the minute, however, cannot be overemphasized. Therefore, in this discussion, I propose to illustrate for you some of the startling instances, drawn primarily from our own experiences, wherein small, even vanishingly small, proportions of stranger elements in otherwise common aggregates have com-pletely changed the customary pattern of behavior. No one property has a monopoly as to being dis-proportionately affected by minor elements. Nearly all properties are affected, but there is time here to include only a selected few. I have chosen, there-fore, three of general interest: strength, magnetic, and electrical properties. I shall inquire into both the mechanisms and consequences of these disproportionate effects and try to share with you the fascination and challenge of this field. Strength Properties of Lead and Lead Alloys To illustrate the effect of the minute on strength properties I have selected lead and its alloys, with which we have worked extensively for many years. Lead has the advantages of being available in quantity in a state of high purity and of being fairly easy to melt and fabricate without contamination to any extent detectable by the spectrograph. It has the interesting disadvantages of recovery and recrystallization at room temperature. Whether I

Jan 1, 1951

By H. L. Luo, P. Duwez, C. C. Chao

BY rapidly cooling alloys from the liquid state, it is possible to obtain solid solutions beyond the equilibrium concentrations, provided that the components are miscible in the liquid state. Typical such cases include CU-Ag,1 Pt-Ag,2 CU-Rh,3 nickel-base alloys with silicon, germanium, and tin,4 and cobalt-base alloys with silicon, germanium, tin, aluminum, and gallium.5 In the present note it is shown that terminal solid solutions can be appreciably extended in A1-Mg alloys. The alloys whose compositions are given in Table I were prepared by induction melting in tantalum crucibles under an argon atmosphere. Both aluminum and magnesium were 99.99 pct pure. Weight losses after melting were less than 0.2 pct for the aluminum-rich alloys and less than 0.4 pct for the magnesium-rich alloys. From these weight losses it was estimated that the compositions of the ingots after melting were accurate within 0.3 at. pct for aluminum-rich alloys and within 0.5 at. pct for magnesium-rich alloys. As indicated in Table I, the compound AuCd10 in which there is an ionic contribution to the bonding. The authors thank Dr. J. H. Westbrook of the Research Laboratory, General Electric Co., for arranging the supply of materials and for his interest. This investigation was supported by the U.S. Atomic Energy Commission under Contract AT(30-1)-1002, Scope I. some of the alloys were also chemically analyzed and the results confirmed the limits of uncertainty based on weight losses. Rapid quenching from the liquid state was achieved by techniques previously described.8,7 The principle of these techniques consists of propelling a small globule of liquid alloy (about 20 mg) onto a copper substrate. The thin foils easily detached from the copper substrate were analyzed by X-ray diffraction using a Debye-Scherrer camera 114.6 mm in diameter and either nickel-filtered copper Ka or iron-filtered cobalt Ka radiation. Since the back-reflection doublets were resolved, the wavelengths used in the computatioas were CuKal = 1.54050A and CoKa1= 1.78892A. Lattice parameters were obtained by extrapolation of the Nelson-Riley function, and the tables compiled

Jan 1, 1964

By Henry A. Stiff, J. P. Hammond, A. B. Westerman, H. C. 195-000-000-014 Cross, and Lawrence E. Davis

The phases in Cr-Fe-Mo alloys have been investigated with homo-genization, aging temperature, composition range, and alloy addition as variables. Metallography, three X-ray methods, and hardness were used as methods of study. The behavior of s, M23,C8, and Z phase are reported for cornpasition range 60 pct Cr-15 to 25 pct Fe-15 to 25 pct Mo-<0.005 to 0.36 pct C with aging at 1400º to 2000°F. With 2 pct Ti, Tic and TiC-TiC are formed; with nitrogen Cr2N. THE recently developed class of chromium-base heat-resistant alloys shows appreciably higher strength than commercially used high temperature alloys. However, further developmental work is required to impart needed shock resistance and some degree of room-temperature ductility to these alloys. Extensive exploratory work on chromium-base alloys was begun in a program initiated by the War Metallurgy Committee of the National Defense Research Council at the Climax Molybdenum Co. in the early part of 1942.&apos; Alloys were sought for gas-turbine blades for use at 1600°F. A minimum of 5 pct elongation in the stress-rupture test was a requirement. From the Climax work, ternary alloys of chromium, iron, and molybdenum appeared to show the greatest promise as materials for gas-turbine blades. The composition line in the ternary diagram joining the 60 pct Cr-15 pct Fe-25 pct Mo and 60 pct Cr-25 pct Fe-15 pct Mo alloys was indicated as representing the most useful combination of strength and ductility.&apos; Strength increased while ductility decreased as molybdenum was raised in this composition range.&apos; The 60 pct Cr-15 pct Fe-25 pct Mo type alloy was thought to have the most suitable properties for gas-turbine blades.&apos; Concurrent with the study reported here, other investigations were being made on Cr-Fe-Mo alloys. The liquidus temperatures on a series of low carbon, ternary alloys were being determined, and isothermal sections drawn at 2370°, 2010°, and 1650°F (1300°, 1100°, and 900°C).2 Also, various methods of preparation and some mechanical and physical properties of chromium-base alloys, particularly the 60 pct Cr-15 pct Fe-25 pct Mo type, were being investigated., At the inception of the present program, only a limited study had been made of etchants for developing the microstructures of chromium-base alloys; X-ray analysis of the microconstituents had not been made. A review of the literature revealed that no phase-diagram work had been reported on the Cr-Fe-Mo system. Scope of Work The work on chromium-base alloys includes the following: 1—The development of etching methods for differentiating between the microconstituents; 2—The identification of microconstituents by X-ray diffraction methods; and 3—A comprehensive metallographic and hardness study after various heat treatments. The phases were studied by three standard X-ray techniques: 1—The block-sample focusing-camera method; 2—The powder-diffraction method on elec-trolytically separated residues; and 3—The powder-diffraction method on cold-worked aggregate samples. The results by the first two methods were correlated with the metallographic data. The third method was used largely to study conditions approaching equilibrium, since cold working prior to heat treating accelerated precipitation. Seven types of alloys were investigated: 50 pct Cr-50 pct Fe, 40 pct Cr-40 pct Fe-20 pct Mo, 55 pct

Jan 1, 1953

By S. A. Mersol, C. T. Lynch, F. W. Vahldiek

The microhardness of single crystals of tungsten disilicide has been investigated by the Knoop method. The average random room-temperature hardness of the WSi, matrix was 1350 kg per sq mm. Hardness crnisotropy was noted with respect to plane and indenter orientation as determined by single-crq.stal X-rny studies. Annealing at 1600" and 1800°C decreased the average hardness to 1310 and 1230 kg per sq tnm, respectively, and produced a second phase identified by X-ray diffraction and electron-microprobe analysis to be wSio.7. Ball-impact experiwzents produced rosettes at 850°C. Optical and electron microscopy showed evidence of slip and cross slip and twinning produced by microhardness indentations. Prismatic (100), [001] slip was found and cor~elated with hardness data. THE present study was undertaken to investigate the hardness anisotropy of as-grown and annealed single crystals of tungsten disilicide. The existence of the silicide WSiz in the W-Si system has been well-established and its structure thoroughly investigated zachariasen2 found WSi, to have a tetragonal C type of structure, similar to that of MoSi, with lattice parameters a = 3.212A, Kieffer et al. studied the W-Si system and measured the density and microhardness (at a 100-g load) of both polycrystalline WSi, and WSi,.,. The values found were 9.25 g per cu cm and 1090 kg per sq mm for WSi,, and 12.21 per cu cm and 770 kg per sq mm for WSi0.7, respectively. According to Samsonov et a1.5 the microhardness of polycrystalline WSi2 is 1430 kg per sq mm (at a 120-g load). EXPERIMENTAL The WSi, single-crystal boules investigated in this paper were grown by a Verneuil-type process using an electric arc by the Linde Division of the Union Carbide Corp.6 The largest specimens were 8 mm in diameter by 16 mm long. The crystals had an average density of 9.01 g per cu cm with a tungsten • silicon content of 99.9 wt pct. The major impurities were: 87 ppm O, 41 ppm N. 54 pprn C, 500 ppm Zr, 50 ppm Na, and 50 ppm Mn. The crystals were silicon-poor, the average silicon content being 22.20 pct (stoichiometric value is 23.40 pct), and tungsten-rich, the average tungsten content being 77.70 pct (stoichiometric value is 76.60 pct). As-received single crystals were ground and analyzed by powder X-ray diffraction technique using Cu Ka radiation. Laue and layer line rotation patterns were obtained on cleaved sections of WSi, single crystals. Electron-microprobe traverses of representative crystals were done using a Phillips-AMR electron microanalyzer. Carbon replicas were used to prepare electron micrographs. This work was done with a JEM-6A electron microscope. Prior to the metallographic examination, the specimens were mounted in Lucite and then polished for short times on polishing wheels using 9-, 3-, and 1-p diamond-grade pastes. Finally they were fine-polished with Linde A powder for 24 hr on a Syntron vibratory polisher. The samples were etched with 4H 2 O:1HF:2HNO3, which is a medium fast-acting etchant. The combination 1HF:2HNO3:5 lactic acid is also a satisfactory etchant. Annealing runs for selected specimens were made at 1600" and 1800°C for 3 hr at 1.0 to 3.0 x 10-5 mm Hg. A Brew tantalum resistance furnace with WSi2 powder for setters was used. The WSi2 powder was the same as that used for the crystal growth. Temperatures were measured with a calibrated W, W-26 pct Re thermocouple and a microoptical pyrometer. Powder X-ray diffraction, emission spectrographic, and electron-microprobe analyses were done after the annealing runs. For microhardness measurements a Tukon Microhardness Tester Type FB with a Knoop indenter was used. Although measurements were taken at loads ranging from 25 to 1000 g, the 100-g load was chosen as the standard load. All measurements were taken at room temperature. Only indentations of cracking classes 1 and 2 were considered.&apos; DISCUSSION OF RESULTS Powder X-ray diffraction analysis showed the as-received crystals to be single-phase WSi2. Laue and layer line rotation patterns obtained on cleaved sections of WSi2 single crystals proved them to be tetragonal WS 2 2 The results also indicated that the c axis of the crystal was oriented parallel to the boule or growth axis. Electron-microprobe traverses across the matrix of the as-grown crystals showed them to be homogeneous WSi,. Optical and electron microscopy of etched crystals, however, revealed that they contained minute amounts of the "golden" and the "blue" second phases as opposed to the "white" or WSi2 phase. These two second phases were concentrated in inclusion and etch-pit

Jan 1, 1965