Search Documents

By J. J. Frawley, W. J. Childs, W. R. Maurer

The object of this investigation was to determine the growth habit of bismuth and bisrrtuth alloy dendrites as a function of supercooling. To do this, techniques were developed to increase the amount of supercooling in bismuth and bismuth alloys. For pure bismuth, the growth habit was dependent on the amount of supercooling. At low amounts of supercooling, about 10" C, prismatic dendrites were obtained. With increased supercooling, about 20 C, a hopper growth habit was observed. In many cases where hopper growth had occurred, the hopper dendrites were twinned during the growth process. This twinned surface enable prismatic dendrites to nucleate and grow by a twin plane mechanism. When the amount of supercooling was increased to about 25 °C, the growth habit was a triplanar growth. With still greater supercooling, about 3s°C, a branched growth habit occurred. The exposed planes on the prismatic, hopper,, triplane, and branched dendrites have been determined. The growth habit of the dendrites which grew along the crucible wall was found to have the (111) as the exposed plane, with <211> growth direction. It is apparent that dendritic growth of a metal is dependent on its purity and the solidification variables present. One of the solidification variables is the degree of supercooling. Supercooling, although often observed, has not been studied extensively until recent years. For dendritic growth to occur in a pure metal, the metal must be thermally supercooled. After the dendrites grow into the supercooled melt, the heat of solidification raises the temperature of the specimen to the melting point of the material and the remaining liquid will solidify at this temperature. Decanting is the removal of this remaining liquid before complete solidification. This removal of the remaining liquid after recalescence had occurred is a great aid in the study of dendritic growth. In this investigation, decanting was accomplished by a vacuum-decanting technique . Other investigators1-5 have studied the growth characteristics of various low-melting-temperature pure metals and alloys as a function of supercooling. However, large degrees of supercooling were not included. For their study of dendritic growth of lead, Weinberg and chalmersl employed a decanting technique which was achieved by pouring off the remaining liquid, exposing the solid/liquid interface. This method was employed later by Weinberg and Chalmers2 for the investigation of tin and zinc dendrites. The method for obtaining a solid/liquid interface was improved by Chalmers and Elbaum. They employed a triggered spring which was attached to the solidifying section of the specimen. Upon activation, the spring jerked the solid interface away from the liquid melt. In the study of growth from the supercooled state, a metal of low melting point which exhibited a high degree of supercooling was desired. Bismuth gave very consistent supercooling when a stannous chloride flux was employed. The maximum supercooling obtained was 91°C, with an average supercooling of between 65" and 75°C. The consistency of supercooling greater than 50°C was very high. The use of vacuum to aid in the rapid decanting of molten metal has proven to be very successful in this investigation. The vacuum gives a rapid decantation, usually leaving the solidified metal structure sharply defined. The purpose of this investigation was to study the effects of supercooling and the effects of alloy additions on the growth habit of bismuth dendrites. The structure of bismuth has been variously defined as face-centered rhombohedral, primitive rhombohedral, and hexagonal. However, bismuth has only one plane with threefold symmetry, the (111) plane, and the crystal-lographic structure is considered a 3kn structure. MATERIALS The bismuth which was employed in this investigation was obtained from the American Smelting and Refining Co. of South Plainfield, N. J. The accompanying spectrographic analysis data indicated the bismuth to be 99.999+ pct pure. The tin was obtained from the Vulcan Materials Co., Vulcan Detinning Division, Sewaren, N. J. It was classified as "extra pure". Nominal analysis was 99.999+pct. In order to prevent contamination of the bismuth melt from the atmosphere, an anhydrous stannous chloride (Fisher certified reagent grade) was added to each melt. The fluxing action obtained from the use of the chloride provided a large amount of supercooling in the specimen. APPARATUS A 30-kw, 10,000-cps motor-generator set, connected to a 6+-in.-diam air induction coil, was employed to melt and superheat the specimens. The temperatures were recorded by means of a chromel-alumel thermocouple and a potentiometric recorder. The thermocouples were 0.003 in. in diam, and were encapsulated with Pyrex glass to prevent the thermocouple from acting as a nucleating agent and also from contaminating the melt. Fig. 1 illustrates the vacuum-decanting apparatus when a liquid flux was employed. A standard 30-ml Pyrex beaker was placed on top of an asbestos insulating block. A 5-mm-ID Pyrex tube with aA-in. spacer tip attached to its end was used for the decanting tube. The spacer tip contributed significantly to a successful decanting operation. The tip located the opening of the decanting tube about -^ in. from the bottom of the

Jan 1, 1969

By H. Conrad, V. Damiano, J. Hanafee, N. Inoue

The effects of hydrostatic pressure up to 400 ksi at 25" to 300°C on the mechanical properties of three forms of commercial beryllium (hot-pressed block, extruded rod and cross-rolled sheet) were investigated. Three effects of pressure were studied: mechanical beharior under pressure, the effect of pressure-cycling, and the effect of tensile prestraining under hydrostatic pressure on the subsequent tensile properties at atmospheric pressure. For all three materials the ductility increased with pressure whereas the flow stress did not appear to be significantly influenced by pressure. An increase in the subsequent atmospheric pressure yield strength generally occurred as a result of pressure-cycling or prestraining under pressure, whereas either no change or a decrease in ductility occurred. The only exception to this was sheet material, which exhibited some improvement in ductility following a pressure-cycle treatment of 304 ksi pressure. The effects of pressure-cycling and prestraining were relatively independent of the temperature at which they were conducted. Stabilized cracks of the (0001) type were found in hot-pressed specimens and {1120) type in extruded and sheet specimens following straining under pressure. Also, pyramidal slip with a vector out of the basal plane, presumably c + a, was identified by electron transmission microscopy for extruded rod and for sheet strained under pressure. Small loops similar to those previously reported were found after straining at pressures of the order of 300 ksi. THE use of beryllium in structures is limited because of its poor ductility under certain conditions. Therefore, one objective of the present research was to determine if the ductility of beryllium at atmospheric pressure could be improved by prior pressure-cycling or prestraining under hydrostatic pressure. Another objective was to study the mechanisms associated with the plastic flow and fracture of the polycrystalline form of this metal with pressure as an additional variable. Since the early work of Bridgman,1 it has been recognized that many materials which are brittle at atmospheric pressure exhibit appreciable ductility when strained under high hydrostatic pressure. This effect has been reported for beryllium by Stack and Bob-rowsky2 and by Carpentier et al.3 and has been attributed to the operation of pyramidal slip systems with slip vectors inclined to the basal plane while cleavage or fracture is suppressed.4 That such slip may occur simply by the application of pressure alone without external straining (pressure-cycling) is suggested by the results on polycrystalline zinc5 and polycrystalline beryllium,6 where nonbasal dislocations with a vector (1123) were reported. A significant improvement in the ductility of the bee metal chromium by pressure-cycling has been reported.7 On the other hand, limited studies on the pressure-cycling of the hcp metals zinc67819 and beryllium6 indicated no improvement in ductility; there only occurred an increase in the yield and ultimate strengths. The study on beryllium was limited to hot-pressed material. Consequently, additional studies on the effects of pressure-cycling on other forms of beryllium seemed desirable, especially since for chromium some authors10 have been unable to detect any improvement in ductility while others find a large improvement.7 That the ductility of polycrystalline beryllium at atmospheric pressure might be improved by prior straining under hydrostatic pressure was suggested by the known beneficial effects of cold work on the ductile-to-brittle transition temperature in the bee metals. It was reasoned that, by straining under hydrostatic pressure, fracture would be suppressed, and during the propagation of slip from one grain to its neighbor dislocations with a vector inclined to the basal plane"-&apos;4 would operate. Upon subsequent straining at atmospheric pressure, these dislocations with a nonbasal vector would continue to operate and thereby reduce the tendency for fracture to occur, by assisting in the propagation of slip across grain boundaries and by interacting with any cracks that may develop. It was recognized that maximum improvement in ductility would probably occur at some optimum amount of prestrain under hydrostatic pressure. If the pre-strain was too small, an insufficient number of dislocations with a nonbasal vector would be activated; if it was too large, internal stresses (work hardening) might increase the flow stress more than the fracture stress, or incipient cracks or other damage could develop. EXPERIMENTAL PROCEDURE 1) Materials and Specimen Preparation. The materials employed in this investigation consisted of hot-pressed block (General Astrometals, CR grade), extruded rod (General Astrometals, GB-2 grade with a reduction ratio of 8:1), and cross-rolled sheet (Brush S200, 0.065 in. thick). The analyses of these materials and mechanical properties at room temperature and atmospheric pressure are given in Table I. The grain size of the hot-pressed block was 15 to 16 µ, that of the extruded rod 10 to 11 µ, and that of the sheet 7 to 10 µ in the rolling plane and 5 to 6 µ in the thickness, all determined by the linear intercept method. Al-

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 A. Paul Bond

Two series of 17pct Cr iron-base alloys with small, controlled amounts of carbon and nitrogen were vacuum-melted in an effort to detertmine the meclz-uniswls of inter granulur corrosion in ferritic stain-less steels. An alloy containing 0.0095 pct N aid 0.002 pct C was very resistant to intergranular corrosion, even after sensitizing heat treatments at 1700" to 2100o F. However, alloys containing more than 0.022 pct Ni and more than 0.012 pct C were quite susceptible to intergranular corrosion after sensitizing heat treatments at temperatures higher than 1700°F. This corrosion was observed after the usual exposure tests and after potentiostatic polarization tests. Electronmicroscopic examination of the alloys susceptible to intergranular corvosion revealed a small grain boundary precipitate; this precipitate was absent in the alloys not susceptible to such corrosion. Thc electronmicrographs indicate that intergranu1ar corrosion of ferritic stainless steels is caused by the depletion of chromium in areas adjacent to precipi-tates of chromium carbide or chromium nitride. It also seems likely that the precipitates themselves are attacked at highly oxidizing potentials. Confirma-tion of the proposed mechanisms was obtained in tests on air-melted ferritic stainless steels containing titanium. The titanium additions greatly reduced susceptibility to intergranular corrosion at moderately oxidizing potentials but had no beneficial effect at highly oxidizing potentials. A major obstacle to the use of ferritic stainless steel has been their susceptibility to intergranular corrosion after welding or improper heat treatment. It appears that sensitization of ferritic stainless steel occurs under a wider range of conditions than for austenitic steels. In addition, a greater number of environments lead to damaging intergranular corrosion of sensitized ferritic stainless steels than to sensitized austenitic steels. The chromium depletion theory of intergranular corrosion is widely accepted for austenitic stainless steels&apos;" although there: are some objections.3 On the other hand, several alternative mechanisms proposed for ferritic stainless steels include precipitation of easily corroded iron carbides at grain boundaries,&apos; grain boundary precipitates that strain the metal lat-tice,5 and the formation of austenite at the grain bound-arie.6 The application of the chromium depletion theory to ferritic stainless steels has been discussed extensively by Baumel.7 The present investigation was undertaken to determine which of the proposed mechanisms can be sub- A PAUL BOND IS Research Group Leader, Climax Molybdenum Co of Michigan, Ann Arbor, Mich. stantiated with experimental data obtained on ferritic stainless steels. High-purity 17 pct Cr alloys containing small controlled additions of carbon or nitrogen were therefore prepared, and then examined electro-chemically and metallographically. EXPERIMENTAL PROCEDURES Materials. Two series of experimental alloys were prepared from electrolytic iron and low-carbon ferro-chromium using the split-heat technique. In this technique, the base composition is melted, and part of the melt is poured off to produce an ingot. To the balance of the melt, the required addition is made and the next ingot cast. This process is repeated until a series of the desired compositions is cast. By this procedure the impurity levels are essentially constant within each series. All the alloys in the carbon-containing series were melted and cast in vacuum. The base composition in the nitrogen series was melted and cast in vacuum; subsequent ingots in the series were melted with additions of high-nitrogen ferrochromium, and cast under argon at a pressure of 0.5 atmosphere. Two additional alloys were produced starting with normal purity materials. They were induction-melted while protected by an argon blanket and cast in air. Table I gives the composition of the alloys. The 2-in.-diam ingots produced were hot-forged and hot-rolled to a thickness of 0.3 in. and then cold-rolled to 0.15 in. All specimens were annealed at 1450°F for 1 hr. The indicated sensitizing heat treat-s s ments were performed on annealed material. All heat treatments were followed by a water quench. Specimen Preparation. For the 65 pct nitric acid test, 1 by 2 by 0.14-in. specimens were wet-surface ground to remove surface irregularities and polished through 3/0 dry metallographic paper. For the modified Strauss test, $ by 3 by 0.14-in. specinlens were similarly prepared. Immediately prior to testing, the Table I. Compositions of the Alloys Composition, pct Alloy Cr hio C N 270A 16.76 0.0021 0.0095 270B 16.74 0.0025 0.022 270C 16.87 0.0031 0.032 270D 16.71 0.0044 0.057 271A 16.81 0.012 0.0089 27 IB 16.76 0.018 0.0089 271C 16.69 0.027 0.0085 271D 16.81 0.061 0.0O71 4073&apos; 18.45 1.97 0.034 0.045 4075† 18.5 2.0 0.03 0.03

Jan 1, 1970

By J. A. Bailey, J. H. Tundermann

The dihedral angles of the solid-liquid interfaces were measured at various temperatures above the solidus and the interfacial energies calculated when small additions of copper, indium, lithium, magnesium, antimony, and silicon were made to an aluminum alloy containing 3 pct Sn. When the results were compared with those of the Al-Sn alloy some differences were found which could be interpreted in terms of the ability of the added element to enter into solution or form intermetallic compounds with the aluminum and tin. It was shown that in some cases considerable changes in the shape of intergvanular liquid films can be brought about by comparatively small compositional changes in the alloy. DURING the melting or solidification of an alloy a temperature range is usually found where the presence of a liquid phase may be detected at the grain boundaries of a solid. It is believed that the presence of this liquid phase is responsible for hot tearing in castings and welds and hot shortness in the working of some alloys at elevated temperatures. Rosenberg, Flemings, and Taylor1 in a study of the solidification of aluminum castings have indicated the importance of intergranular liquid films and shown that their shape and distribution at the end of solidification effect the hot tearing characteristics of the material. The shape of such intergranular liquid films are determined largely by the ratio between the solid-liquid interfacial energy (yLS) and the grain boundary energy (ySS). A measure of this ratio (yLS/ySS , relative interfacial energy) is the dihedral angle 8. The dihedral angle 0 is related to the relative interfacial energy by the following expression: Rogerson and Borland 2 have also suggested that the shape of the intergranular liquid is an important factor in determining the susceptibility of a material to hot shortness. They showed that on a comparative basis materials having the lowest dihedral angles at a given temperature gave the greatest severity of cracking. They stated that liquid in the form of globules should be less harmful than liquid in the form of extensive films as more intergranular cohesion should be possible. Rogerson and Borlland 2 also showed that the susceptibility of an A1-Sn alloy to hot cracking can be reduced by small additions of cad- mium. It was found that the cadmium gave an increase in the dihedral angle at all temperatures. Ikeuye and smith3 investigated changes in the dihedral angle and relative interfacial energy with temperature for a number of ternary alloys formed when small additions of bismuth, cadmium, copper, lead, and zinc were made to an A1-Sn alloy. They found that in most instances changes in the dihedral angle were caused by compositional changes in the liquid phase; as the composition of the liquid approached that of the solid the dihedral angle decreased. They noted that the addition of a third element which was soluble in both the liquid and solid phases at a given temperature may decrease the dihedral angle (e.g., the addition of copper or zinc) but otherwise the ternary alloys formed exhibited dihedral angles between those of the A1-Sn binary alloy and those of the binary alloy of aluminum with the added element. Dwarakadasa and Krishnan4 investigated the changes in dihedral angle and relative interfacial energy with temperature when small additions of magnesium, iron, silicon, manganese, sulfur, cobalt, and silver were made to a copper alloy containing 3 pct Bi. They found that in all cases the added elements gave an increase in the dihedral angle and relative interfacial energy when compared with the values obtained for the simple binary alloy at the same temperature. It was noted that an increase in temperature gave a decrease in dihedral angle and relative interfacial energy in each of the ternary alloys studied. Similar results have been obtained by Ramachandran and Krishnan5 for the addition of small quantities of lead. This paper describes the application of dihedral angle measurement to the determination of the shapes of liquid phases at various temperatures above the solidus when small additions of copper, indium, magnesium, lithium, antimony, and silicon are made to an aluminum alloy containing nominally 3 pct Sn. An attempt is made to correlate the measurements with the relative solubility of the added elements in tin and aluminum. The work was undertaken to provide more data concerning the effects of temperature and composition on the shape of liquid films above the solidus. EXPERIMENTAL PROCEDURE In the present work ternary aluminum alloys containing nominally 3 pct Sn and small additions of high-purity copper, indium, lithium, magnesium, antimony, and silicon were made. The alloys were melted in a graphite crucible under an inert atmosphere of argon and cast into ingots 6 in. long by 0.5 in. diam. The ingots were then cut into rods 1.5 in. long, given a 50 pct cold reduction, and machined into test pieces 0.5 in. long by 0.5 in, diam for heat treatment. The alloy samples were annealed at the various test temperatures between the liquidus and solidus for approxi-

Jan 1, 1967

By P. M. Kelly, E. P. Butler

Four Mn-CLL alloys, containing 60, 70, 80, and 90 pct Mn, respectively, have been examined in the quenched and the quenched and aged conditions using electron microscopy and electron, neutron, and X-ray diffraction. After certain heat treatments the alloys transform from fee to fct and in the tetraom1 condition show a domain structure parallel to {101} planes. Neutron diffraction indicates that the domains are antiferrornagnetically ordered. The domain boundary contrast has been examined using bright- and dark-field microscopy, and the contrast effects observed under favorable conditions have been used to deduce the c axis orientation in each domain. The domains are extremely mobile and can be nucleated at precipitate particles and screw dislocations. The domain mobility is responsible for the high damping capacity. In the aged material a Mn precipitates in the Kurdjumov-Sachs orientation and results of both electron microscopy and neutron diffraction indicate that the matrix separates into two components—one rich in manganese and the other rich in copper. ALLOYS of manganese and copper have the unusual combination of a high damping capacity and good mechanical properties and have been the subject of a number of investigations as part of a general interest in high damping capacity alloys for engineering purposes.&apos;,&apos; SO far, however, there has been no reported electron metallographic study of these alloys. The Mn-Cu system has an extensive range of solid solubility at high temperatures, and the equilibrium phases are expected to be y (fee) and a Mn. The high damping capacity is associated with a metastable tetragonal structure of variable c/a ratio, which forms from the high-temperature y phase. This latter phase becomes more difficult to retain as the manganese content increases, and alloys containing more than 82 wt pct Mn undergo a reversible martensitic fcc — fct transformation on quenching. The X-ray work of Basinski and christian3 showed that the Ms temperature for the transformation was below room temperature for alloys in the range 70 to 82 pct Mn and increased linearly with manganese content. When quenched from the y region, alloys in the range 50 to 82 pct Mn are cubic at room temperature, but become tetragonal if aged at temperatures between 400" and 600°C. The martensite transformation occurs on cooling from the aging temperature. Tetragonal alloys have a banded microstructure and the bands analyze to be traces of (110) planes. Similar microstructures have been observed in In-Tl4 and in other manganese-base systems, such as Mn-Au5 and Mn-Ni.6 The mobility of the bands in Mn-Cu alloys can be demonstrated by optical examination of a polished specimen surface subjected to a cyclic stress.7 The bands appear and disappear as the stress is varied, and X-ray measurements of the (200,020) and (002) peak intensities confirm that a reversible reorientation of the tetragonal structure occurs. Meneghetti and sidhu8 investigated the magnetic structure of Mn-Cu alloys and found antiferromagnetic ordering in furnace-cooled alloys of composition >69 at. pct Mn. Magnetic super lattice reflections occurred at the (110) and (201) positions and the proposed structure was fct with the spins along the c axis. A more complete investigation by Bacon et al.9 confirmed this structure. The magnetic ordering temperature Tn was found to increase linearly with manganese content in the same way as the Ms temperature, and at any composition, Tn > Ms. This relationship suggested that the magnetic ordering was responsible for the cubic — tetragonal transformation in the manganese-rich alloys. The purpose of this investigation was to study the mechanism of high damping and the structural changes that occur on aging. The main technique used was transmission electron microscopy, but X-ray and neutron diffraction experiments were also carried out. EXPERIMENTAL Materials and Heat Treatment. The four alloys, provided by the Admiralty Materials Laboratory. were of nominai composition 60, 70, 80, and 90 Mn and all had low impurity levels, <0.05 pct C, <0.2 pct Fe. This material was cold-rolled to 200-µ strip with intermediate annealing and then given a final heat treatment of 24 hr in the range 800° to 900°C followed by water quenching. An identical heat treatment was given a length of 3/4-in.-diam bar of the 70/30 alloy from which the neutron diffraction specimens were machined. It was suspected that the tetragonal structures would be metastable at room temperature, and so the alloys were not aged until required for experiments. After aging in a salt bath the alloys were water-quenched. Thin Foil Preparation. Initial thinning to 50 to 75 µ was possible in a solution consisting of: 50 ml nitric acid 25 ml acetic acid 25 ml water The surface deposit and grain boundary etching was removed by a final electropolish at around 20 V in an electrolyte consisting of:

Jan 1, 1969

By W. L. Phillips

Stress-strain curves were obtained for single crystals of 70 pct Ag-30 pct Zn tested in tension and shear. Samples tested in tension and shear had comparable resolved shear stresses and stress-strain curves. The {111} <110> slip system was observed. It zoas found that the9.e is a barrier to slip in both latent close -packed directions and that the magnitude of these barriers is proportional to prior strain during easy glide. It was observed that cross-slip in tension and shear was most frequent in crystals with an initial orientation near <100> "Oershoot" zoas observed in tension. The amount of this "overshoot" was independent of initial orientation. AN idealized concept of plastic deformation indicates that a single crystal should yield at some stress that is dependent on crystal perfection and it should then continue to deform plastically by the process of easy glide which is characterized by a linear stress-strain curve and a low coefficient, d/dy, of work hardening. Hexagonal metal crystals generally conform to this ideal concept of laminar flow. In fcc metals the range of easy glide is always restricted in magnitude and it is strongly dependent on orientation, composition, crystal size, shape, surface preparation, and temperature. Since one of the principal differences between the two crystal systems, both of which deform by slip on close packed planes, is the existence of latent slip planes in the fcc crystals, it has been proposed that the transition from easy glide to turbulent flow, characterized by rapid linear hardening, is due to slip on secondary planes intersecting the primary plane.ls Several theories have been proposed to explain the linear hardening and parabolic stages of the stress -strain curve.6"10 The easy-glide region is the least understood of the three stages. The stress-strain characteristics of Cu-Zn, which shows a long easy-glide region, have been extensively investigated."-" In light of recent ideas on dislocations, cross-slip, effect of solute atoms, and stacking fault energy, it was felt that the certain features of this earlier work might be compared with another alloy, Ag-30 pct Zn, which also exhibits a long easy-glide region. Tension and shear stress at room temperatures were employed. The results obtained, together with some interpretation of the observations, are described below. EXPERIMENTAL PROCEDURE The silver and zinc used for mixing the alloys were 99.99 pct pure. The two components were weighed to within 0.1 pct of the weights required fo the alloy composition. They were then placed in a closed graphite mold and the mold and contents were heated in 100°C stages from 500&apos; to 900°C with sufficient time and vigorous agitation at each stage provided to dissolve the silver. The crucible was then heated to 1150°C and agitated violently before being quenched in oil. The resulting alloy rod was machined free of sur face defects and then placed in a graphite mold designed for growing single crystals. The graphite mold was closed with a graphite plug and was encased in a pyrex glass tube which was connected to a vacuum system. The tube and mold assembly were placed in a furnace; the tube was evacuated and the furnace was rapidly heated to a temperature sufficient for fusing and sealing the glass. The glass-encased evacuated mold and contents were then lowered through a vertical furnace. The top section of the furnace was held at 100 °C above the melting point of the alloy. The lowering rate was 1.5 in. per hr. The tension specimens were 1/4 in. diam; the shear specimens were 1/2 in. diam. These specimens were then removed from the mold, etched, and chemically polished with hot (60°C) Chase etch reagent (Crz03-4.0 g, NH4C1-7.5 g, NHOs-150 cc, HzS04-52 cc, and Hz0 to make 1 liter). In preparation for tensile testing, the specimens were carefully machined to a diameter of about 0.200 in. to permit a gage length of 6 in., annealed for 16 hr at 800&apos; to reduce coring, and then cleaned and polished. A modified Bausch-type shear apparatus which has been described previously18 were employed. The gage length was 1/8 in. This shear apparatus was placed in an Instron tensile testing machine. EXPERIMENTAL RESULTS A) Tension. Several specimens were extended at room temperature to determine the effect of initial orientation on the stress-strain curves of Ag-30 pct Zn. The initial orientation and the resolved shear stress supported by the active slip system at various total strains are plotted in Fig. 1. The critical resolved shear stress, t,, initial rate of work hardening, d/dy, and length of the easy-glide region are independent of orientation. The arrival at the symmetry line is shown by an arrow in Fig. 1. During the easy-glide region of the stress-strain

Jan 1, 1963

By R. G. Ward, D. R. Gaskell

Using the maximum bubble pressure technique, the densities of iron silicates at 1410°C have been measured blowing helium, nitrogen, and argon. By ensuring equilibrium between the melt and the blowing gas with respect to oxygen potential and by minimizing tempcrature cycling of the furnace, iron precipitation in the melt has been prevented. Thus the previously reported effect of blowing-gas composition on the densities of the melts has been eliminated. Consideration of the oxygen densities of the melts gives an indication of the structural changes accompanying composition change. The density-composition relationship of iron oxide-silica melts in contact with solid iron has been the subject of several investigations1-7 and considerable disparities exist among the various results obtained. Of these investigations, all except one5 have employed the maximum bubble pressure method. In the most recently reported of these investigations1 the density-composition relationship obtained blowing nitrogen differed from that obtained blowing argon. The measured densities obtained under nitrogen were greater than those obtained under argon, the difference being a maximum at the pure liquid iron oxide composition and decreasing with increasing silica content. This observation rationalized the disparities existing among the results of the earlier investigations, showing that two lines, one for nitrogen and the other for argon, could be drawn to fit all the earlier results. No explanation for this phenomenon could be offered. Chemical analysis of rapidly quenched samples of melt for dissolved nitrogen, and direct weighing measurements, excluded solution of nitrogen in the melt from being the cause of the increase in density. The range of blowing gases was extended by Ward and Hendersons who measured the density of liquid iron oxide bubbling helium, nitrogen, neon, argon, and krypton. The measured density was found to decrease smoothly with increasing atomic number of the bubbling gas. The work reported here is a continuation of the program initiated by Ward and Sachdev7 to study the densities in multicomponent melts in which the iron oxide-silica system is the solvent. As such it is necessary to explain or eliminate the anomalous densities of iron silicates under different atmospheres, and the present rede termination was carried out towards this end. EXPERIMENTAL The maximum bubble pressure method of density determination was again employed and the experimen- tal apparatus used was essentially the same as that used by Ward and Sachdev.7 A molybdenum-wound resistance furnace heated an ingot iron crucible of internal diameter 1 in. containing a 2-in. depth of melt. The bubbling gas was blown through a 1/4 -in.-diam mild steel tube onto the end of which was welded a 2-in. extension of 1/4 -in.-diam ingot iron rod, drilled out to 5/32 in., and chamfered to an angle of 45 deg. The blowing tube was introduced to the furnace through a sliding seal and its position was controlled by a vertically mounted micrometer screw which allowed the depth of immersion to be determined with an accuracy of ± 0.01 cm. A Pt/Pt-10 pct Rh thermocouple was located below the crucible and temperature control was effected initially by means of an on-off controller and later by a saturable core reactor. The bubble pressure was determined by measurement of a dibutyl phthalate manometer using a cathetometer. PREPARATION OF MATERIALS Iron oxide was produced by melting ferric oxide in an inductively heated iron crucible in air. The liquid was quenched by pouring onto an iron plate. Silica was prepared by dehydrating silicic acid at 650°C for 12 hr. RESULTS Before any measurements of the density of a melt were made, the density of distilled water at room temperature was measured bubbling helium and argon. Both gases gave the density as 1.00 ± 0.01 g per cu cm which showed that the density of the manometric fluid (dibutyl phthalate) was not affected by contact with the blowing gas. With the furnace controlled by an on-off temperature controller an attempt was made to measure the density of pure liquid iron oxide by bubbling argon. The furnace atmosphere gas and bubbling gas were dried over magnesium perchlorate and deoxidized over copper turnings at 600°C. It was found that the pressure required to blow a bubble at a given depth increased slowly with time, and thus it was impossible to obtain a unique value for the density of the melt. Inspection of the blowing tube after removal from the furnace showed that rings of dendritic iron had precipitated from the melt onto the immersed part of the tube. This is shown in Fig. l(a) where the various "steps" correspond to different depths of immersion. The precipitation of iron was considered to be due to one or both of two possible causes: i) The composition of the liquid iron oxide is that of the liquidus at the temperature under consideration and can be expressed by the equilibrium

Jan 1, 1968

By G. A. Zeito

Detailed visua1 examination of outcrops was used to ob-tain data on the lateral extent of shale breaks. Thirty vertical exposures belonging to maritie, deltaic and channel depositiorral environrrrents were exatmind, surveyed and photographed. The dimensions of the outcrops ranged from 356- to 8,240-ft long and 25- to 265-ft thick. Shale breaks were found to extend laterally for significant distances. and in some sands terminates by joining other break v much more frequently than by disappearance. Consequently with regard to flaw, a gross sand consisted of both continuous and discontinuous subunits. The degree of continuity of shale breaks as well as the occurrence and spatial distribution of discontinuities were different for the three depositional environments. Statistical eva1uations were performed to determine the confidence level with which estimates derived from outcrops can be applied to reservoir sands. Results of these evaluations revealed that: (I) the lateral continuity of shale breaks in marine. sands is si~nificatit, and the estimates of lateral extent can he applied to reservoir sands with a high degree of confidence (80 to 99 per cent of the shale breaks continued more than 500 ft, with a confidence of 86 per cent); and (2) the tendency for adjacent shale breaks to converge upon each other over small distances in deltaic and channel sands is highly significant (62 to 70 per cent of the shale breaks converged in less than 250 ft, with a confidence of 50 per cent), hut the probable magnitude of the resulting sand discontinuities cannot yet he predicted with adequate confidence. INTRODUCTION Almost all of the efforts devoted to characterization of the variable nature of reservoir sands have been focussed on permeability variations. Among the widely used concepts that have emerged from these efforts are those of stratified permeabilities, random permeabilities, and communicating and noncommunicating layers of different permeabilities. This study is concerned with the presence of interbedded shales and silt laminations. These features are impermeable or only slightly permeable to flow. Therefore, knowledge of the extent to which they continue laterally and the manner in which they terminate within the bodies of gross sands is important for proper description of reservoir flow. Initial field observations made on outcrops revealed that shale breaks and the relatively thinner silt laminae have impressive lateral continuity. They appeared to divide sand sections into separate individual sand layers. Although most of the layers were continuous across the total lengths of the outcrops, some were discontinuous because the- bounding shale breaks converged. Furthermore, the discontinuous layers appeared more prevalent in channel and deltaic sands than in marine sands. Based on these initial findings, a detailed investigation was carried out to determine, quantitatively: (1) the degree of continuity of shale breaks in marine. deltaic and channel sands; and (2) the frequency and spatial distribution of discontinuities in the three environments. PROCEDURE The procedure used to obtain field data from outcrops included visual examination, surveying and photographing each outcrop. The photographs were examined carefully and important outcrop features were traced, measured and recorded. The selection of outcrops for this study was made on the basis that each outcrop should be exposed clearly to permit detailed visual examination of vertical lithology. and it should also be sufficiently long (over 200 ft) to provide useful data on the lateral continuity of lithology. Identification of the depositional environment for each outcrop was made on the basis of bedding characteristics, vertical sequence of lithology and the presence of indicative sedimentary features. Whenever possible, hand specimens of associated shales were collected to determine depositional origin. Almost one-half of the outcrops used in this study required environmental identification; the remainder had already been identified by previous investigators. Several photographs of each outcrop were usually required to cover the entire length of the outcrop. These photographs were taken from one station or several, depending on the terrain, size of the outcrop and distance to the outcrop. A Hasselblad camera, with a standard 80-mm lens and a 250-mm telephoto lens, was used. The telephoto lens permitted photographing outcrops as far as two miles away. Slow-speed films were used. either Panatomic-X or Plus-X. The final operation conducted in the field was that of surveying the outcrops. The distance of an outcrop from a point of observation was determined by a triangulation method using the plane table. The measured distance was then combined with the angle of view of the camera lens to establish a scale to be used on the photographs. Films were processed using standard processing techniques and 4.5X enlargements made. The enlargements of each outcrop were butted together to form a single panorama. Slides were also prepared on several outcrops; these were used whenever greater magnification (wall projection) was required to bring out maximum lithologic detail. The shale breaks and bedding planes in each outcrop were traced on transparent acetate film superimposed on

Jan 1, 1966

By M. Murakami, Y. Murakami, O. Kawano

The formation and growth of Guinier-Preston zones in Al-Zn alloys containing 4.4, 6.8, 9.7, and 12.4 at. pct zn have been studied by the X-ray small-angle scattering method. Particular attention was paid to the effects of small amounts of third elements silver, silicon, and magnesium on the formation and growth of G.P. zones. It was noticed that an appreciable number of G.P. zones were formed during the course of rapid cooling and that the size, volume fraction, and number of these G.P. zones were influenced by the existence of the third elements. During subsequent aging it was also found that the addition of both silver and silicon lowered the temperature for the growth of G.P. zones, whereas the addition of magnesium raised it. These results were explained in terms of the mutual interactions among zinc atoms, vacancies, and the third elements. A number of studies on the formation and growth of Guinier-Preston zones in Al-Zn alloys have been reported.1-4 Panseri and Federighii have found that the initial stages of zone growth take place at temperatures as low as around -100°C. For investigation of the mechanism of the initial stages of zone growth, growth studies must be carried out at low temperatures. In order to investigate the possibility of the formation of G.P. zones by the nucleation mechanism or the spinodal decomposition during quenching which was reported by Rundman and Hilliard,5 the examination of the as-quenched structure must be performed. In this paper the investigation of the early stages of the formation and growth were determined by means of the X-ray small-angle scattering method. With this technique, change of X-ray scattering intensities was measured while quenched specimens were heated slowly from liquid-nitrogen temperature to room temperature. At as-quenched state and after heated to room temperature, investigation of zone size, volume fraction, and zone number per unit volume was carried out. Measurements on these specimens yielded information on the early stages of zone formation and growth. Measurements were made also on specimens quenched to and aged at room temperature. From these measurements the previously reported model6 for the later stages of growth is confirmed; namely, the larger zones grow at the expense of smaller ones. Three elements, silver, silicon, and magnesium, were chosen as the third elements for the following reasons: Silver. In the binary A1-Ag alloy the spherical disordered 77&apos; zones were observed immediately after quenching.7 Therefore, in the Al-Zn-Ag alloys, it is suggested that silver atoms might induce cluster formation during quenching. Also, since the migration energy of the zinc atoms was found to be raised by the addition of silver atoms,&apos; silver atoms may have a great effect of the zinc diffusion, especially during low-temperature agings. Silicon. The effects of the addition of silicon atoms were found to be marked, especially at low-tempera-ture aging. In the binary Zn-Si system, no mutual solid solubilities between silicon and zinc9 and no in-termetallic compounds10 are reported to exist. Shashkov and Buynov11 investigated the behavior of silicon atoms in Al-Zn alloys and showed that silicon was not in the G.P. zones. The interaction between silicon atoms and vacancies is strong enough to increase the quenched-in vacancy concentration.* Magnesium. Magnesium atoms are reported to trap quenched-in vacancies and after much longer aging times these trapped vacancies will become free and act as diffusion carriers.13 Therefore at intermediate aging times, the diffusion of zinc atoms in Al-Zn-Mg alloys will be slower than in the binary Al-Zn alloys, whereas at longer times zinc diffusion will become faster. EXPERIMENTAL PROCEDURE The alloys used in this investigation had compositions of 4.4, 6.8, 9.7, and 12.4 at. pct Zn with or without 0.1 and 0.5 at. pct Ag, Si, or Mg. The alloys were prepared from high-purity aluminum, zinc, silver, silicon, and magnesium, with each metal having a purity better than 99.99 pct. The analyzed composition of the specimens is given in Table I. The measurements of the X-ray small-angle scattering were carried out with foils of 0.20 mm thick. The change of the scattering intensity was always measured at the fixed scattering angle of 20 = 2/3 deg. This angle exists nearly on the position of the intensity maximum. The value of the interparticle interference function14 which has large effect in this range of angles may not change abruptly in the case of the spherical shape of small zones. Therefore, from the above considerations, it is concluded that an increase of the intensity measured at this constant angle corresponds to an increase of the average radius and volume fraction of G.P. zones. The specimens were homogenized at 500°, 450°, and 300°C for 1 hr in an air furnace. For the study of the formation and growth at low temperatures, the foil

Jan 1, 1970

By A. S. Odeh

The mechanism of two-phase flow in porous media has been a subject of wide controversy. One of the properties essential for understanding the dynamic behavior of two-phase flow is relalive permeability. Relative permeability to a certain phase is defined as the ratio of the effective permeability of that phase to its permeability when it is the only fluid present and powing. In this research, a theoretical analysis was made to determine the effect of viscosity ratio between the non-wetting and the wetting phase on relative permeability. Experimental work was conducted to test the validity of the derived equations. The experiment was conducted on four natural cores. Four oils were used as the non-wetting phases with a viscosity range of 0.42 to 71.30 cp and two wetting phases with a viscosity range of 0.86 to 0.96 cp. Oil and bring were made to flow simultaneously at various ratios, and relative permeability curves were constructed. A total of eight relative pertileability cycles representing eight viscosity ratios were run oil each sample. It was found that relative permeability to the non-~cletting phase varies with viscosity ratio. The relative effect of this variation on relative permeability values was a function of the sample&apos;s single-phase permeability, decreasing with its increase. It was concluded that, for .samples of single-phase permeability over I darcy. the effect of viscosity ratio could be disregarded, and relative permeability would be, in effect, a function of satrtration only. INTRODUCTION Two-phase as well as multiphase flow occurs in many fields of science. This type of flow is of particular interest in petroleum production. The knowledge of relative permeability, which describes the dynamic behavior of two-phasc as well as multiphase flow, is essential for solution of problems arising in that field. Thc relative permeability ot a porous medium to a given phase in multiphase flow. is generally considered to be only a function of the saturation of that phase, independent of the properties of fluids involved and ranging in value from zero to unity. Work by Leverett&apos; and Leverett and Lewis&apos; apparently supports this concept. In his experiments Leverett used a clean, packed unconsolidated sand of high permeability (3.2 to 6.2 darcies) with two phases (water and oil) flowing and a viscosity ratio range of 0.057 to 90.0. His results showed that the wide range of viscosity had practically no effect on relative permeability-saturation relationship. Recently accumulated evidence from work performed by several laboratories and a paper by Nowak and Krueger,2 in which relative permeability to oil of a few core samples in the presence of interstitial water was considerably greater than single-phase permeability to water, cast some doubt on the conclusions reached by Leverett&apos; and subscribed to by a large number of individuals in the oil industry. One explanation advanced to explain this behavior states that it is caused by the variable extent of hydra-tion of clay minerals present in the sand. The greater the water saturation, the greater will be the area of contact between water and clay minerals; therefore, the greater will be the extent of swelling with corresponding reduction in permeability. Yuster4 presents another explanation for the recently accumulated evidence. Utilizing Poiseuille&apos;s law, he analyzed concentric flow in a single capillary where the non-wetting phase flows in a cylindrical portion of the capillary and concentric with it. The wetting phase flows in the annulus between the non-wetting phase and the capillary wall. The equations obtained indicate that relative permeability to the non-wetting phase is a function of saturation and viscosity ratio. Although Yuster&apos;s equations show that fractional rel-ative permeability to oil could be greater than unity, as was indicated by the data of Nowak and Krueger,1 they failed to present an explanation to the experimental data of early investigators such as Leverett.1 Due to the importance of relative permeability in understanding the flow behavior of petroleum reservoir fluids, this work—theoretical as well as experimental —was undertaken to determine whether relative permeability is a function of saturation only as was concluded by Leverett1 or a function of saturation and viscosity ratio as was theorized by Yuster.4 THEORETICAL ANALYSIS An equation will be derived for the rate of oil flow through a porous medium that is initially filled with water. Based on this equation, an analytic expression for relative permeability will be developed. The porous medium will be assumed to consist of .straight circular capillaries of different radii. It will also be assumed that there are no interconnections among the capillaries and no mass transfer across the oil-water interface. Consider a porous sample initially saturated with a wetting phase (water). As a non-wetting phase (oil) is

By Harold M. Feder, Robert V. Schablaske, Irving Johnson, Ewald Veleckis

The stoichiometry, structure, and stability of the internzediate phases formed between zinc and some of the rare earth (RE) metals were systematically exarnined by means of a recording effusion balance and X-ray diffraction analyses. In the La-, Ce-, PY-, Nd-, and Y-Zu systems, at or below about 600 C, the following sequences of phases (REZnx) were found: La, x = 1, 2, 4.0, 5.25, 7.3, 17/2, 11, and 13.0;&apos; Ce, x = 1, 2, 3, 11/3, 4.3, 5.25, 7.0, 17/2,* and 11; Pr,x = 1,2, 3, 11/3 ,* 4.3, 5.3(?), 7.0, 17/2,* and 11; Nd,x = 1,2, 3,* 11/3,* 4.3, 6.5, 8.5,* and 11; Y,x = 1,2,3, 11/3, 4.5, 5.0, 17/2,* and 12.* The structure types of all these phases were classified. In addition, lattice parameters were obtained for the first time for the pluses denoted by asterisks. In the absence of de tectable valency or electronegativity effects the systesnatic trends in the results have been ascribed to the effects of&apos; the lanthanide contraction. For example, the maximum number of zinc atoms in the coordination polyhedron surrounding the RE atom decreases from twenty-four to twenty-two to twenty as the size of the RE atom decreases. THE structures and compositions of a great many intermetallic phases (e.g., the Laves phases) are known to be based primarily, but not exclusively, on the space-filling efficiency of various modes of packing together atoms of different sizes. The valencies and electronegativities of the constituent atoms are, however, also influential. In extreme cases hypothetical intermetallic phases which fulfill the efficient spacefilling requirements may not be present in the constitutional diagram because of thermodynamic instability brought about by the operation of valency or electronegativity factors. Hence, for a detailed study of the influence of atomic size on alloy structure and composition, it would be desirable to minimize variations of valency and electronegativity. The intermetallic phases formed by the rave earths (RE) with some common partner offer an excellent opportunity for isolating the effects of size from those of valency and electronegativity. The rare earths exhibit a large, but smooth, decrease in size (the lanthanide contraction) in the series from lanthanum to lutetium when inter comparison is made for a common valence state, e.g., isolated atoms or trivalent ions. The elements yttrium and scandium are frequently included as pseudo rare earths; their sizes place them in the vicinity of dysprosium and lutetium, respectively. The electronegativities of RE elements vary by less than 10 pet. The trivalent state is the most common; however, the well-known tendency of cerium, praseodymium, and terbium to achieve higher valencies, and of samarium, europium, and ytterbium to seek lower valencies, requires that caution be exercised in the assumption of equal valencies. In the present study the existence, constitution, and structure of each of the numerous intermediate phases formed by zinc with lanthanum, cerium, praseodymium, neodymium, or yttrium were examined systematically and in detail. The investigation was conducted by a recording effusion balance technique and by X-ray diffraction analysis. The results enrich our knowledge of the phase diagrams of these systems. In addition, they present some clear-cut evidences of the operation of the size factor alone. EXPERIMENTAL PROCEDURE Apparatus. The mode of operation of the recording effusion balance and its application to phase studies have been discussed in detail elsewhere.&apos; In this work, an effusion cell containing a finely divided alloy was suspended within an evacuated tube from the beam of an analytical balance. The tube was immersed in a massive molten salt bath whose temperature was controlled to within 0.5o C during each experiment. The loss in weight of the alloy owing to effusion of zinc* was continuously recorded. Two effusion cells, 1/2 in. diam by 1 in. high, were machined from tantalum rods. Two orifices were drilled laterally into the walls of each cell. The orifice areas were determined by calibration with pure zinc: cell A had a total orifice area of 6.5 x 10-41 sq cm, and cell B an orifice area of 9.8 x 10-3 sq cm. By appropriate choices of orifice area and temperature the wide range of volatilities from pure zinc to pure rare earth metal could be investigated. X-ray diffraction powder photographs were made at room temperature with a 114.6-mm Debye-Scherrer camera with both filtered CuKa radiation and filtered CrKa radiation. Lattice parameters were refined by a computer-programmed least-squares analytical treatment which incorporated appropriate extrapolation techniques.2 Frequent use was also made of a special computer program3 designed to generate a powder pattern from an assumed structure in order to verify structural assignments. Materials. Lanthanum, neodymium, and yttrium were purchased from the Lunex Co., cerium from the Cerium Metals Corp., and praseodymium from the St.

Jan 1, 1968

By E. F. Koch, J. L. Walter

oriented crystals of iron and iron with 3, 5, and 6.25 pct Si were rolled to reductions of 10 and 70 to 97 pct at room temperature. Similarly oriented crystals were deformed in tension. Dislocation substructures of the deformed crystals were observed by transmission electron microscopy to determine the effect of silicon on the formation of substructures. Pole figures were obtained to relate orientation changes to substructure. When rolled 10 pct, the iron crystals and the 3 pct Si-Fe crystals formed cells, 1 and 0.2 u in diameter, respecliuely. Cells were absent in the higher-silicon crystals. Extended dislocations and possible stacking faults were observed in the 6.25 pct Si-Fe crystal rolled 10 pct and annealed at 650°C. The stacking-fault energy was estimated to be 20 ergs per sq cm. Rolling to 70 pct resulted in the formation of sub-bands (0.9 µ wide) ill the iron crystals and transition bands (containing 0.2-µ-wide subbands) in the 3 pct Si crystals. No subbands formed in the 5 pct Si-Fe crystal until it was ankzealed. SliP occurred on (112) planes ill tension. The slip traces on the 3 pct Si crystal were wary while those on the 5 pct Si crystal wvere straight. The strain-hardening coefficient for the 5 pct Si crystal was nearly zero. Cells did not form, at least at elongations up to 10 pet. The results suggest that cross slip of iron is restricted by additions of silicon beyond about 3 pct possibly by formation of immobile extended dislocations. IN a previous paper&apos; the authors described the substructures developed in (100)[001]-oriented crystals of 3 pct Si-Fe which were rolled to reductions of 10 to 90 pct at room temperature. At low reductions (10 to 20 pct) cells, approximately 0.2 to 0.3 ja in diameter, were formed. The cell walls consisted mainly of edge dislocations. With increasing reduction (up to 50 pct) the cells were seen to elongate in the rolling direction. In certain regions of the crystal there were significant reorientations which were characterized as rotations about an axis normal to the (100) or rolling plane. These regions were called "transition bands". The regions in which there were no reorientations were called (&apos;deformation bands". At reductions of 60 to 70 pct the elongated cells in the transition bands became sub-bands separated by low-angle tilt boundaries with angles of disorientation of about 2 deg. The elongated cell structure in the deformation band was replaced by a general distribution of dislocations. It was noted that the width of the subbands in the transition bands remained 0.2 to 0.3 µ; i .e., the width of the subbands was the same as the initial cell diameter for reductions up to at least 70 pct. From this, and from considerations of the mechanism of formation of the transition bands,&apos; it was concluded that the subbands evolved directly from the initial cells. In order to check this conclusion, it was decided to examine the relationship between initial cell diameter and width of subbands produced by large rolling reductions. Cell size is known to be dependent upon the temperature of deformation.2,3 However, preliminary experiments with 3 pct Si-Fe crystals indicated that the change in cell size with increasing temperature of deform,ation was not sufficient for the present purpose. On the other hand, cell diameters generally reported for iron deformed at room temperature2&apos;3 range from 1 to 2 p, a factor of 3 to 10 larger than the cells in 3 pct Si-Fe rolled to 10 pct reduction,&apos; indicating the possibility of a marked dependence of substructure (at least in terms of cell size) on the amount of silicon in iron. Thus, the investigation was enlarged to include the study of the effects of varying silicon content on substructure in lightly rolled as well as in heavily rolled crystals of iron and iron with 3, 5, and 6.25 pct Si. The crystals used in this study all had the same orientation, (100)[001], with respect to rolling plane and rolling direction. These were rolled to reductions of from 10 to 97 pct and the substructures determined by electron transmission microscopy in both the rolled state and after annealing. In addition, stress-strain curves were obtained from (100)[001]-oriented crystals of iron and 3 and 5 pct Si-Fe to determine the effect of silicon on tensile properties. The dislocation substructure of the tensile specimens was also determined for Samples pulled to 2 and 10 pct elongation at room temperature for comparison with the substructures produced by rolling. 1) EXPERIMENTAL PROCEDURE Crystals with 3, 5, and 6.25 pct Si were prepared by annealing 0.012-in.-thick sheets of high-purity Si-Fe in purified argon at 1200°C to effect growth

Jan 1, 1965

By R. Gibson, F. S. Turneaure

The tin deposit of Monserrat, Bolivia, consists of one major vein 1600 m in length. The ore is unusual because of the notable quantity of teallite, even though cassiterite is the principal tin mineral. The deposit, formed at shallow depth under a wide range in temperature, may be classed as xenothermal. Polished sections reveal a complex history of replacement, with low-temperature minerals deposited before high-temperature minerals. THE Monserrat mine1&apos;2 of the Compania Minera Monserrat is located 11 km east of Callipampa, a station on the Antofagasta and Bolivia Railway some 55 km south of Oruro. The mine lies in a group of low hills on the east slope of a broad valley of northerly trend. The valley is separated from the altiplano to the west by a prominent ridge that rises several hundred meters above the surrounding country (fig. 1). Callipampa is situated a short distance west of the ridge, near the east margin of the altiplano. The elevation at Callipampa is 3700 m and at the mine 4100 m. Monserrat is near the northeast limit of what may be called the Poopo-Pazna district, an area of northwesterly trend about 25 km in length and 15 km in width. The district includes the tin-silver prospects of Poopo to the north, the zinc-tin deposits of Salvador to the southwest, and the tin-tourmaline veins of Avicaya to the south. Along the prominent ridge already mentioned, which forms the western limit of the district, there are several tin and antimony prospects including the Trinacria mine, which is famous for its fine specimens of cylindrite. Although the principal ore mineral is cassiterite, the tin deposit of Monserrat contains an unusual amount of teallite. Cassiterite occurs in part as a finely granular mixture with sulphides of iron and zinc and in part as needle tin of late hypogene age. The regional structure is dominated by broad folds typical of the Andes of Central Bolivia and similar to those of the Llallagua district. The area adjacent to the Monserrat mine is underlain by thin-bedded shale somewhat variable in color but predominantly dark grey to black. The beds strike northwest and dip at low angles southwest, forming part of the northeast limb of a major syncline. A resistant sandstone formation, which underlies the black shale, crops out along a ridge east of the mine and also accounts for the high ridge to the west that was previously mentioned. No igneous rock of any kind is found at Monserrat. The nearest intrusive bodies known are the irregular dikes and masses of quartz porphyry at Avicaya about 10 km to the south. Mine Workings The Monserrat property includes one main vein, which can be followed on the surface for 1600 m, and two or three branch veins of distinctly minor importance. The principal haulage tunnel, referred to as the San Carlos adit or level III, extends northeasterly for 1700 m, following the main vein throughout most of this distance. Above the adit, there are

Jan 1, 1951

By F. S. Turneaure, R. Gibson

The tin deposit of Monserrat, Bolivia, consists of one major vein 1600 m in length. The ore is unusual because of the notable quantity of teallite, even though cassiterite is the principal tin mineral. The deposit, formed at shallow depth under a wide range in temperature, may be classed as xenothermal. Polished sections reveal a complex history of replacement, with low-temperature minerals deposited before high-temperature minerals. THE Monserrat mine1&apos;2 of the Compania Minera Monserrat is located 11 km east of Callipampa, a station on the Antofagasta and Bolivia Railway some 55 km south of Oruro. The mine lies in a group of low hills on the east slope of a broad valley of northerly trend. The valley is separated from the altiplano to the west by a prominent ridge that rises several hundred meters above the surrounding country (fig. 1). Callipampa is situated a short distance west of the ridge, near the east margin of the altiplano. The elevation at Callipampa is 3700 m and at the mine 4100 m. Monserrat is near the northeast limit of what may be called the Poopo-Pazna district, an area of northwesterly trend about 25 km in length and 15 km in width. The district includes the tin-silver prospects of Poopo to the north, the zinc-tin deposits of Salvador to the southwest, and the tin-tourmaline veins of Avicaya to the south. Along the prominent ridge already mentioned, which forms the western limit of the district, there are several tin and antimony prospects including the Trinacria mine, which is famous for its fine specimens of cylindrite. Although the principal ore mineral is cassiterite, the tin deposit of Monserrat contains an unusual amount of teallite. Cassiterite occurs in part as a finely granular mixture with sulphides of iron and zinc and in part as needle tin of late hypogene age. The regional structure is dominated by broad folds typical of the Andes of Central Bolivia and similar to those of the Llallagua district. The area adjacent to the Monserrat mine is underlain by thin-bedded shale somewhat variable in color but predominantly dark grey to black. The beds strike northwest and dip at low angles southwest, forming part of the northeast limb of a major syncline. A resistant sandstone formation, which underlies the black shale, crops out along a ridge east of the mine and also accounts for the high ridge to the west that was previously mentioned. No igneous rock of any kind is found at Monserrat. The nearest intrusive bodies known are the irregular dikes and masses of quartz porphyry at Avicaya about 10 km to the south. Mine Workings The Monserrat property includes one main vein, which can be followed on the surface for 1600 m, and two or three branch veins of distinctly minor importance. The principal haulage tunnel, referred to as the San Carlos adit or level III, extends northeasterly for 1700 m, following the main vein throughout most of this distance. Above the adit, there are

Jan 1, 1951

By C. S. Yust, C. S. Morgan

ThIS note reports the observation of masses of dislocation etch pits around the weld necks of small single-crystal particles of calcium fluoride sintered to a cleaved face of a larger CaFz crystal. Crystal particles in the -50 +I00 mesh size range were placed on freshly cleaved CaFz surfaces and heated at 1250°C for 30 min in a tantalum container in an argon atmosphere. The sintered specimens were then etched at room temperature for 40 to 50 min in a 2 pct sulfamic acid solution which is a selective etch for dislocations in caF2.&apos; Figs. 1 through 3 show the masses of dislocation etch pits observed around weld necks after etching. In some cases, particles were gone after removal of the specimens from the furnace although weld necks were readily visible. In other instances, no etch pits formed around a weld neck. A possible cause of concentrations of dislocations on the crystal surface is mechanical deformation of the base crystal when particles are dropped on it. If such a deformation does occur, it would be much smaller than that caused by the light punching of a crystal with a sharp instrument which results in large concentrations of etch pits. However, crystals deformed by punching with the sharp instrument and annealed at the conditions of these experiments (1250°C for 30 min) before etching showed no concentrations of dislocation etch pits. It is obvious that dislocations from the much smaller deformations, possibly created when particles are placed on the surface, would also anneal out. Etching of large crystals which had particles placed on them in the usual manner but which were not heated showed no dislocation concentrations such as shown in Fig. 1. The magnitude of dislocation etch-pit concentrations did not vary with extensive variation of the cooling rate. The appearance of many of the etch-pit clusters is typical of a well-annealed condition, indicating that the dislocation concentrations formed before the specimen temperature was lowered. Therefore, it is evident that thermal stresses in the neck area did not create the deformation indicated by the presence of the dislocations. The possibility exists that the etch-pit concentrations at places where particles had been removed may be the result of deformation accompanying the fracture of the sintered bond. That this is not so was demonstrated by breaking off particles around which no etch pits occurred. Re-etching never resulted in the large concentrations observed at sintering sites. The stress available to effect material movement during sintering of two particles will depend on the geometry at the contact point but can easily exceed the macroscopic yield stress in CaFz systems. It appears that the plastic deformation observed results from sintering or simply from the weight of the small particles. It has been previously argued that plastic flow makes an important contribution to the initial densification of oxides having the fluorite crystal structure.2p3 If plastic deformation occurs, it would begin as soon as the temperature is sufficiently high

Jan 1, 1967

By P. Niessen, S. J. Bercovici

RECENTLY Aust et al.&apos; proposed a model of non-equilibrium grain boundary segregation based on a vacancy gradient induced uphill diffusion process of solute to grain boundaries. According to their proposal, solute atoms which are attracted to vacancies would, during the cooling of a sample, migrate with vacancies toward grain boundaries (vacancy sinks) and thereby enhance the solute concentration in boundary regions. For solute atoms which are not attracted to vacancies no such boundary solute enrichment would be expected. These concepts were given experimental support by boundary and bulk mi-crohardness measurements of various thermally treated dilute zinc and lead alloys and also doped aluminum oxide. The underlying assumption in their work was that solute enrichment in boundary regions is indicated by higher microhardness values. From thermodynamic considerations1&apos;2 it appears that the solid-liquid solute distribution coefficient (K), defined as the concentration of solute in the solid to the concentration of solute in the liquid at equilibrium, indicates whether attractive or repulsive forces exist between vacancies and solute atoms. K < 1 indicates a solute-vacancy attractions, K > 1 indicates no, or a repulsive, vacancy-solute interaction. This note is to report on observations of different grain boundary etching phenomena in high purity zinc alloys. These phenomena appear to depend on whether a K < 1 or K > 1 solute is present. In experiments designed to measure directly the solute enrichment in grain boundary regions, samples of zone refined zinc with 0.1 at. pct solute additions were cooled from 380°C at a rate of 3°C per min. A surface layer of approximately 50 was then removed from the samples by chemical polishing. The samples&apos; surfaces were then protected by a chromating treatment such that in a subsequent etch only grain boundary regions were dissolved. The dissolved regions were approximately semicircular troughs, 10 µ in width. The grain boundaries were usually in the middle, i.e., at the bottom, of this trough. For zinc containing the K < 1 solutes cadmium and aluminum, the grain boundary was always indicated by a ridge as shown in Fig. 1. For pure zinc, and zinc containing the K > 1 solutes copper and gold, a groove at the bottom of the trough indicated the boundary position, Fig. 2., To test if these different grain boundary etching behaviors were possibly connected with the segregation process discussed above, the Zn-Cd alloy was again heated to 380°C and quenched into brine. After surface protection and etching it was found that this specimen no longer exhibited the grain boundary ridges but rather grain boundary grooves as shown in Fig. 2. It would appear, therefore, that the boundary ridge is a consequence of a process occurring during the slow cooling of the samples. From absorption spectrophotometric analysis it was found that for slowly cooled samples containing K < 1 solutes, the solute/zinc ratios of the material from the boundary trough were consistently considerably higher than the solute/zinc ratios of the bulk alloys. This boundary region solute enrichment was not observed in quenched samples. It is concluded therefore, that the boundary ridge shown in Fig. 1 is directly or indirectly connected with nonequilibrium solute segregation.

Jan 1, 1970

By Charles Luner

ALTHOUGH the kinetics of the atmospheric oxidation of tin have been studied,1-3 the kinetics in pure oxygen have not been reported. This note presents some results of the kinetics of the oxidation of tin foil in pure oxygen. The tin foil used in this investigation was 99.78 pct pure, the two major impurities being Pb (0.17 pct) and Sb (0.024 pct). The foil was degreased and air-dried prior to oxidation. The air-formed film was estimated by coulometric reduction4 of the surface oxides to be about 25A. The samples, which were in strip form and had a total geometric surface area of about 300 sq cm, were first evacuated at room temperature in an oxidation bulb to 1 X 10 -5 mm Hg and subsequently degassed for 1 hr at the temperature of the experiment. Spectroscopically pure oxygen was then introduced into the bulb. The rates of oxidation were measured by following the rate of pressure change due to oxygen consumption in a closed system, the volume of which was sufficiently large so that the pressure change during an experiment was 10 to 15 per cent of the total pressure. An oil-mercury manometer,5 with a sensitivity of 3 X x mm Hg (which corresponds approximately to 5 X 10 -7 gm of oxygen) was used to measure the pressure change. The oxidation bulb was heated by an oil-bath and controlled to within -10.3 C. The reproducibility of the rates was good, as determined by the coincidence of rates at 190oC for duplicate experiments. Fig. 1 shows the oxidation curves in the temperature range 168 to 211.5oC at 8 mm Hg pressure. The effect of pressure on the rate of oxidation at 190°C is also shown. The rate of oxidation was not markedly affected by changes in pressure in the range 4 to 9 mm Hg, except perhaps at the lowest pressure, 4 mm Hg, where after about 70 min there appeared to be a decline in the rate, as compared with the rate at the higher pressures. At the lower tem- perature, 168oC, and for short reaction times, it is difficult to distinguish between a linear relationship and a slight curvature in the oxidation rate. However, for longer times, there was a somewhat larger indication of curvature. The samples after oxidation were gold-colored in appearance. The oxide that was formed at 170°C was identified as a-SnO by reflection electron diffraction. This is in agreement with results obtained by other workers.6, 7 The rate data best fitted the logarithmic-oxidation rate law, w = K1n ln(1 + -t/to) [1] where w is the weight of oxygen consumed, t is the time, and K In, and to are constants. First estimates to were obtained according to the method of Taylor Thon8 and were then employed to obtain the best simuItaneous estimates of to and K In, that would fit the logarithmic expression. These estimates were found numerically, so that the residual variance could be minimized. The calculations were performed on an

Jan 1, 1961

By M. M. Slotnick

IT was once aptly said that a sign of approaching senility is ceasing work on a subject and beginning to talk about it. Perhaps that explains why, after many years in which part of my duties has been the training of college men in various branches of petroleum exploration geophysics, I have now begun to talk about it. In making an outline of what I believe ought to be discussed under the general heading of the title, I found it almost impossible to subdivide the ideas into an ordered set of discrete subjects. Rather, the pertinent remarks seemed to interlock almost everywhere. The consequence is that it will be necessary to start with the conclusions and then try to justify them by jumping back and forth. However, based on the types of men with whom I have had to deal, the subject naturally divides itself into two parts. In the first part, I should like to deal with the case of those undergraduates whose natural bent is toward the physical sciences and who may decide to enter the geophysical fold as a career. The other part will deal with those many men, geologists and engineers for the most part, who have drifted into exploration geophysics by one means or another, and whom it is necessary to train for geophysical work while they are occupied in their routine jobs. Here it may be in point to remark that most men in exploration geophysics at present have been developed from precisely the latter group, and that the problem of training here is of great importance even though, in this paper, it will perforce occupy the secondary place. TRAINING OF A GEOPHYSICIST The outstanding reason for the perplexing problem on the training of a geophysicist is that ideas differ on the answer to the question: "What is a geophysicist?" In any of the scientific "specialties," like physics, for example, it is relatively simple to pigeonhole a man as being qualified to call himself a physicist. That appellation applied to an individual does not mean that he has mastered only the branches of intellectual endeavor usually associated under the broad name of "physics." We expect him also to have a more than mere acquaintance with mathematics and chemistry and some understanding of most of the other sciences. But note this important point-we expect our physicist, whom we have chosen as an example, to be intelligently trained so that, if necessary, he can and will know how and where he can get the proper information on a subject in which he is not a specialist; he will know how to absorb that information and turn it to his uses. It seems to me that this is the outstanding characteristic of a man who can truly call himself a scientist: that he is a specialist in one of the broad branches of science and that he has enough training and discipline in the scientific approach so that, when called upon to do so, he can intelligently absorb knowledge from another bordering science (and all sciences not only border upon one another to some extent, but more often, overlap one another), and

Jan 1, 1941

By A. C. Losekamp, R. M. Fincel, J. B. Conway

TANTALUM like several other metals exhibits a great affinity for or reactivity with certain gases. Tested in atmospheres which are not completely pure this metal becomes contaminated by certain impurities (notably nitrogen, oxygen, and hydrogen) with a resultant change in various properties. Well-known are the drastic changes in hardness, ductility, and electrical resistivity. Also previously recorded are the distortions of the lattice1,2 accompanying the increased content of oxygen and nitrogen in tantalum. This pronounced affinity for certain gases along with the significant property variations thereby produced makes it necessary to observe additional experimental precautions in making various property determinations with tantalum. Some recent measurements of the linear thermal-expansion characteristics of tantalum have made this point quite emphatically. Failure to observe the greatest precautions in reducing the contaminating influence has led to some extremely distorted results. Not only does such operation lead to different heating and cooling curves during the thermal-expansion measurements, but upon cooling to room temperature the sample is found to have suffered a permanent (actually semipermanent since the specimen can be returned to its original length by a 3-hr degassing treatment in vacuum at 2300°C) elongation. In addition, subsequent heatings will not follow the initial heating curve unless the expansion measurements are based on the actual specimen length at the beginning of the heating cycle. These thermal-expansion measurements were made by positioning the specimen horizontally at the longitudinal midpoint of a 20-in.-long, 4-in.-diam resistively heated tungsten tube furnace. The specimens were in the form of 20-mil sheet formed into a sharp U-shape about 0.3 in. in width and 0.3 in. in depth. Fiducial marks in the form of 0.010-in. holes drilled at either end of the 2.5-in.-long sheet specimens were viewed by a paired filar micrometer telescope system mounted on an Invar bar on the top of the furnace. Tests were made in helium with temperatures measured by a Pt/Pt-lORh thermocouple to 1000°C; above 1000°C temperature was measured by means of an optical pyrometer sighted into a black-body hole drilled into the specimen-holding fixture in the vicinity of the specimen. Previous tests with black-body holes drilled in a 0.25-in.-diam rod specimen had confirmed the temperature uniformity between specimens and specimen-holding fixture in this furnace. A typical thermal-expansion curve for arc-cast tantalum in helium is shown in Fig. 1 for the case where no attempt is made to remove all the impurities from the cover-gas atmosphere. The initial heating curve appears smooth and has a shape characteristic of all metals. However, it is known that the sample begins absorbing impurities at temperatures above 1000°C which are sufficient to distort the lattice and lead to specimen lengths which are somewhat larger than would be obtained in the absence of contamination. During the cooling cycle the expansion curve is seen to be significantly different from the heating curve. This is due to the impurity content causing a semipermanent (i.e., permanent until the impurities are removed by vacuum degassing) deformation which will not allow the speci-

Jan 1, 1965