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By C. R. Watts

The feasibility of producing composites containing nickel or molybdenum fibers in a beryllium matrix was inrestigated. The composties studied were jabricaled by powder mallurgical techniques. The 1-mil-diarr nickel fibers reacled completely below 900°C, converling the fibers .from nickel to Ni5Be2,. As the /LO/-pressing temperalure as raised above 1110oC, tlie nickel diffused outward from the beryllide fibers. The solid solubility of nickel in beryllium was clboul 20 wt pet at the 1100°C pressing temperature a1 the zone-fiber interface. The 1.5-mil-diam molybdenum fibers slzolred no evidence of reaction and little evidence of diffitsion after pressing at 900°C. Between 1000° and 1050°C pressing conditions, the fibers began lo react , producing 1ayers of MoBe2 and MoBe12, respectively surrounding the molybdenurn core. The struture remained the same at 1100°C with no evidenre of solid solubility of the molybdenum in the berylium or vice versa. In recent years a considerable amount of attention has been devoted to the determination of methods for improving the mechanical properties of materials through the use of fiber or whisker reinforcement. Previous work with metal matrix composites indicates that the study of the chemical compatibility of the fiber and matrix is an area requiring greater understanding. The metal-metal or ceramic-metal interface is frequently subject to chemical reactions that may result in the formation of hard brittle intermetal-lic compounds and/or low melting point eutectic compositions. The reaction products may reduce both the low-temperature and elevated-temperature strength of the composite by weakening the fiber-matrix bond, producing premature failure at the interface. It is well-known that most metal-metal systems and many metal-ceramic systems of interest for structural composites are thermodynamically unstable,'-" particularly at elevated temperatures. If, however, the rate of reaction under the conditions of fabrication is sufficiently low. composites can be fabricated that can be used efficiently for indefinite periods at low temperatures and for short periods at elevated temperatures. This paper presents the results of a series of tests to determine the compatibility of nickel and molybdenum fibers with beryllium at various hot-pressing temperatures. Nickel was selected as a candidate fiber material primarily because the relatively ductile fibers might be useful as crack arresters in applications such as ballistic impact where crack growth can result in catastrophic failure. The high density and the reactivity of nickel were primary factors detracting from its selection as a possible reinforcement. Molybdenum with a modulus of elasticity of 52 Xlo6 psi is one of the few metallic materials having a modulus higher than beryllium (42 X lo6). Its high modulus, coupled with its refractory characteristics, made molybdenum an attractive candidate for a relatively stable fiber reinforcement for beryllium. Its density, being higher than that of nickel and over five times that of beryllium: detracted from its other characteristics. EXPERIMENTAL PROCEDURE The specimens were prepared from beryllium powder with a dispersed phase of fibers by powder metallurgical techniques. P-20 grade powder, Table I, from Berylco was used as the matrix material. Short lengths of 0.001-in.-nominal-diam nickel fibers supplied by the Sigmund Cohn Corp. and 0.0015-in.-nominal-diam molvbdenum fibers obtained from the General Electric Co. were used as the dispersed phase. The composite constituents were combined under an argon atmosphere by mechanically mixing the powders and fibers. The compositions used were nominally 1 vol pct fibers. After mixing. the composites were hot-pressed into a-in.-diam pellets under an argon atmosphere at 900°, 1000". 1050". and 1100°C at a pressure of 6000 psi with no hold time at these temperatures so that a comparison could be made between the resultant microstructure and hot-pressing temperature. The billet was heated at a rate on the order of 30°C per min to the desired temperature and then cooled at a somewhat slower rate. The microstructure obtained should be considered as characteristic of the integrated time-temperature history of the sample, as well as the maximum temperature attained. Upon removal from the hot-pressing dies. the specimens were cut. mounted. and polished by standard procedures. No etchant was used in specimen preparation. Photomicrographs, electron microprobe scans, and electron back-scatter pictures were made. X-ray dif-fractometer patterns were made of several of the specimens. but only the lines for beryllium could be resolved. Specimens for optical and electron microprobe examination were selected partially for the roundness of the cross section. A round cross section was taken to indicate that the body of the fiber was approximately normal to the surface and that therefore effects due to fiber material immediately below the surface could be neglected. RESULTS AND DISCUSSION The microprobe scans indicated that nickel reacted as low as 900°C, converting the entire fiber cross section to NisBe21. Fig. l(a). There was no evidence of further reaction from the optical or the back-scatter pictures, Figs. 2(n) and 3(a).

Jan 1, 1970

By Klaus Schwerdtfeger

Activities of lead in Pt-Pb and Pd-Pb melts in the temperature range of 800° to 1200°C have been detev-mined from electromotive-. force measurements 202th the cells Both systems display strong negative deviations from Raoult's law. The data obtained with cell [1] were combined with available data on the activity of PbO in silica-satuvaterl PbO-SbO2 melts to calculate the standard free cnergy of formation 01- liquid PbO. FREE energies of formation of oxides and activities of components in metal and oxide melts can be determined with galvanic cells consisting of a metal phase, an electrolyte containing the oxide of one of the components of the metal phase, and an oxygen electrode. This technique has been used previously to measure the standard free energy of formation of solid sio2, 1 and activities in Fe-si, CO-si,2 Ni-Si,2 and CaO-P2O5 3 melts. The present paper reports activities in Pt-Pb and Pd-Pb melts as measured with the same experimental technique. EXPERIMENTAL METHOD General Considerations. The following cells were used: Pbl (PbO-SiO2)liquid, SiO2 Pt-Pb 1 (PbO-SiOz)liquid, SiO2solidO2 [2] Pd-Pb (PbO-SiOz)liquid, SiO2solid O2 [3] Liquid alloy and' oxide melt were contained together in a silica glass crucible of essentially the same design as described previously.1'2 The PbO-SiO2 melts are ionic conductors.' During the experiment, the silica glass crystalizes in a layer adjacent to the electrolyte. The electrolyte equilibrates with solid silica and hence attains the composition of the Si02-liquidus curve in the system PbO-SiO2 at any particular temperature. Molybdenum wires were used to establish contact with the liquid metal. The oxygen electrode, which reaches the surface of the PbO-SiO, electrolyte from above, consists of a platinum wire inserted into a ceramic tube and provided with a 2-mm-diam platinum bead at its end. Gas of known oxygen partial pressure (pure oxygen of 1 atm: air, or N2 with 1.04 pct 0,) is blown through the ceramic tube onto the surface of the electrolyte. The cell reaction is Pb (metal) + 1/2O2 (gas) = PbO (electrolyte) [4] No oxidation of platinum or palladium ("displacement reaction") occurs. This is to be expected from the noble character of platinum and palladium, but was also shown experimentally, as described in the next section. The galvanic electromotive force of the cell is given by where AG is the change in free energy for Reaction [4], E(=2) is the number of electrical equivalents necessary to form 1 mole of PbO, and F is the Faraday constant. Formula [5] is valid only if no junction potential exists within the electrolyte. Junction potentials occur only when the compositions of the electrolyte are markedly different at the electrodes. Such differences are negligible in the PbO-SiO, electrolyte, as shown in the next section. Since molybdenum contact leads are used, appropriate corrections were made on the measured electromotive forces to account for the thermoelectric effect of the Mo-Pt couple. The thermoelec-tromotive forces were measured separately with a Mo-Pt couple, and were found to vary linearly from 19 mv at 740°C to 40 mv at 1310°C with molybdenum being positive and platinum negative (cold junction at 25°C). Extrapolation of these values to higher temperatures yields values which are in satisfactory agreement with those obtained previously in the temperature range 1440° to 1630°c.1,2 The change in free energy for Reaction [4] is expressed as where chemical potentials of the species. The value of constant for a given temperature because the slag composition is fixed. Inserting [6] into [5] and using appropriate expressions for upb and uO2 the relation

Jan 1, 1967

By Peter Beardmore, Michael B. Bever

The effects of the temperature of deformation and the degvee of deformation on the annealing spectrum of a Au-Ag alloy have been determined by vesistance measurements. Specimens were deformed in torsion at 4°, 78K and room temperature up to strains nd/l of about 1.0 and were isochronally annealed. Discrete annealing stages similar to those found for pure metals were observed. Stage A occurred below room temperature; the decrease in reszstance associated with this stage increased as the temperature of deformation was lowered or the strain was increased. Stage B manifested itself as an increase in resistance; this is attributed to the restoration of short-range order promoted by vacancy or vacancy aggregate migration. At temperatures above 48S0K, recrystallization or Stage C occurred. Stages A, B, and C in the annealzng curves of this alloy may be considered to correspond to Stages II, Ill, and V, respectively, in the terminology used to describe the annealing spectrum of pure metals. ThE annealing behavior after deformation below room temperature has been thoroughly investigated on pure metals, in particular gold and copper. The occurrence of several discrete stages in the annealing spectrum of these metals has been established, but the interpretation of some of these stages in terms of specific mechanisms is still controversial.' The annealing of alloys deformed below room temperature has been the subject of only a few investigations. In the investigation reported here, a Au-Ag alloy was annealed after deformation at and below room temperature. This continues a research program on the deformation and annealing behavior of Au-Ag alloys.2-8s EXPERIMENTAL PROCEDURE An alloy rod of composition 82.6 wt pct Au-17.4 pct Ag was reduced to wire, 0.0428 in. diam, by swaging and drawing. After a recrystallization treatment, the grain size was 0.031 mm, as obtained from the average linear intercept.7 The ends of wires about 6 in. long were flattened and sealed into short brass tubes with cold setting cement to form the grips of the torsion specimens. The equipment used for deformation has been described elsewhere.6 The specimens were deformed at room temperature, 78", and 4°K to various strains nd/l, where n is the number of turns, d the diameter of the specimen, and 1 its length between grips. The strain rate ?max was 0.1 min-' at the sur- face of the specimen except where noted otherwise. The specimens were annealed isochronally for 30 min at intervals of approximately 30°K from the temperature of deformation to approximately 800°K, except that after deformation at 4°K the lowest annealing temperature was 78°K. A potentiometric method was used to measure the resistance: all measurements were made at 78°K with the exception of some measurements at 4°K mentioned below. Data obtained with a single specimen yielded a complete annealing curve: in several cases duplicate specimens were used to confirm the reproducibility of the curves. Since the surfaces of the specimens were rough after deformation, their diameters could not be measured accurately. The resistance increments after deformation and annealing are therefore reported as percentages of the resistance of the same specimen measured after completion of the annealing, that is, after full recrystallization. The corresponding resistivity values can be calculated by obtaining the effective diameter of a deformed specimen from the ratio of its resistance after recrystallization to the true resistivity, which was determined with a smooth specimen of known dimensions. This method of calculation was used to obtain data shown in several of the figures. RESULTS AND DISCUSSION The isochronal annealing curves after deformation to various strains at 4", 78K, and room temperature are shown in Figs. 1, 2, and 3, respectively. The resistance increment of the as-deformed specimens as a function of strain is shown in Fig. 4. For the specimens deformed at 4°K. values measured at 78°K are plotted with the exception of those for the as-deformed

Jan 1, 1970

By A. H. Cottrel

SINCE metallurgy exists to provide strong, tough, engineering materials it must inevitably be perpetually concerned with the problem of brittle-ness. The steel-making industry was created because chemically unrefined iron is brittle. The steel-working and alloy-steel industries exist partly because hardness and ductility are mutually exclusive qualities in structurally unrefined steel. Yet, in spite of these immense industries, the brittle failure of steel ships hulls, bridges, pressure vessels, and pipelines, is still a contemporary problem. In fact, brittleness is a normal property of most solids, including metals and alloys, at low temperatures. Only face-centred cubic metals are commonly ductile at the lowest temperatures, and even here exceptions are known.'," Expensive are-melting processes. under inert gases or vacuum, have been developed to overcome brittleness in titanium, zirconium, columbium. and molybdenum. Polycrystal-line zinc, magnesium, and uranium have little ductility at room temperature. Beryllium, chromium, and tungsten have even less; similarly for antimony, bismuth, germanium, silicon, intermetallic compounds, and metallic carbides, nitrides, silicides, and borides. Oxides and other ceramics would be ideal creep-resistant materials but for their extreme brittleness when cold, and great efforts have been made to overcome this problem by mixing ceramics with metals. In fact, the traditional use of the name metallurgy for what is really the science of engineering materials is a recognition that most non-metallic solids have so far been precluded, by their extreme brittleness, from use as major structural materials in mechanical engineering. Most of what we know about brittleness in metals has come from studies of structural steel, and it is this material that shall mainly be considered. The things we have learned from it have a wider application, at least to other body-centred cubic transition metals, although the extent to which similar ideas can be applied to hexagonal metals and other materials is not yet clear. Fracture and Plastic Deformation The theoretical breaking strength of an ideal solid, about E/10 where E is Young's modulus, has been approached reasonably closely in experiments on fibres. But large specimens break at much lower stresses. For example, brittle cracks in large structural steel assemblies have been observed to spread catastrophically at speeds of 6000 ft per sec under stresses of about 10,000 psi, i.e. about E/3000. There are two sources of weakness; stress concentrations, and chemical agents in grain boundaries or on crack faces that lower the surface energy y of the material. Although we shall deal mainly only with the first of these, much of the discussion is also applicable to the second when different values of y are used. Griffith's well-known formula p = [ 2Ey/p(1 - v2)c]1/2 [1] gives the smallest tensile stress p able to propagate an atomically sharp surface crack of length c or interior crack of length 2c through a thick plate (compared with c) of elastically isotropic material of

Jan 1, 1959

By R. L. Rickett, W. C. Leslie

The influence of deoxidation practice, prior thermal history, and aging time and temperature on the strain-aging behavior of low-carbon open-hearth steels was investigated. The criterion of aging employed was the increase in yield strength in the tensile test, after straining and aging. Composition, prior heat treatment, and aging conditions were all found to be important in governing the strain-aging characteristics of these steels. THAT deoxidation changes the strain-aging propensities of low-carbon steels has been known for a long time, but there has been little agreement, and even contradiction, between results obtained by different investigators and between results obtained in the laboratory and in the mill. This investigation was begun in the hope that some of the uncertainties connected with the strain aging of commercial steels could be eliminated. In considering this problem, it was necessary to define strain aging and to examine the methods used to measure this property. Strain aging can be defined as the changes in properties of a metal or alloy with time, after cold working. The rate at which these changes occur increases as the temperature is raised above atmospheric. The requisite plastic strain is the principal distinction between strain aging and quench aging, the latter being due to precipitation from supersaturated solid solution. Strain aging is also characterized by rapid attainment of maximum hardness at high aging temperatures and lack of softening (overaging) at low aging temperatures. Several possible criteria of strain aging have been listed by Sachsl and by Davenport and Bain.' Because changes in mechanical properties are the most easily measured and the most commonly used, consideration of methods to be used in this investigation was confined to three tests: tensile, notch-impact, and hardness. Hardness tests are the most economical and easiest to perform, but produce only one measure of strain aging. Also, as pointed out by Felmly, Hartbower, and Pellini,³ hardness changes due to aging are not pronounced for steels containing more than 0.15 pct C. Notch-impact tests require careful preparation of large numbers of specimens. Above and below the transition temperature the test lacks sensitivity; furthermore, it is extremely difficult to impart a uniform strain to the specimens, followed quickly by aging and final testing; machining must generally take place after straining. For these reasons, the tensile test was selected for use. Although this test requires a considerable expenditure of time, labor, and money in preparation of the specimens and performance of the test, more information can be gained than from any other single mechanical test, information which includes upper and lower yield points, yield-point elongation, tensile strength, strain-hardening exponent, reduction of area, and elongation. Low and Gensamer' and Schwartzbart and Low5 lso used the tensile test, taking the increase in flow stress after straining in tension and aging as a measure of strain aging. In our work, as in theirs, each specimen was strained an arbitrary amount, sufficient to pass through the

Jan 1, 1954

By Ben Gumpertz

The important factors in any study of the screening of sand with a gravel envelope, as applied to use in oil wells, are: (I) sand size and shape, (z) gravel size and shape, (3) ratio of gravel size to sand size, (4) flow velocity, (5) viscosity of the fluid. Perhaps the first extensive investigation of the function of gravel in screening sand was performed by Coberly and Wagner,' from which the following conclusion was drawn: "The diameter of the largest grains in a single classified sand suitable for gravel packing is approximately 13 times the grain size at the ten-percentile analysis of the formation sample." ?;his applies to sands classified by Tyler screens and is for gravel grains of the maximum size that could be used to form a stable bridge. Field practice has shown that the screening effect of a given gravel for a given sand apparently varies with the flow velocity." Also, it has been assumed by some operators that the thickness of the walls of the gravel envelope surrounding the well has little effect upon the screening process. It is thought by others that a narrow envelope of gravel might form an ineffective screen. Thus the purposes of this work are: 1. To investigate the effect of gravel-sand size ratio upon screening action under the condition of varying flow velocities. 2. To investigate the effect upon screening action of varying the thickness of the gravel screen. 3. To investigate sand migration in the gravel screen and the effect of flow velocity and gravel size upon sand migration. Description of Apparatus In an attempt to reproduce field conditions for the purposes of this investigation, a flow tube was constructed, according to the manner of Urenj3 to represent a radial drainage segment of an oil sand. To arrive at the dimensions of the flow tube, a radial drainage segment of rectangular cross section was assumed to define an area of z sq. in. on the face of a well 6 in. in diameter. From this the dimensions of the segment were calculated out to a distance of 5 ft. from the face of the well. By computing cross-sectional areas at a number of sections along the rectangular segment and transforming these areas into the circular form, a drainage cone was obtained having everywhere the same cross-sectional area as the drainage element of rectangular cross section. To construct the apparatus, two sections of pipe of 7%-in. inside diameter, one 13 in. and the other 4 ft. long, were joined by a bolted flange. A mandrel having the dimensions of the drainage cone was centered in the pipe and a neat cement mixture was cast around it. A protective gasket was placed between the two sections of pipe so that the cement body could be separated at that point. When the mandrel was withdrawn a drainage cone was obtained (Fig. I).

Jan 1, 1941

By Ben Gumpertz

The important factors in any study of the screening of sand with a gravel envelope, as applied to use in oil wells, are: (I) sand size and shape, (z) gravel size and shape, (3) ratio of gravel size to sand size, (4) flow velocity, (5) viscosity of the fluid. Perhaps the first extensive investigation of the function of gravel in screening sand was performed by Coberly and Wagner,' from which the following conclusion was drawn: "The diameter of the largest grains in a single classified sand suitable for gravel packing is approximately 13 times the grain size at the ten-percentile analysis of the formation sample." ?;his applies to sands classified by Tyler screens and is for gravel grains of the maximum size that could be used to form a stable bridge. Field practice has shown that the screening effect of a given gravel for a given sand apparently varies with the flow velocity." Also, it has been assumed by some operators that the thickness of the walls of the gravel envelope surrounding the well has little effect upon the screening process. It is thought by others that a narrow envelope of gravel might form an ineffective screen. Thus the purposes of this work are: 1. To investigate the effect of gravel-sand size ratio upon screening action under the condition of varying flow velocities. 2. To investigate the effect upon screening action of varying the thickness of the gravel screen. 3. To investigate sand migration in the gravel screen and the effect of flow velocity and gravel size upon sand migration. Description of Apparatus In an attempt to reproduce field conditions for the purposes of this investigation, a flow tube was constructed, according to the manner of Urenj3 to represent a radial drainage segment of an oil sand. To arrive at the dimensions of the flow tube, a radial drainage segment of rectangular cross section was assumed to define an area of z sq. in. on the face of a well 6 in. in diameter. From this the dimensions of the segment were calculated out to a distance of 5 ft. from the face of the well. By computing cross-sectional areas at a number of sections along the rectangular segment and transforming these areas into the circular form, a drainage cone was obtained having everywhere the same cross-sectional area as the drainage element of rectangular cross section. To construct the apparatus, two sections of pipe of 7%-in. inside diameter, one 13 in. and the other 4 ft. long, were joined by a bolted flange. A mandrel having the dimensions of the drainage cone was centered in the pipe and a neat cement mixture was cast around it. A protective gasket was placed between the two sections of pipe so that the cement body could be separated at that point. When the mandrel was withdrawn a drainage cone was obtained (Fig. I).

Jan 1, 1941

By J. E. Ostberg, G. Phragmen, A. Hultgren, S. Wohlfahrt

Detailed study was made of a number of rimming ingots, both low and high carbon, and especially upon effects of superimposed air pressure. Requirement to suppress core bubbles is between 10 and 15 atm; at 6.5 atm freezing was in semikilled manner and at 3 atm, steel was of rising type. Probable mechanism of freezing under various conditions is discussed. AN earlier paper' reported an investigation made by a committee for studying rimming steel ingots appointed by Jernkontorets in Stockholm. The present paper is the outcome of some further work done by the same committee. Since the characteristics of ordinary rimming steel are connected closely .with the amount of gas liberated during freezing and since this amount of gas is governed by the pressure, it was considered of interest to ascertain in what manner and to what extent definite pressures applied to the top of the liquid steel in the mold would affect the solidification process and the consequent structure of a rimming steel of ordinary composition. The experiments were made at the Domnarfvets Steel Works. The steel was made according to normal practice in a 4-ton Rennerfelt electric furnace. Ferromanganese was added in the furnace; no aluminum was added, with one exception. Analyses of the four heats are given in Table I. The top-poured ingots measured about 12 in. sq x 48 in. and weighed about 1300 lb. One or two ingots of each heat were allowed to solidify under pressure, using a special device for admitting compressed air to the upper closed part of the mold, as shown in Fig. 1. A heavy plate sealed with asbestos was bolted to the top of the mold. The plate had a tapered aperture for pouring. Immediately after pouring the hole was closed by a wedged plug, and compressed air was admitted through a hole in the plug. Because of some delay in applying the plug, full pressure was not reached immediately. The pressure was adjusted to the desired value as indicated by a manometer. In order that the interior of the ingot might have the benefit of the pressure, the freezing of the top crust was delayed by a refractory lining applied to the top part of the mold, Fig. 1. Ingots were also cast from each heat without applied pressure, and with and without refractory lining at the top. Axial sections of ingots were cut either of the whole ingot or of some part of it of special interest; sections were polished and usually etched.' To facilitate description of structures the following terms may be used for different types of ingots solidified under gas evolution: 1. Box-hat or boot-leg ingot: Abundant gas evolution during casting and during rimming; no rim holes. 2. Normal rimming ingot: Lively gas evolution during rimming; usually rim holes in lowest part of

Jan 1, 1952

By R. J. Walter, W. T. Chandler

The Ch-H phase diagram was determined for by-drogen concentrations up to ChHo.9 at temperatures below 400°P'. The phase diagram includes a mis-cibility gap and a eutectoid transformation. A peri-tectoid transformation is postulated at the hydrogen-rich end of the diagram, Phase diagrams were determined for two levels oj purity, of the columbium. A single solid solution exists in the Cb-H system above 400°F. There has been considcrable disagreement among investigators concerning the system at temperatures below 400°F. Albrecht, Goode, and ~allett' proposed a miscibility gap containing two bcc phases with the two lattice parameters converging at about 140°C (285-F), and Brauer and ~erman' found a two-phase room-temperature region between 10 and 41 at. pct H. At sufficiently high hydrogen concentrations in the one-phase region, the hydrogen-rich phase was found to be face-centered orthorhombic. Wainwright, Cook, and Hopkills3 recently reported that the face centered orthorhombic hydride phase is derived from a unit cell which is slightly tetragonal with a small departure from 90 deg of the angle (y) opposite the r axis. The orthorhombic hydride phase was observed for hydrogen concentrations between 0.2 and 0.8 H/Cb atom ratio. Paxton and coworkers4 found that needlelike hydride plates formed in a hydrogen-charged columbium single crystal and suggested that this transformation possessed the characteristics of a diffusionless phase transformation. On the basis of room-temperature, X-ray diffraction data, komjathy' suggested that an order-disorder or martensitic transformation occurs. In the present study, the Cb-H system was investigated to resolve the discrepancies found in the literature for this system. PROCEDURE The columbium specimens were prepared from two heats of wrought 1/2-in.-diameter electron-beam melted columbium rod and from two columbium powders of -80 mesh size of different impurity contents. The columbium bar stock was pur chased from Urah Chmg Corp.; the 99 and 99.5 pct purity colulnbium powders were obtained from Fansteel Metallurgical Corp. and Kern Chemical Co.. respectively. The chemical analyses of the columbium bar and powders are listed in Table I. Hydrogen charging was performed by exposing the columbium specimens to hydrogen at 1 atm pressure at various temperatures. After exposure the specimens were quenched to prevent the hydrogen pickup which would take place if cooled in hydrogen, or the hydrogen loss that would occur if cooled in an inert gas. Adequate hydrogen purity was achieved by passing high-purity tank hydrogen (maximum 5 ppm total impurities) through an Engelhard catalytic Deoxo unit, magnesium per chlorate desiccant, and finally through activated charcoal at the temperature of boiling nitrogen. Activated charcoal at -321°F has been reported6 to remove impurities from hydrogen to a nondetectable level. A schematic representation of the heat-treating apparatus is shown in Fig. 1. A metal-sheathed thermocouple embedded in the colun~bium specimen was used to control the temperature during heat treatment and to pull the specimen boat into

Jan 1, 1965

By J. G. Benford, E. B. Stanley

THERE have been numerous papers in the literature1 on the subjects of secondary and tertiary recrystalli-zation in silicon steels. Secondary re crystallization is believed to occur in silicon steel by either a surface-energy phenomenon such as in the usual development of cube texture or by a second-phase phenomenon such as in the usual production of cube-on-edge texture, (110)[001]. Tertiary recrystallization in silicon steel is thought to be a surface-energy phenomenon in which, for example, grains having a (110) plane parallel to the sheet grow at the expense of other grains in the matrix including those having a (100) plane parallel to the plane of the sheet. In all these instances, the orientations involve either a preferred (100) or (110) plane in the plane of the sheet. Until very recently, there had been no experimental evidence reported of the occurrence of a texture by secondary or tertiary recrystallization that involves a (111) plane in the plane of the sheet, although Kohler reported that grains having the (111) plane parallel to the sheet surface can also grow by a surface energy mechanism. Stickels observed a secondary texture in iron described as "near {554}(225)" about 5 deg from {lll}(211).3 Mee reported that in a vacuum-remelted commercial 3 pct Si steel {lll}(hkl) secondary recrystallization took place in a high vacuum and in pure hydrogen.4 Recently in our Laboratory, large-grained structures such as shown in Fig. 1 having an orientation near (111)[211] or (111)[2ii] have been observed. The arrows point to areas of relatively small matrix grains of the kind that the much larger (111) grains consumed while growing. It is of interest that the matrix grains of samples annealed at 2000°F were essentially the same size as those in samples annealed at 2200°F, a matrix-grain-size stability that is characteristic of secondary recrystallization processes. A torque disc taken from Grain 4 of the sample shown in Fig. 1 revealed a very flat magnetic-torque curve, as expected, with a maximum torque of 7000 dyne-cm per cu cm compared to the typical 180,000 dyne-cm per cu cm observed for conventional (110)[001] textured material. A back-reflection Laue pattern for Grain 4 is shown in Fig. 2 and indicates a near-perfect (111)[211] orientation. The other six numbered grains in the sample of Fig. 1 had a similar orientation. The small circles next to each number were the target areas for the X-ray beam. The starting material was an 0.011-in.-thick oriented silicon steel, (110)[001] texture, containing 3 pct Si. It was lightly pickled, cold-rolled to 0.005 in., and annealed 4 hr at 2200°F within a nickel box (not gas-tight) inside a tube furnace through which dry hydrogen was flowing. The samples were heated to 1500°F in 1 hr and then at 60°F per hr to 2200°F. There were other

Jan 1, 1969

By Nathaniel Arbiter

T. M. Morris (School of Mines and Metallurgy, Rolla, Mo.)—Rate studies promise to help quantify flotation operations. The author's exposition of rate studies is therefore laudable. However his exposition of a second order rate equation rather than a first order rate equation is not convincing. It is important to use the correct equation, otherwise erroneous conclusions may be drawn. The data assembled by the author and plotted according to a second order rate equation can be plotted according to a first order rate equation. As a matter of fact much of the data used reveals that a second order rate equation is not applicable. According to the method used by the author for plotting data, the reciprocal of the slope of the line is the maximum possible recovery. Physically this cannot exceed 100 pct, yet several graphs yield maximum recoveries greater than 100 pct. For example: l—Curve 2, Fig. 1 yields a value of 120 pct; 2—Curve 2, Fig. 2 yields a value of 115 pct; 3—Fig. 7 yields a value of 110 pct. The real test of the graphical method is, as the author points out, whether or not the earliest points agree with a straight line. The second order rate plot does not fulfill this requirement. Fig. 10 shows the data used by the author to obtain Curve 2 in Fig. 1, plotted according to both a second and first order rate equation. Fig. 11 shows the two rate plots made from data published by Ludt and DeWitt.19 In Fig. 10 the first order rate plot gives a very good fit and obeys the boundary condition of passing through the origin. For the second order rate plot a straight line can be drawn through the last three points but the earliest points are not in agreement with this line. The reciprocal of the slope of the straight line gives a value of maximum possible recovery of 112 pct. The maximum possible recovery according to the first order rate plot is 78 pct. In Fig. 11 the first order rate plot again fits all of the points very well and passes through the origin. The second order rate plot shows wide deviation of the earliest point, indicating that the second order rate equation is not applicable. The reason for the fit of data to the second order rate equation during longer flotation times is that R, the cumulative percent recovery, changes slowly toward the end of the flotation operation, so that when t/R is plotted against time, one is, in effect plotting t against t and one would certainly expect a straight line. The author attempts to show that the second order rate equation is correct by citing evidence which shows that recovery is a function of initial concentration. This is a debatable point especially since, in the author's original presentation of this paper at the St. Louis

Jan 1, 1952

By Charles H. Moore

In the study of the properties of rutile pigments it became apparent several years ago that certain physical and optical properties could not be determined on particles of pigmentary size. Since reflected light is the dominant type which reaches the eye from small particles, the true color of pure rutile was not known. Most rutile pig-ments are acicular in habit, elongated parallel to the "c" axis. It was considered important to know the nature and tone of light transmitted, for example, by a basal plate. Further, as shown by spectrophotometric curves, there is a very strong absorption of light of 4000 A as measured on particles with random orientation. It would be interesting to see whether this absorption position varied with predetermined and selected orientations. Also, since the behavior of titanium pigments in a vehicle is important, a knowledge of the surface wettability of single crystals by various media should prove very fruitful. Finally, the optical properties of rutile are such that it should show, in a single pure crystal, greater fire and brilliance than the diamond. Mineralogists had long speculated that this would be the case and curiosity was strong to produce a single crystal large enough to cut. In light of the above, a project was initiated for the formation of single crystals of rutile. Method of Formation of Rutile Single Crystals Fortunately, purification of TiO2 produced from both titanium tetra-chloride and titanyl sulphate solutions had reached the stage where spectro-graphically pure starting material could be made. Spectrographic analysis of the feed material used in the initial experiments is compared with the present feed material in Table 1. It is apparent that the present large scale purification is approximately as good as the original experimental, small scale purification. Verneuil1 produced synthetic ruby and corundum in 1904 by the well-known flame fusion process, which today bears his name. Except for mechanical improvements the present commercial production of synthetics by flame fusion is essentially unchanged from his initial method. His burner consisted of an inner orifice through which was fed the feed material and oxygen. Surrounding this was a larger outer orifice through which was fed hydrogen at lower pressure. This arrangement consists then of a lance of oxygen burning in an atmosphere of hydrogen. The proportions of hydrogen to oxygen usually used in corundum production is about 3:1, providing there is sufficient temperature to reach the 2050.°C required for the fusion of alumina. From work done in the Titanium Division Laboratories2 and from the published work of Erlich3 it was known that rutile appears to lose oxygen near its melting point and that it would not be possible to grow single crystals in a strongly reducing environment. Consequently, in order to determine whether single crystals could be grown at all, an Airco oxygen-acetylene torch with

Jan 1, 1950

By Charles H. Behre

This paper discusses education and training for economic geologists other than petroleum geologists. Candidates enter economic geology through liberal arts colleges, engineering schools and university graduate study. Whatever their backgrounds, rigorous courses are desirable—now conceded in theory, but not adequately recognized in practice. Besides basic sciences (each studied long enough to give a fair comprehension of its basic tenets), a functional command of English and two modern foreign languages is needed, as well as a broad understanding of mining, milling and metallurgy. A year of economics and finance is recommended. Surveying and drafting are essential skills. Yet geology should be represented in each term; otherwise the initial enthusiasm for the science, once contact is broken, may never be regained. A five-year curriculum is thus designed to take care of all major requirements and culminate in the M. S. degree. This curriculum reduces "cultural" courses below the average liberal arts requirements, but this is regarded as necessary. The pursuit of "culture" is assigned, as in most engineering and medical curricula, to extra college years or extracurricular time. To avoid the danger of over-crowding the schooling, the Doctorate in geology is preferred wherever possible. Its two added years should permit wider professional education; more browsing in "cultural" pastures; due attention to broader social implications; and some training in the research now increasingly required of the mineral industry. "In-course" training through cooperation between school and industry is especially advo- cated. The Institute should take the initiative in stimulating this practice. Introduction Training a student in geology for a career in the mineral industry is still a moot question, one that is likely to be looked at from many different angles, each of which will reflect the background of the individual considering it. From what follows, the training of petroleum geologists is omitted since, although theirs is an equally important phase of economic geology, it is based upon different essentials. The general subject was recently effectively discussed, but from a somewhat different viewpoint, by Professor McKinstry.' The practical problems that confront the young mining geologist are highly varied and in the eyes of his employer apparently almost any demands seem justified. The mining executive wants from the mining geologist results related mainly to overall operations, reports or forecasts that are largely recordable on paper and chiefly in terms of "discovery thinking." The local mining engineer may have many specific questions of his own, chiefly relating to details of geology that apply to mining practice, which he will address to the mining geologist; these usually deal with production quantities; frequently also they necessitate the immediate handling of pressing but apparently minor matters: shall the drill be moved; how soon will we encounter the watercourse which made so much trouble for us above? The client employing a consultant often wants advice or good judg-

Jan 1, 1949

By Charles H. Behre

This paper discusses education and training for economic geologists other than petroleum geologists. Candidates enter economic geology through liberal arts colleges, engineering schools and university graduate study. Whatever their backgrounds, rigorous courses are desirable—now conceded in theory, but not adequately recognized in practice. Besides basic sciences (each studied long enough to give a fair comprehension of its basic tenets), a functional command of English and two modern foreign languages is needed, as well as a broad understanding of mining, milling and metallurgy. A year of economics and finance is recommended. Surveying and drafting are essential skills. Yet geology should be represented in each term; otherwise the initial enthusiasm for the science, once contact is broken, may never be regained. A five-year curriculum is thus designed to take care of all major requirements and culminate in the M. S. degree. This curriculum reduces "cultural" courses below the average liberal arts requirements, but this is regarded as necessary. The pursuit of "culture" is assigned, as in most engineering and medical curricula, to extra college years or extracurricular time. To avoid the danger of over-crowding the schooling, the Doctorate in geology is preferred wherever possible. Its two added years should permit wider professional education; more browsing in "cultural" pastures; due attention to broader social implications; and some training in the research now increasingly required of the mineral industry. "In-course" training through cooperation between school and industry is especially advo- cated. The Institute should take the initiative in stimulating this practice. Introduction Training a student in geology for a career in the mineral industry is still a moot question, one that is likely to be looked at from many different angles, each of which will reflect the background of the individual considering it. From what follows, the training of petroleum geologists is omitted since, although theirs is an equally important phase of economic geology, it is based upon different essentials. The general subject was recently effectively discussed, but from a somewhat different viewpoint, by Professor McKinstry.' The practical problems that confront the young mining geologist are highly varied and in the eyes of his employer apparently almost any demands seem justified. The mining executive wants from the mining geologist results related mainly to overall operations, reports or forecasts that are largely recordable on paper and chiefly in terms of "discovery thinking." The local mining engineer may have many specific questions of his own, chiefly relating to details of geology that apply to mining practice, which he will address to the mining geologist; these usually deal with production quantities; frequently also they necessitate the immediate handling of pressing but apparently minor matters: shall the drill be moved; how soon will we encounter the watercourse which made so much trouble for us above? The client employing a consultant often wants advice or good judg-

Jan 1, 1949

By C. W. Spencer, F. G. Hochgraf, R. F. Cheney

Columnar grained specimens of nickel, containing 0.25 pct Si and 0.22 pct Mn, have been exposed to liquid bismuth in the temperature range 670° to 1050°C. Under isothermal conditions the liquid penetration rate is constant. The activation energy for the process is 22,000 cal per g-atom. Small amounts of plastic deformation, introduced into specimens prior to exposure, increase the penetration rate. The slou. step in liquid film penetration is associated with a reaction which occurs at or near the leading edge of the film. Either transfer of nickel across the liquid-solid inteqace or diffusion in the grain boundary ahead of the liquid film is suggested. Aliquid metal, if brought into contact with the surface of an unstrained solid metal, will usually penetrate to some extent into the grain boundaries of the solid. Under isothermal conditions the extent of penetration after any particular time of exposure is related to the relative magnitudes of the interfacial tensions concerned.1,2 If the liquid-solid interfacial tension is less than one-half the grain boundary tension the liquid may penetrate at a relatively rapid rate for an indefinite distance into the grain boundary surfaces. If the liquid-solid interfacial tension is greater than one-half the grain boundary energy, liquid penetration occurs at a continually decreasing rate so that after the liquid has penetrated to a relatively short distance below the surface the process essentially ceases.3 Many observations of a qualitative nature concerning inter crystalline attack by liquid metals have been reported, for example, liquid bismuth upon copper,' liquid mercury upon brass,4 and liquid mercury upon nickel.' Scheil and Schessl determined the rate of penetration of liquid bismuth into the grain boundaries of hot rolled copper rod? At constant temperature, penetration rate was found to be independent of the depth penetrated, the rate in- creasing with increasing temperature corresponding to an activation energy of 20,000 cal per g-atom for the process. It was suggested that at lower temperatures the liquid travelled mainly along lines of three grain intersections while at temperatures greater than 1000°C essentially all grain boundary surfaces were covered. Recently, in a study of copper bicrystals having a common [loo] axis it was found that at 649°C bismuth penetrated 22, 25, and 63 deg boundaries while it did not penetrate 2, 12, 15, and 72 deg boundaries.' Elbaum reported that liquid gallium penetrates aluminum grain boundaries to a depth of 0.6 cm after 11 hr at 27°c.8 Assuming that the rate controlling step in the process was diffusion down the liquid film to the specimen surface, a diffusion coefficient of 10-5 cm2 per sec was calculated. This paper reports a study of the penetration of bismuth-nickel liquids into the grain boundaries of a nickel alloy, containing 0.25 pct Si and 0.22 pct Mn as principal alloying elements. The phase diagram

Jan 1, 1962

W. S. GRESLEY, Erie, Pa.: Mr. Henrich's Fig. 1 and reference thereto remind me of a section of sand, gravel, clay, etc., which I sketched near Hellesylt on Stor Fjord, Norway, some years ago. Vertical Section of Glacial Morainic Material, containing Angular Masses of Banded Sand. Observed June 29, 1887, about 14 English miles south of Hellesylt, at head of Stor Fjord, near Aalesund, Norway. The accompanying figure reproduces my sketch. It was the angular and tilted blocks of sand in this glacial débris, or moraine, that particularly attracted my notice. The sand was moist; and I could only account for the phenomenon of blocks of sand

Jan 1, 1897

H. F. MOORE and W. J. PUTNAM (author's reply to discussion?).-The writers are inclined to question whether it has been experimentally established that steels will endure an indefinite number of repetitions of low range of stress. It is difficult to see how such a conclusion can be reached except by extrapolation from test data,. and such extrapolation always gives results of questionable value. From the viewpoint of the designer and the user of steel the writers believe that the exponential formula, which gives results on the safe side of what test. data we have, for steel subjected to tens or hundreds of millions of repetitions is a safer

Jan 7, 1919

By Erwin J. Durrer

The development of planning in the petroleum industry is de- scribed and the current status analyzed. Worldwide transportation networks led to corporate models which caused a differentiation between operations research and planning groups. Ranking of projects solely by ROI proved infeasible because of the diversified nature of the industry. Qualitative elements such as synergism with ongoing operations and the external socio-economic environment had to be included, leading to business plans based on scenarios of possible futures and stressing growth-opportunities over cash-flow rich mature product lines. In addition, decision analysis is finding applications in large capital, high uncertainty situations such as planning for synthetic fuel development.

Jan 1, 1977

By E. A. Khopunov, V. I. Revnivtsev

The process of triboelectric separation from the point of view of its potential for selective separation of various mineral particles can be described as "dry flotation." Large scale practical applications of this technique are limited because suitable models which can describe contact charging of mineral particles have not been developed. Among the various concepts a promising one is an attempt to change development in dielectric minerals within the limits of contact phenomenon in semiconductors. Experimental investigations reported in this paper indicate that the charge development is mainly a result of contact electrification of dielectric minerals characterized by "donor" and "acceptor" type energy spectra due to lattice defects.

Jan 1, 1980

By G. S. Cole, H. Biloni, G. F. Bolling

An experimental investigation of sovlze low .melting point alloys sJtows that a substvucture of isolated depressions can be the first manvestation of constitutional supercooling on solid-liquid interjaces veuealed by decanting. Electron-tni cvop vobe and wletallo gvaplic esanzinations, in tlze bulk belzind the interjace, oj the segregation associated with these isolated areas substantiate tlzei&apos;v depressed nature, since a solute of ko < 1 is enriched, and a solute of ko > 1 depleted. In contrast, the pox structuve, a set of projections often veported in the literature, leaves no trace oj. segvegation. These obserl;atims, accovlrpanied by a brief review of recent literature, point to inconsistencies between experirrental obsevvation and the idea that the fornzation of a projection is a causal step in the development of a cellular substructure. An argument is presented to show instead how it is plausible for substantial depvessiom to form in the pvesence of constitutional supercooling at dislocations threading the solid-liquid interjace. THE development of constitutional supercooling during growth from the melt leads to the formation of the cellular solidification substructure. This well-founded association between structure and instability has been basic in understanding cellular substructure and micro segregation; however, the initial formation of structure seems unclear. Rutter and Chalmers,&apos; in definitive experiments and theory, noted that in the presence of constitutional a planar interface might break down: "resulting in the formation of a small projection on an initially plane or uniformly curved interface." That is, the breakdown from a planar to a cellular interface was implied to be initiated via a projection into the unstable liquid. Later, Walton et (11. found that a structure of isolated projections, termed "pox", appeared at solid-liquid interfaces decanted under growth conditions near the onset of constitutional supercooling; the pox were taken as the indication of the instability promoted by the supercooling. Tiller and Rutter4 in their extensive work studied the shape transitions at decanted interfaces which were generally observed to proceed as— pox, "irregular cells", elongated cells, regular (hexagonal) cells, and so forth. The pox varied in size from lo-&apos; to 1CT4 cm, and tended to disappear as cells increased in number and regularity, but as noted,4 the first real array of cells did not seem to be a development from the pox. In fact these authors implied a lack of connection because they stated that the pox are denser on "irregular cells", and as cell boundaries increase in number (i.e., the cells become smaller) there is less need for the pox which do dis- appear. Thereafter, most authors dealing with either experiment or theory have accepted the reality of pox and have used them as a criterion for the onset of constitutional supercooling. In contrast, Spittle, Hunt, and smiths have now suggested that pox are irrelevant artifacts comprised of such things as entrapped oxide. This proposal invokes the observations of weinberg6 and chadwick7 each of whom have shown that the act of decanting leaves a residual liquid on a decanted interface; the remnant solid layer of the order 10 p may thus contain particles that might have been transported from the external surfaces, or elsewhere, during decanting. With the incentive of this suggestion,= some further experiments and a reexamination of the literature have been conducted, in order to question the validity of pox as evidence of an instability and to examine the initial development of the cellular substructure. 1) EXPERIMENTS Single crystals of zone-refined tin (-99.9999 pct) were grown from the melt in a controlled fashion with various, small concentration additions of lead and antimony, for which ko < 1 and > 1, respectively. The crystals were decanted at conditions near the onset of constitutional supercooling and were thus appropriate for observation of slight perturbations. It was possible to observe two types of small departure from smooth or "planar" interfaces in both cases of lead or antimony additions. Some were projections and others, if in regular array of any type, were depressions. The crystals were etched with suitable reagents progressively dissolving the decanted interface surface; projections left no record, but depressions were continuously associated with spotlike areas contrasting with the rest of the interface. Traverses were made with the beam of an electron microprobe across the regions of contrast; with lead addition the persistent spots were lead-rich, and with antimony addition the persistent spots were antimony-poor. This is consistent only with a dominant role for depressions, because if the projections had left spots but were incorrectly catalogued, a reversed observation should have been made; that is, the Pb(ko < 1) should have been depleted and the Sb(ko > 1) enriched. In the work of Cole and inegard, and elewhere, regular arrays of structure associated with the initial stage of instability have been shown, in photographs and represented as pox or projections. We believe this to be erroneous, by inference, since whenever a regular array was observed, in the present examination, it consisted of depressions, regardless of the nature of the solute, ko 1. Fig. 1 is reproduced8 as an ideal example of the possible optical illusion involved; the observer can satisfy himself from the distribution of illuminated areas that the markings are depressions. Fig. 2 from the present investigation is an interference photograph of an interface similar to that in Fig.

Jan 1, 1967