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By S. J. M. van Leeuwen, R. Feenstra

The effect of jets on bit penetration has been investigated by means of a 50-ton drilling machine and 8½-in. commercial jet bits, drilling under representative bottom-hole conditions. The conclusions apply to the drilling of impermeable rock only. Penetration rate is in all cases primarily hampered by a differential pressure effect, known as dynamic hold-down. Jet action can reduce this slightly. Major gain in penetration rate, up to 25 or 50 per cent, is already ohtained at medium-high jet power. At high bit load, penetration by soft to medium-hard-formation bits is further hampered by bit-balling. Its alleviation requires intensive tooth scavenging, which is best performed by slanted nozzles with trailing, high-velocity, high-volume jets, hitting bottom in front of the teeth. Penetration may then improve by a 100 per cent. At high bit load, bottom-balling limits the penetration of insert-type bits. In this case bottom scavenging is required, which is most effectively performed with high velocity jets from nozzles extended close to bottom. As a result of this measure, penetration may improve 70 per cent in non-friable rock, and less in friable rock. This will make the insert-type bit more versatile. Toothed hard-formation hits suffer at high bit load from both bit- and bottom-balling. Slanted nozzles, possibly much extended, with high-velocity, high-volume jets then have best prospects. INTRODUCTION For years the use of jet bits in oil well drilling has been increasing, in conjunction with ever greater hydraulic horsepower. To the same extent, the need for efficient use of the horsepower has grown.' This paper, it is hoped, will contribute to an understanding of how effective jet action may be obtained. It deals with the effect of jets on phenomena that are known' " to hamper bit penetration. To study this effect, laboratory drilling tests were performed with 8½-in. commercial bits under bottom-hole pressures representative of deep wells. The investigation has been restricted to the drilling of practically impermeable rock. In the following sections, the increase in bit penetration rates due to jetting is discussed for conditions which made the troublesome phenomena stand out one at a time. A brief definition and interpretation of these phenomena is given in Appendix A. Appendix B gives the results of measurements of fluid velocities along the hole bottom, performed in stationary flow tests. Descriptions of equipment, bits, rocks and mud are collected in Appendix C. Unless otherwise mentioned, drilling conditions were kept standard as given in Table 1. CUTTING TRANSPORT TO THE ANNULUS Jet action was for some time believed to merely improve the transport of cuttings from bottom to annulus, resulting in a clean hole bottom. Flow tests performed in 1954 at the Battelle Memorial Institute6 showed, however, that jet velocities of the order of 40 ft/sec sufficed to clear even large (0.4-in.) chips from bottom in the time between two successive tooth actions. In the field, optimum jet velocities are appreciably higher, indicating that other effects must be involved. This much is confirmed by the results of our drilling experiments in soft rocks performed under atmospheric pressure, i.e., in absence of pressure-differential effects. Fig. 1 shows that variation in the nozzle velocity from 40 to 330 ft/sec had no effect on penetration rate, unless the bit penetrated more than 7 mm per revolution, which is about half the tooth height. At such high rates—150 ft/hr at 100 rpm—cuttings would be caught in the tooth cavities, leading to bit-balling, which was noticed on inspection of the bit. The jets thus assisted in keeping the tooth cavities clean. This is just perceptibly reflected in the penetration-rate curves of Fig. 1: Much the same results were obtained in hard rocks with hard-formation three-cone bits. The conclusion is that transport of loose cuttings towards the annulus does not require a powerful jet action. In the following sections we shall see that in deep-well drilling other phenomena are of greater importance. DYNAMIC HOLD-DOWN It is generally accepted that, in deep-well drilling, bit penetration is hampered primarily by the existence of a difference in pressure between the fluid in the hole and that in the rock at the depth of cutting.2-5 In the drilling

Jan 1, 1965

By Paul G. Shewmon

The migration of slightly solzrhle spherical particles through a solid under the infllrence of a temperature gradient is analylzed for the cases of various transport mechanisms. It is shown that the variation of the velocity of the particles with radius, r, depends on the dominant mechanism of matter transport around or through the inclusion. Thus the velocity varies as r-1 jor surface-dijf1~sion controlled migratzon. is independent of r for volume diffusion in either phase, and varies as if the rate is determined by an interfacial reaction (n is the order of the interfacia1 reaction). These same results hold tor the migration of a cvlinder of length much greater than its radius. and .for other types of potential gradients, e.g., an electrical field. These equations are combined with recent electron-microscopic ohservations to show that the rate of migratzolz of small helium-silled bubbles through copper is determined by surface diffusion of the metal atoms. With these equations and the temperature gradients attainahle in an electron-microscope joil, the dominant transpar/ mechanism (or any migrating pnrtzclos can he determined. AS a result of fission, rare-gas atoms are created in the hot fuel element of a nuclear reactor. These insoluble atoms precipitate to form bubbles of the gas in the fuel. The subsequent migration and coalescence of these bubbles is thought to play a dominant role in the swelling of fuel elements which in turn can limit the fuel-element life. As a result of this practical problem and because of the relative simplicity of the system, workers in several laboratories have imbedded rare-gas atoms in metals with the aid of an accelerator and studied the formation and behavior of the bubbles that form on annealing. Recently Barnes and Mazey have studied the migration of such helium-filled bubbles in copper foils using the electron microscope and the temperature gradient that can be induced in the foil by the electron beam. They found that the smaller bubbles moved faster than the larger ones. It is shown below that, if this is true, the rate-controlling step in their migration is surface diffusion of metal atoms instead of volume diffusion, vapor transport, or an interfacial reaction. The analysis given is in no way limited to gaseous inclusions so the variation of velocity with particle size for any relatively insoluble precipitate particles could be used to obtain information about the relative importance of surface diffusion, volume diffusion, and interfacial reaction in such two-phase systems. VOID MIGRATION IN A TEMPERATURE-GRADIENT ANALYSIS Barnes' studies indicate that helium does not dissolve or diffuse in metals to a measurable extent, so that when the voids move they must do so through the movement of metal atoms from the leading to the trailing sides of the void.' Thus voids might move by surface diffusion, diffusion of vacancies in the surrounding lattice, or vapor transport. We consider first the case of flow by surface diffusion alone. We assume that there is a force, in the sense of irreversible thermodynamics, tending to move the atoms around the bubble in a given direction. We designate this direction as the x axis and the force per atom as Fa. The net rate of flow of atoms from one side of the bubble to the other, under the influence of this force, is the surface flux, Js, times the cross-sectional area available for flow, A,. A, is taken as the circumference times the thickness of the high-diffusivity surface layer 6. Thus where 51 is the atomic volume. For bubbles to advance a distance dx, a volume equal to nr : dx must flow around the void so that The minus sign enters because the bubble moves in the direction opposite to that of the force on the atoms. Equations for volume diffusion and diffusion through the vapor can be obtained in the same manner. For vapor transport we have Ag = and the ratio of the densities of metal atoms in the gas and the solid (pg/pl) enters so that

Jan 1, 1964

By R. Simon, D. J. Graue

This paper presents correlations for predicting the solu-lility, swelling and viscosity behavior of CO2-crude oil sys8i.m~. The correlations were developed from experimental data obtained by the authors. These data are also presented. The data were determined by measuring the properties of mixtures of CO, and nine different oils. Experiinental conditions covered a range of 100 to 250°F and pressures up to 2,300 psia. Properties predicted by the correlations have average deviations, expressed as per cent of experimental value, of 2 per cent for solubility, 0.5 per cent for swelling and 12 per cent for viscosity. INTRODUCTION Interest in CO2 injection as an oil recovery process has led to the development of performance prediction methods which can be applied to specific reservoirs.1 iS To use these performance prediction methods, it is necessary to know the solubility, swelling and viscosity properties of CO2-crude oil mixtures at reservoir conditions. Some information on these properties has appeared in the literature; however, this information did not cover the range of different oils and conditions needed to prepare generalized correlations for reservoir engineering purposes. Consequently, an experimental program was undertaken to collect the data needed. The data obtained and the correlations developed from the data are described in the following sections of this paper. SOLUBILITY OF CO2 IN CRUDE OILS CO2 solubility data in the literature come from six principal sources. The solubility prediction method of Welker and Dunlop3 is limited to 80F. The information in Ref. 4 is of two types: the first includes binary and ternary mixtures of CO, and light hydrocarbons (C1 to C6), and the second gives data for CO1 and heavy hydrocarbons for a temperature range of 40 to 90F. Ref. 5 contains a KCO2 chart for systems whose convergence pressure is 4,000 psia. The KCO2's are based mainly on CO2-natural gas mixtures. Poettmann's work covered CO2 solubility in one condensate and one crude oil6,7 Ja-coby and Rzasa measured CO? solubilities as a function of pressure and temperature for two natural gas-absorber oil mixtures and two natural gas-crude oil mixtures.'8 CO, concentration in these four systems was fixed at 5 mol per cent. The work reported in this paper extends CO, solubility data to a variety of different crude oil types in a temperature range from 110 to 250F and pressures up to 2,300 psia. The experimental procedure used by the authors to obtain the solubility data consisted of combining known amounts of pure CO, and crude oil in a visual cell at a fixed temperature and measuring the bubble point of the mixture. Measurements were made for a total of 40 different CO2-oil mixtures and the results are shown in Table 2. The mixtures included nine different oils (seven crude oils and two refined oils) whose properties are listed in Table 1. All nine oils had vapor pressures less than 1 atm at the experimental temperatures. Consequently, analysis of the bubble-point vapor showed a CO, concentration over 99 mol per cent. At no time during these experiments was a second, more dense, liquid phase observed. The solubility correlation which was developed from the data in Table 2 is presented in Figs. 1, 2 and 3. In these figures, solubility is expressed as xco2 the mol fraction of CO, in the CO2-oil mixture. Fig. 1 shows solubility as a function of CO2 fugacity6 and temperature. Fig. 2 shows the same solubility data expressed as a function of saturation pressure and temperature. The solubility shown in Figs. 1 and 2 is for an oil whose UOP characterization factor is 11.7. UOP characterization factors of crude oils can be determined from Ref. 10 if the viscosity and APT gravity of the oil are known. Fig. 3 gives the solubility correction factor for oils whose UOP characterization factors differ from 11.7. The solubility correlation in Figs. 1, 2 and 3 predicted

Jan 1, 1966

By G. J. Dickman, W. N. Thomas

The factors involved in selecting, a drive system for a grinding mill, including gearing arrangement, motor selection, and electric-supply system limitations are reviewed. Equipment costs are evaluated on a dollar per horsepower basis and starting performance is analyzed, the latter making use of a recently developed computer program. The present interest in large-diameter grinding mills and the rapidly rising cost of the drive in proportion to the cost of the mill establishes a need to explore the drive system in detail. The drive for a 7 to 8,000 hp mill will cost from $350 to $600,000 which represents nearly half the total cost of the mill package, and requires as much building space as the mill proper. Some of the drive components require a longer time to manufacture and the installation time and costs are equal to those for the mill. It is apparent that the drive has become a dominant factor in the overall mill design consideration. A new plant requires a tremendous investment in both time and money. With the high degree of competition in the mining industry, low capital cost is an exceedingly important factor in the development of a project. It is just as important, however, to insure that the equipment is going to perform satisfactorily for the anticipated life of the project without adding unplanned operating, maintenance, and replacement costs. This is the position in which the engineer or designer usually finds himself and is really one of his primary functionsestablishing a realistic compromise between cost and performance. Large primary grinding mills can represent a major portion of the cost of a plant and the drive system accounts for a substantial part of this cost. These facts justify a careful analysis of the drive requirements and all of the factors involved in ultimately arriving at the best system for the lowest cost. A number of excellent papers have been published on various aspects of mill drives. The authors have used information from these papers in making a study of a drive for a 7600-hp, 32 x 12-ft autogenous mill. This was a broad investigation, including mechanical and electrical design, layout, performance, and maintenance considerations, and overall economics leading to the selection of the optimum system for that mill. This paper was developed from the study and includes information applicable to large mills in general. For a successful and economical application, the drive must be considered as a system and all of the components analyzed to determine their effect on the system. This requires the participation of the mill designer, gear, and other mechanical component manufacturers, motor manufacturer, plant designer, and operator. A careful analysis of the mill torque requirements is first necessary to provide a basis for selection of the mechanical and electrical drive components. Because of manufacturing limitations on the size and capacity of gearing available for these low-speed applications, an evaluation of costs for various gear ratios and configurations in conjunction with motor speeds is required. Consultation with the power-supply company is necessary to determine limitations on motor-starting disturbances and to analyze operating costs on the basis of existing rate structures and low characteristics. Finally, consideration must be given to the drive arrangement and its affect on plant layout, space requirements, and location of auxiliary equipment for the selected process. There are presently three basic schemes for driving a mill. The first is a direct drive by a motor operating at mill speed with no gearing. The second is by a higher-speed motor through a trunnion-connected gear drive. The third is by a motor through the more conventional pinion and ring-gear with the option of an interposing gear box to permit greater motor speed than pinion shaft speed. [(Fig. 1.)] Several manufacturers have or are presently developing motors which drive the mill directly without the use of gears. One arrangement has the motor armature intimately surrounding the mill shell-discharge spout or extension of the trunnion journal. The motor stator is then supported independently and surrounds the shell or trunnion-mounted rotor. Another variation utilizes an independent mill-speed motor connected to the trunnion by a drive shaft and flexible couplings.

Jan 1, 1972

By N. K. Chen, R. B. Pond

IN the study of slip band* formation, there have been many examples to show that they do not always appear as lines traversing the entire crystal, but as segments whose ends seem to vanish in their path through the crystal. This characteristic appearance of slip bands has been witnessed under the optical microscope at various magnifications'-' and also under the electron microscope.' A typical example of this behavior seen with the optical microscope is shown in Fig. 1. However, the slip band studies were generally conducted on polished surfaces of single or poly-crystalline metals which had been previously deformed; i.e., the load was generally released so that the observation could be made. Any picture of slip bands so obtained can represent the surface phenomenon only in a static state of the strained material. The conditions prior to their formation cannot be definitely and clearly assigned. Thus, while a segmented slip band may suggest that slip is a growth process as supposed by the theory of the nucleation of slip,V he usual appearance of suddenly and fully developed slip bands around the crystal has generally been considered as a consequence of uniform shear of the entire slip plane akin to a cataclysmic process. Little clear-cut information is available with regard to the speed at which a slip band forms, its direction of motion, the geometry of its position with regard to its neighbors, and its dependence on orientation. A description is given in this paper of experimental apparatus by which the progressive formation of slip bands can be recorded while the specimen is undergoing deformation. Qualitative and quantitative data on the dynamic formation of slip bands will be presented with special interest concerning the propagation of slip bands, the spacing of slip bands, and their relations to strain hardening. Views on the formation of slip bands are discussed and a mechanism of the unit process involved in the formation of a slip band is proposed. Preparation of Specimens Single-crystal specimens of high purity aluminum (99.997 pct), 1/8 in. square in cross-section and 1% in. long in gage length, were made by the method of gradual solidification from the liquid state. Since no machining work could be introduced in preparation of crystals of such small size, a special mold was designed for casting them to final shape. The mold consisted of two, separate, high purity graphite blocks. Generally, 20 molds were packed together in one container so that 20 specimens could be obtained by one casting operation. This was desirable since it was possible by this method to obtain groups of crystals with similar orientations. The as-cast crystals were carefully clipped from the gate, etched, and homogenized for 24 hr at 600°C. They were then very gently polished using a 4/0 paper, re-etched, and finally electrolytically polished after the method previously described by Chen and Mathewson.6 The crystallographic orientations were determined using a back-reflection, Laue method. Tensile Testing and Photographic Method The tensile testing equipment for these tests was composed of a specially designed microtensile machine, microload cell and microclip gage with necessary appurtenances. The members of the microtensile machine consisted of three parts, as shown in Fig. 2. The chassis is equipped with an oil cylinder, A, and piston, the piston being part of the movable cross-head, B. Pressure in the oil cylinder is controlled and regulated by an external pneumatic-hydraulic cell, C, which is connected to the cylinder by a Vs in. high pressure copper tube. This cell is half filled with hydraulic oil and has a needle valve, D, on the oil exit side as well as a needle valve, E, on the gas inlet side. A quick-acting valve, F, as well as a pressure gage is provided for the gas side. The oil exits into the load piston on the microtensile machine. By connecting a tank of inert gas to the gas inlet, regulated pressures were provided over the oil so that the oil would leave the cell at a rate determined by the setting of the exit needle valve, the gas pressure, and the pressure of the oil in the load piston of the microtensile machine. With this pneumatic-hydraulic appurtenance it was possible to

Jan 1, 1953

By G. G. Hancock, H. H. Johnson

Hydrogen gas at atmospheric pressure is shown to cause substantial embrittlement in a martettsitic high-stretzgth steel. Subcritical crack growth is observed at very lom stresses and with high growth rates. It is suggested that an adsorbed layer of hydrogen atoms at the crack-tip surface provides the damaging hydrogen. Oxygen in small quantity, as little as O.7 pct by volume, is shown to eliminate subcritical crack growth in gas environments caused by hydrogen or water vapor. However, dissolved oxygen in water has little or no influence upon crack-growth rates. Oxygen-stopped cracks may be restarted by water, or by hydvogen or water vapor if oxygen is removed from the environment. These observations are interpreted in terms of preferential adsorption of oxygen at the crack tip and the formation of an oxide barrier. RECENT investigations1-3 have demonstrated that environmental factors are frequently responsible for delayed failure in martensitic high-strength steels. The environment causes crack initiation from preexisting cracklike flaws at unexpectedly low stresses, often far below the uniaxial yield strength. The crack then propagates at a rate controlled by the environment and the crack-tip stress-field intensity; during this period crack propagation will cease if either the stress or the aggressive environment is removed, and this may be considered a definition of subcritical crack growth. Fracture occurs when the crack has grown to a critical length, such that the fracture toughness of the steel is exceeded. Several liquids are known to cause delayed failure, but water and water vapor are the most severely damaging of the environments investigated to date.'-3 It has been suggested that hydrogen produced during corrosion reactions may be the actual embrittling agent2 The severe embrittlement caused by water vapor inevitably raises the question as to whether other gas environments are damaging. Previous work4'5 has demonstrated that high-pressure hydrogen (2250 psi or greater) is an effective embrittling medium, as measured by such criteria as reduction in area, notch tensile strength, and time to failure. Moreover, the embrittlement was eliminated by the addition of small quantities of air or oxygen to the high-pressure hydrogen, but it was not influenced by additions of nitrogen or argon.4 In the present study attention is focused upon gas environments at atmospheric pressure, in particular hydrogen and oxygen. The influence of these constituents upon the initiation and growth of a crack from a pre-existing cracklike flaw in a high-strength steel was determined directly by the electric-potential method of monitoring crack growth. MATERIALS AND PROCEDURE The H-11 steel was supplied by the U.S. Naval Research Laboratory as 3 by 12 by 0.065 in. sheet specimens with 1-in. transverse center slots. The slot tips were finished by Elox machining to a radius of 0.001 in. or less. The yield strength was 230,000 psi; chemical composition and heat-treatment schedule are given in Table I. The experimental apparatus, precracking procedure, and incremental loading sequence have been described previously.3 In the only significant change, precracking was sometimes carried out by a hydrogen embrittlement and baking technique. All experiments were conducted at room temperature; the hydrogen gas environment was purified by a commercial palladium purifier. Crack initiation and propagation were followed by the electric-potential method,'-3 using a calibration that has been recently dicussed. Stress-field intensities at the crack tip were computed by the conventional Irwin frmula; the plasticity correction was negligible and therefore not included. EXPERIMENTAL RESULTS A striking brittleness associated with molecular hydrogen at atmospheric pressure is demonstrated by the data in Table I1 and Fig. 1, which indicate that subcritical cracks in hydrogen initiate at lower stress-field intensities and propagate more rapidly than in fully humid argon. Ki and Kf are the crack-tip stress-field intensities at initiation and termination of subcritical crack growth, respectively. Termination, of course, corresponds to fracture. In both hydrogen and humid argon Ki is less than Kf

Jan 1, 1967

By H. S. Thomsen, W. C. Duesterhoeft, R. E. Hartline

The attenuation and phase shift which formations produce in the electromagnetic field of an induction-type electrical well-logging instrument are great enough to substantially affect the response of the tool to formation conductivity under normal logging conditions. The application of the general equations for the propagation of an electromagnetic field in a conductive medium to the transmitter-receiver coil pair of an induction-logging-tool coil system gives an expression for the response which properly takes the propagation effects into account. A comparison of a calculation of this type with the response computed from the commonly used geometric factor concept, which does not include the propagation effect, leads to a factor Go representing the ratio of the responses computed by the two methods. The value of Go decreases not only with increasing formation conductivity, but also with increasing transmitter-to-detector coil spacing. For a single coil pair with a 40-in. spacing, the value of Go is 0.972 in a 20-millimho/m formation. The value is reduced to 0.915 and 0.812 for conductivities of 200 and 1,000 millimhos/m. As a result, the basic signal generated by the induction-logging coil system is not linearly related to formation conductivity as expected from the geometric factor concept. A uniform conductivity scale can be obtained only by adding a suitable nonlinear element to the recording system. The addition of auxiliary coils, having spacings less than the main-coil span, to achieve focusing results in an even greater departure of the basic signal from linearity with conductivity. The solution of the field equations near the interface between two formations of different conductivity gives the curve shape on an induction logging tool in crossing the interface. The addition of auxiliary coils to achieve focusing can add anomalous character to the curve shape in crossing the interface, which might be mistaken for lithological detail. Preliminary calculations which include the propagation effects in the determination of the conductivity correction for thin beds lead to correction factors which are substantially smaller than those obtained from geometric factor considerations. It is apparent that thin-bed corrections derived from geometric factor calculations are of doubtful validity. INTRODUCTION Although the electromagnetic induction type of electrical well log has been used for a number of years and has gained general acceptance in quantitative well-log interpretation, no technically complete investigation of the mechanism and of its operation has been published. The studies which have been presented are based upon the premise that neither the shape nor the intensity of the induction field of the logging tool is in any way affected by the electrical characteristics of the formation. From the inception of induction logging it has been recognized that under some formation conditions the performance of the instrument could be expected to be substantially different from that predicted by the simplified analysis. This anomalous performance has been called "skin effect" since it is the result of the same phenomenon which causes high-frequency alternating currents to flow only near the surface of metallic conductors. In the range of conductivities encountered in the sediments, the formation actually does not exhibit the sharply defined conducting "skin" shown by metals. The gradual modification of the distribution of the currents in the formation, produced by the induction field of the logging tool, is the direct result of phenomena associated with the propagation of the electromagnetic field through the formation. Therefore, it can be much more appropriately described as the "propagation effect". One purpose of this paper is to review the results of a solution of the equations for the performance of a single transmitter-receiver coil pair induction-logging system which takes into account the propagation effect, showing the manner in which the tool performance established by this analysis differs from that derived from the less comprehensive analyses currently in use. PRINCIPLE OF OPERATION OF THE INDUCTION LOGGING INSTRUMENT The high-frequency alternating current which is maintained at a constant value in the transmitter coil

By N. J. Grant, R. Nordheim

An extensive study was made of the aging characteristics of alloys based on the 80 pct Ni-20 pct Cr composition hardened with aluminum and/or titanium, each up to 4 pct. Aging was followed by means of hardness and hot electrical resistance measurements as well as by X-ray and microscopy. Stress rupture tests at 1500°F were utilized as a check on the predicted behavior. THE titanium and aluminum hardened Ni-Cr alloys, exemplified by Nimonic 80 and Inconel X, constitute one of the more important groups of alloys developed to meet the demand for materials retaining their strength at elevated temperatures. For service in the temperature range 1200" to 1500°F, these alloys offer high creep resistance. With increasing service temperature, however, the strength of the simpler Ni-Cr base alloys falls off rapidly so that above 1500°F there is a significant loss of strength. The present investigation was undertaken with the hope that a better understanding of the factors controlling the precipitation hardening of these alloys would make it possible to increase the useful service temperature range. Primarily this investigation involved the study of the effects of titanium and aluminum on the hardening and the subsequent softening at elevated temperatures. The titanium and aluminum contents were each varied between 0 and 4 pct by weight at a constant nickel to chromium weight ratio of about 4:1. (Except when otherwise stated, all compositions are expressed on a weight basis.) The major part of the investigation was confined to alloys with less than 0.06 pct C. Recently several papers dealing with the identity of the microconstituents in the titanium and aluminum hardened Ni-Cr alloys have been published. Using X-ray analysis of the residues from anodic dissolution, Rosenbauml was only able to identify carbides and nitrides in Nimonic 80 and Inconel X. However, since Rosenbaum worked with alloys in the hot rolled rather than in the aged condition, his results are inconclusive. Recently Hignett' reported that the hardening of Nimonic 80 was due to the controlled precipitation of Ni,(TiAl) having the cubic Ni3A1 structure. Taylor and Floydv-" published the results of an investigation of the nickel-rich corner of the Ni-Cr-Ti, Ni-Cr-Al, and Ni-Ti-A1 systems. In the Ni-Ti and the Ni-A1 systems the hexagonal Ni,Ti phase, 7, and the cubic Ni3A1 phase, -y', respectively, exist in equilibrium with the nickel-rich solid solution. The interatomic distances in the basal plane of Ni,Ti and the octahedral planes of the matrix are almost equal, thus explaining the Wid-manstaetten type structure formed when Ni,Ti precipitates from solid solution. When Ni:,Al precipitates from solid solution, it appears usually in globular form, often dispersed along rows corresponding to definite crystallographic directions. The 7 and phases are also the only intermetallic compounds which occur in the nickel ternary alloys with up to 25 pct Cr and 10 pct Ti or Al. Taylor and Floyd found that Ni,Ti takes practically no nickel, chromium, or aluminum into solution. Nial, on the other hand, dissolves a considerable amount of chromium and titanium and some nickel. Up to three out of every five aluminum atoms could be replaced by titanium in Ni,Al. This substitution caused a slight increase (less than 1 pct) in the lattice parameter. With respect to the effect of variation in the titanium and aluminum contents on the high temperature strength of Nimonic 80 type alloys, Pfeil, Allen, and Conway" reported that an 80 pct Ni-20 pct Cr alloy containing 0.20 to 0.30 pct A1 had the highest creep resistance when the titanium content was kept between 1.65 and 2.75 pct. Experimental Procedure The materials used for this investigation were electrolytic nickel, electrolytic or low carbon chromium, sponge titanium and 2s aluminum. The alloys were melted in an indirect carbon arc furnace under

Jan 1, 1955

By V. C. Williams

Some of the physical, chemical, and electrical processes for conversion of saline water to potable or industrial water are economically surveyed from an engineering viewpoint. Since all these processes require energy for drive and equipment for containment, the correlative economic factors are developed which indicate directive influences in the choice of particular regional processes. The supply of natural waters and its distance also affect decision. Any one process will probably not prove dominant in the field because auxiliary considerations such as the saline water source; types and continuing availability of fuel; electric power use or recovery; area economic status and advancement; and the political pressures of population, group demands, and land use tend equivocally to obscure capital and operation cost decisions. Basic engineering considerations, data, and economic factors are presented to assist in the direction of these decisions. An exploding world population, increasing industrialization, advancing standards of living, and the desire of less-privileged nations for betterment focus attention sharply on a major problem: water. *19 Up to now, in retrospect, people have had it relatively easy in the handling of this problem. All the better dams in the most advantageous sites, the better aquifers, the shortest aqueducts have been built. In another phase of the problem, concern is evident that wastes cannot indefinitely be disposed of merely by keeping them dilute and discharging them promiscuously. 7-9 And, perhaps, as past civilizations have done,l5 water, watersheds, streams, and irrigation may have been mismanaged or, at the least, not adequately studied.3,5,36,37 In this last is perhaps the core of the problem. As Gross states, "Ignorance and too often, indifference are contributing factors. Archaeology and theology both furnish ample testimony to the existence of rich lands where deserts now stand; it was man who ravaged his land. Unless education is a companion to water development, development might as well be forgotten. But without water, there is no beginning."13 The U.S. is showing increasing concern about its water for predictions are that by 1980 the daily withdrawals will be 494 billion gal, a figure nearly equal to the dependable supply.Is This is based on a conservative projected population of 230 million. The major categories of withdrawals are: To make available this per capita average of 2150 gal per day will require an expenditure of $219 billion over the next 20 years. The U.S. is not alone in this concern. The United Nations shows as arid zones of the world: all of Africa north of the equator and south of the 20's parallel; all of the Arabian peninsula; all of the middle east and Iran, Iraq, Pakistan, Afghanistan, northern and central India; a great band about 1000 miles wide along the 40'~ parallel from the Caspian Sea east across Russia through China to the Pacific Ocean; all of Australia except the coastal plain; the Caribbean Islands; the western nations of South America; and the western third of the United States and of Mexico. With one quarter of the earth's 57,500,000 sq miles of land thus suffering from lack of good water, increasing attention goes to the treatment of brackish and sea waters. The U.S. has been a leader in this field4,12, 16123,24 through its Office of Saline Water in the Dept. of Interior because even now some of its cities and regions are short of potable water. 11j'7,M Industrial water is also of vital concern as a result of ever higher industrialization1,14122 Other nations, among them JaPan, Israel,13188 Germany, Union of South Africa, Australia, Netherlands, France, Yugoslavia, Russia, and groups such as the Organization for European Economic Cooperation (OEEC)' are also diligent. The objective is low cost water, which means that both technology and economics have prominent roles in saline water conversion processes. TECHNOLOGY: SALINE WATER CONVERSION A number of reviews of methods have been made, principally by staff members of the Office of Saline Water (U.S. Dept. of Interior). Jenkins,31'32 Gillam,34p

Jan 1, 1962

By Brahm Prakash, R. Schuhmann

Chemical conditions for flotation and nonflotation of quartz with oleic acid as collector and barium, calcium, aluminum, iron, and tin as activators were studied using a simple vacuum-flotation technique in glass-stoppered graduates. The detailed study of barium activation led to an interpretation based on ideal Langmuirian chemi-sorption. FLOTATION of quartz is of practical importance as something to be avoided in soap-floating many types of ores. Clean, unactivated quartz is not floated with fatty acids and soaps, such as oleic acid and sodium oleate, in the quantities normally used for flotation. However, data in the literature indicate that almost any multivalent cation will activate quartz if given an opportunity. Thus, a common problem is to prevent activation of quartz by the various inorganic cations inevitably present in flotation pulps. Wark and his coworkers1 have demonstrated the reversibility of the chemical reactions and adsorptions involved in the activation, depression, and collection of the common sulphide minerals. The procedure in much of their work was to bring a mineral surface to equilibrium with solutions of known pH, collector concentration, and activator concentration, and then to test the floatability of the mineral by contact-angle measurement. From the data, graphs were constructed with pH and reagent concentrations as coordinates. These graphs show fields of flotation and fields of nonflotation, separated by narrow transition regions whose locations are shown by so-called contact curves. From the shapes and locations of the contact curves, which roughly separate fields of flotation from fields of nonflotation, a quantitative understanding of the interaction of the reagents with each other and with the minerals often can be deduced. The study of quartz flotation to be described in this paper follows in broad lines the approach of Wark and coworkers. That is, pH, activator concentration, and collector concentration were varied to find equilibrium conditions of flotation and non- flotation, and the results are presented graphically by means of contact curves. However, instead of testing for floatability by measuring the contact angle on a polished surface, a simple vacuum flotation technique was developed and used. Purified oleic acid was the collector and terpineol the frother. Barium activation was studied in some detail, and exploratory studies were made of activation with calcium, aluminum, ferric iron, and stannic tin. Preparation of Materials Quartz: Large lumps of high-grade vein quartz were crushed dry in a cone crusher and rolls. The —20, +28-mesh portion was screened out and used in the subsequent steps. This material was passed through a high-intensity magnetic separator to discard iron, then leached twice with hot concentrated HCl and washed repeatedly with distilled water. The cleaned sand was then wet ground with porcelain balls in a porcelain pebble mill, deslimed repeatedly by settling and decantation to discard —800-mesh material, and again washed with hot HCl followed by distilled water. The resulting stock of quartz was stored under water. Chemical analysis gave 99.8 pct SiO2. Table I gives the size analysis of the quartz used for flotation tests. Calculations from these data, using shape factors given by Gaudin and Hukki9 indicate a specific surface of about 500 cm2 per g. Blank flotation tests in distilled water, and in water with added frother, showed the prepared quartz to be completely nonfloatable and thus indicated the absence of organic contamination. Oleic Acid: The preparation of oleic acid was based on fractional vacuum distillation of methyl oleate2,3 followed by regeneration of oleic acid, and finally fractional crystallization of oleic acid from acetone solutions at low temperatures." The pure oleic acid was stored in a refrigerator. The iodine number of the oleic acid was found to be 90.0 (theoretical 89.93). Oleic acid was used in the form of a dilute water solution of sodium oleate, after preliminary flotation tests showed no effects of form of addition and order of addition of reagents when an adequate conditioning time (that is, 30 min) was provided. Other Reagents: Sodium hydroxide solutions low in carbonate were prepared by first making 1:1

Jan 1, 1951

By R. J. Quigg, G. S. Doble

Commercial stress -relieved TD Nickel bar was shown to retain room- and elevated-temperature tensile strength after exposure up to 2501°F. Cold swaging increased both room -temperature and 2000°F tensile strength. After annealing at 2500°F the strengthening due to swaging was retained at 2000°F hilt eliminated at room temperature. Annealing produced changes in hardness and X-ray half peak width indicating the presence of recovery processes as 1071° as 1000°F but no recrystallization of swaged material was noted at any temperature. In contrast to swaging, rolling induced a recrystal-lized structure after annealing. The tensile strength of this recrystallized structure was comparable to the cold-worked condition. High-temperature tensile properties of as -received bar were highly anisotropic with the transverse tensile strength being one fifth the longitudinal value. The aniso-/ropy is affected by working direction and may he partially reversed by changing the direction of metal flow. The divergence in tensile strength, beginning above 550°F or- approximate one third the absolute melting point, is strain-rate dependent. T D Nickel is a commercial dispersion-hardened alloy containing 2 vol pct thoria. The dispersion, consisting of spherical particles 0.030 to 0.050 in diameter with an interparticle spacing of less than 1 is reported to maintain stable properties up to 2400°F.1 This stability of second phase results in maintenance of elevated-temperature strength at higher temperatures and longer times than normal nickel-base superalloys.2 The purpose of this paper is to describe the effect of various mechanical working operations on the strength and microstructural stability of TD Nickel bar. MATERIAL AND PROCEDURES All material used in this study was commercial TD Nickel bar. This material is produced by a chemical process which results in a nickel powder containing a dispersion of thoria particles. The powder is then pressed, sintered, extruded, and subsequently worked to bar stock. Three starting materials from three separate lots were used: as-extruded bar. 1-in.-diam stress-relieved bar, and 1/2-in.-diam stress-relieved bar. Since TD Nickel bar stock is cold-worked without a recrystalliza-tion anneal, the accumulated deformation or degree of cold work in these materials increases as the bar diameter decreases. Some of the 1/2-in.-diam bar was swaged to 1/4 in. diameter at room temperature in order to produce an as-worked condition for comparison with the stress-relieved stock. Tensile testing was performed on an Instron Tensile Tester at a constant crosshead speed of 0.020 in. per min. The 0.2 pct offset yield strength was measured from the load-crosshead movement plot. Specimen gage dimensions were 0.080 in. in diameter by 0.40 in. in length, producing a strain rate of approximately 0.050 min-1. Specimens were tested in air and heated within a resistance-wound furnace controlled to ±5°F. A 15-min soak at temperature was employed before testing. Samples were heat-treated in air and specimens machined after exposure with sufficient material removed to eliminate any surface contamination. X-ray line breadth was determined from a diffractometer scan of a transverse face of a bar using copper K, radiation. Metallographic preparation utilized standard mechanical polishing with Carapella's etch. Specimens for electron microscopy were electropolished in a 1:7 sulfuric/methaol solution and chromium-shadowed collodion replicas prepared. RESULTS AND DISCUSSION I) Effect of Elevated-Temperature Exposure on the properties of TD Nickel. The effect of various elevated-temperature exposures on the room-temperature tensile strength of TD Nickel is shown in Table I. In the unexposed condition the tensile strength, reduction in area, and hardness all increase with increasing accumulated deformation while the elongation decreases. After exposure at 2500°F the strength of all three materials decreases to about 65,000 psi and the elongations increase slightly. The apparent increase in strength of the 1-in. bar after a 2000°F treatment is probably experimental scatter. These results indicate that the room-temperature strengthening due to additional deformation is annealed out upon elevated-temperature exposure. In contrast to the room-temperature data, the 2000°F tensile strengths increase in order of increasing deformation even after exposure. Although some loss of strength occurs after exposure, much of the effect of working is still maintained at 2000°F. The room-temperature hardness after various

Jan 1, 1965

By L. L. Handy

The development of a theory for miscible liquid displacement requires evaluation of the variables which affect growth of the mixing zone between solvent and displaced oil. Factors which appear to be important are individual fluid viscosities, viscosity ratios, flood rate, fluid densities, flow characteristics of the porous medium and molecular diffusion coefficients of the fluid components. The primary purpose of this paper is to evaluate diffusion effects. Theoretical treatments to date have been limited to floods for which the viscosity ratio is one. Two principal theories have been proposed. Von Rosenberg adapted for porous media a theory derived for capillary tubes by G. Taylor.' ,' In this theory molecular diffusion perpendicular to the direction of flow is a primary factor in sharpening the flood front. Slow floods give sharper fronts for a given distance traveled than fast floods. An alternative theory considers miscible liquid displacement as a statistical problem.3,4,5 Diffusion is not an important factor in this theory, but it leads to the same general type of equation as von Rosenberg's. Both theories predict S-shaped concentration profiles with the same dependence on distance traveled. The statistical or "dispersion" theory predicts rate independence, however. To supplement rate studies a direct measurement of a diffusion effect would be helpful in evaluating which of the two proposed mechanisms best describes miscible liquid displacement for one-to-one viscosity ratio systems. No quantitative theory has been proposed for floods in which a low-viscosity fluid displaces a high-viscosity fluid. It might be anticipated, however, that the extensive fingering observed in floods with adverse viscosity ratios would increase opportunities for an exchange of components between displaced and displacing liquids by a diffusional process. Even if molecular diffusion were not an important mixing mechanism for one-to-one viscosity ratio systems, it could be significant in systems with adverse viscosity ratios. METHOD FOR EVALUATING DIFFUSIONAL MIXING In solvent flooding the displacing liquid can become mixed with the displaced liquid by a number of processes; in general, either mechanical or diffusional in character. To evaluate the contribution of diffusion, a method was sought that would distinguish diffusional mixing from mechanical mixing. Suppose two soluble tracers are added to the displacing liquid and that one tracer has a diffusion coefficient much greater than the other. Then, if diffusion is important during miscible liquid displacement and if diffusional transport is primarily transverse to the direction of flow, substances with high diffusion coefficients will have sharper concentration profiles than those with comparatively low molecular diffusion coefficients. In order to have material balance the profiles for the two tracers must intersect. For one-to-one viscosity ratios the intersection would occur at the 50 per cent concentration point. It is generally assumed that diffusion in the direction of flow is negligible. This assumption appears reasonable because flow velocities are ordinarily orders of magnitude greater than diffusional velocities. If this is not a valid assumption, however, the shapes of the fronts will be further degraded by longitudinal diffusion. The effects of rate and molecular diffusion coefficients are the opposite for longitudinal diffusion to those for lateral diffusion. Higher rates or lower diffusion coefficients would tend to give sharper fronts. The double tracer method offers several unique advantages in evaluating effect of molecular diffusion. First, the method gives a direct measure of the effect of diffusion on mixing zone size. Second, the effect of a difference in diffusion coefficients is determined from a single experiment. Comparison of several experiments at different rates is not required. Third, the method is applicable for any viscosity ratio. Fourth, the method is unaffected by density differences between the two fluids which might result in rate dependent gravity effects. EXPERIMENTAL PROCEDURE Suitable tracers are substances whose diffusion coefficients differ as widely as possible, but whose adsorptions on rock surfaces is negligible. The two tracers selected were methanol and sucrose in water solutions. The approximate diffusion coefficients for methanol and sucrose, as given in the International Critical Tables, are 1.3 X 10-5 and 0.3 X 10-5 m2/sec, respectively. Concentrations in the water solutions were 200 gm/liter of solution for both methanol and sucrose. These high

By R. E. Zinkham

An investigation has been conducted to compare short transverse and longitudinal fatigue and fracture properties in 4.25-in.-thick, high strength aluminum alloy plates. One plate was produced using standard rolling techniques while the other was pre.forged before rolling. Little difference was shown in fatigue strength of longitudinal specimens taken from mid-thickness of the plate. Howeuer, in the short transverse orientation fatigue strengths at 107 cycles were about 25 and 50 pct less, respectively, for the preforged and standard rolled plate. Differences in fatigue strengths were attributed to grain size and shape as well US orientation of constituents. Fatigue crack propagation rates and fracture toughness were compared at three different stress intensity (K) levels, using a constant compliance, double cantilever, wedge-shaped specimen. In a given plate, comparable fatigue crack Propagation rates were observed in the longitudinal (i9W) and short transverse (TW) orientations. Somezuhat gveater rates were observed in the short transzerse (TR) orientation. The preforged plute gave a lower rate for all three directions. Considerable secondary cracking developed, at times, over portions of the fatigue crack in both plates, particularly at the lower stress intensity levels in the short transverse specimens. Micro structure revealed constituent stringers as possible causes of the crack branching. Fracture toughness was considerably less in both plates in the short transuerse orientation. It is concluded that preforging not only improved directional tensile properties but also the fatigue and fracture properties in general. On occasion, aluminum plates have been milled away for hinges or bolted connections and stressed through the thickness or short transverse direction. Little or no information is available concerning fatigue characteristics or fracture toughness in this loading orientation in aluminum plate, or of the effect of fabrication on these properties. It was the intent of this project to examine, develop, and apply a unique specimen that has been advocated by others to study the fatigue characteristics and fracture toughness of two differently fabricated high strength aluminum plates. Linear elastic fracture mechanics criteria may be applied to the specimen so that the fatigue crack propagation rate and fracture toughness data may be of use for design or inspection applications. Fatigue characteristics are generally measured in the longtudinal or long transverse direction, where fairly large specimens such as center notched panels,' are usually employed. Limitations are evident due to plate thickness, however, in the type and size of specimen that may be tested in the short transverse direction without extensions. Therefore, a specimen that is to be loaded in this direction should, for convenience, be compact. The general type of fatigue crack propagation specimens discussed and employed herein meet this requirement. These specimens are commonly called double cantilever beam specimens and lately "crackline-loaded edge-crack specimens".2 They may vary from a slope of zero (parallel-sides) to a wedge shape, the type employed herein. In general for most specimens the stress intensity KI at the tip of a crack is a function of the load, P and crack length, a. Some varieties of the wedge shaped specimen, however, give essentially a constant stress intensity KI over a considerable range of crack length.' This feature can be a valuable asset in fatigue crack propagation experiments because the stress-intensity can be controlled simply by controlling the load without regard to crack length. MATERIAL AND METHODS Material. A standard rolled (light pass reduction) and a ~reforged and rolled (heavy pass reduction) plate of 7179-T651 material were used for the evaluation. The chemistry, processing history and average tensile properties are shown in Table I. Specimen Selection and Preparation. The specimen selected for the generation of fatigue initiation or S-N data was an axial tension type and is shown in Fig. 1. Specimens were taken from mid-thickness in the longitudinal and short transverse directions from both plates. Specimens were polished with 500 grit paper in a direction parallel to the loading axis. For the fatigue crack propagation tests, the specimen shown in Fig. 2 was used. This is similar to a specimen that has been employed by Mostovoy3 for fracture toughness studies on 7075-T6 aluminum alloy. It also fortuitiously agrees quite well with the dimensions of a specimen for which Srawley and Gross2

Jan 1, 1970

By L. E. Murr, P. J. Smith

A study has been made by transmission electron microscopy of thin foils of 304 stainless steel fatigued external to the electron microscope in reversed bending, and of thin foils fatigued directly within the microscope in alternating tension. The build-up of stacking faults in the thin foils during fatigue zoas correlated with the dislocatirm structures found in thin films prepared fror fatigued bulk specimens. The performance of the special devices designed for fatigue of thin foils so outlined and the importance of alternative methods of preparation of more uniform fatigue specimens bY vapor deposition are emphasized. INVESTIGATIONS on fatigued bulk aluminum1,' and stainless stee13j4 have revealed the existence of dislocation substructure on examination by transmission electron microscopy of electrolytically thinned foils representative of these bulk specimens. While this technique has proved extremely valuable, it has several shortcomings. First, the method of fatiguing bulk specimens and then thinning to foil for electron-transmission observation allows only one observation of internal structure at any one portion of the fatigue life. Second, thinning the bulk fatigued specimens to foil results in the loss of at least one original surface. Thus, what one sees in the remaining electron-transparent sections is an internal dislocation or fault structure which in many cases cannot be correlated with the original surface markings. This is an undesirable feature, since it is well-known that metal surfaces play an important part in the fatigue process.5 An obvious third undesirable feature of the thinning-from-bulk technique is the fact that static observations have difficulty (in the case of fatigue) explaining the mechanism of a dynamic process. What is required then is a method whereby a selected thin area can be continuously observed either while undergoing cyclic deformation or at various fixed stages of fatigue deformation. While Murr and wilkov6 have reported some success with an apparatus designed to fatigue thin metal foils directly within the electron microscope, the nature of the specimen-mounting procedure and the mechanical features involved in the adaptation of the fatigue device to the electron microscope make this method difficult to operate. It was not possible, for example, to make frequent observations of a selected area because of difficulty in maintaining a chosen area in a stable viewing position inside the electron microscope. Except for the build-up of a dislocation substructure and what are commonly referred to as "slip striations", little else has been reported from observations on thin-foil sections prepared from bulk fatigue specimens. segal17 has found "slip striations" in stainless-steel fatigued specimens which were electropolished from both sides, but gave no explanation as to their origin or identity in terms of lattice imperfections. The research to be reported in this paper was undertaken with the following objectives in mind. First, an attempt was made to devise a technique or techniques whereby thin metal foils could be fatigued and repeatedly observed by transmission electron microscopy. Second, it was hoped that some correlation could be made between deformation striations found in fatigued thin transmission specimens and thin foils prepared from bulk fatigued specimens. These investigations illustrate quite convincingly that a feasible method is available for the direct study of the fatigue mechanism and similar dynamic phenomena in thin transmission specimens inside the electron microscope. I) EXPERIMENTAL METHODS Three modes of specimen fatigue and observation of fatigue damage were used. These involved fatigue of thin-foil specimens in a special arrangement external to the electron microscope and observation of a selected area at various stages in the fatigue life, the fatigue of thin-foil transmission specimens inside the electron microscope, and the fatigue of bulk specimens external to the electron microscope followed by thin-foil preparation for direct observation at predetermined stages. Design of the External Fatigue Clip and Specimen Holder for the Hitachi H.U.11 Electron Micro-scope. The purpose of the fatigue clip was to provide a reversed bending fatigue stress to a thin-foil transmission specimen outside the electron microscope. In order to accomplish this, a flat-bottomed, U-shaped brass clip was made as shown

Jan 1, 1965

By Joseph L. Gillson

IT is a somewhat curious circumstance that the newest of the Institute's several awards should be conferred in the oldest of our several professional fields—for there is little question that geology and mining have antedated metallurgy and petroleum. Perhaps so did geophysics. After all, one geophysical instrument, the magnetic compass, has been successfully employed for many centuries. Young in years the Jackling Award may be, but in distinction—whether in terms of the title it bears or in terms of the first three medalists (Reno Sales, E. D. Gardner, and the late Father MaceIwane)—the Jackling Award is already one of the ranking awards of the Institute. The name of the 1957 medalist will bring added luster to an already illustrious roll. J. L. Gillson was born and brought up in Evan-ston, Ill., in an area characterized by singularly flat and uninspiring topography, and devoid of ore deposits and even of bedrock—a most unlikely environment from which to expect a future Jackling medalist to emerge! On graduating from high school he enrolled as a chemistry major at Northwestern University. At the end of his frkshman year his scholastic prowess had won him a prize of two chemistry books. But these went unread, for about this time he came under the spell of U. S. Grant, that distinguished and enthusiastic geologist who for many years was head of Northwestern's geology department. From thence forward Joe was a dedicated geologist. After a Navy interlude in World War I, he went to MIT for graduate work, substituted for the late Professor Palache for one year at Harvard in mineralogy, received his doctorate at MIT and stayed on as a meniber of the MIT faculty, where the geology department was headed by that great dean of all economic geologists, Waldemar Lindgren. In 1926 Joe spent a summer looking into barite deposits for the du Pont Co., and since 1928 he has been du Pont's chief geologist. Do men who lead such active lives in our exploration organizations generally have permission to publish their observations? Do they generally find time to publish, even if they have permission? Alas, no. But in Joe Gillson's case, yes. His bibliography runs to well over two score papers, including one of the very first papers in this country on the applications of petrography to problems of Portland cement. He has written on such topics as the origin of talc and the genesis of ilmenite, fluorspar, and alkaline rocks. Each year for a number of years his annual reviews of industrial minerals in the Mining Congress Journal have been eagerly awaited. - Do men who do so much to advance their science have anything left to give to the advancement of their profession? In Joe Gillson's case, yes. He has been a vice president of the Mineralogical Society of America and has been active in the councils of the Society of Economic Geology, particularly in their research programs. This year he is president of the American Geological Institute, currently perhaps the most challenging post to which a geologist may be elected. His contributions to AIME scarcely need documentation, so I shall mention only three—his chairmanship of the Committee on Democratization of the Institute, a committee whose work and recommendations brought a new and hopeful leaven to AIME at a time when this was sorely needed; his chairmanship, a few years ago, of the Industrial Minerals Division; and his current place on the Board of Directors as Vice President of the Institute. Such' a catalogue of contributions and achievement, even as condensed as I have had to make it, certainly merits the Jackling Award. Yet, implicit although not often expressed in the conferring of most awards is the hope that besides recognizing a distinguished career, it will provide stimulus for further effort. In the present instance, such an expectation is already well on the way to fulfillment. Only recently Joe Gillson has undertaken the editorship of a new and greatly revised edition of the Institute's Seeley Mudd volume, Industrial Minerals and Rocks. And so, Mr. Chairman, it is with pleasure and enthusiasm that I present Dr. J. L. Gillson for the 1957 Jackling Award.

Jan 1, 1958

By Craig R. Barrett

The influence of the stress dependence of the dislocation density on the overall stress dependence of The steady-state creep rate is discussed. Experimental measurements of dislocation densities and creep rates jor an Fe-3.1 pct Si alloy tested over a wide range of stress are presented which indicate a close correlation between the two quantities. EXPRESSING the stress dependence of high-temperature steady-state creep rates has been the subject of numerous investigations over the past decade. From these investigations have emerged a few general equations which fit most of the available data reasonably well. Garofalo 1 has proposed that for a wide range of stress and temperature the creep rate, i, can be expressed by a relationship of the form: where A, ß, and n are temperature-dependent and is the applied stress. Eq. [I] gives a stress dependence of a at low stresses and exp(nßo) at high stresses, both consistent with experimental observation where n = 5. A number of other investigatorshave proposed a similar expression where: where m and w are in general functions of temperature. Theoretical justification for Eqs. 111 and [2J comes from two different approaches, theories based on dislocation glide3-5 and theories based on the balance between work-hardening and recovery.' Dislocation glide theories predict where p is the mobile dislocation density and V is the activation volume. In order for Eq. [3] to predict a on stress dependence at low stresses with n = 5, it is necessary for p to be a strong function of stress, about proportional to u3 or u4.436 Recovery models of creep start with the general expression:' where r is the recovery rate and h is the work-hardening rate, and then employ a detailed model to determine the stress dependencies of r and h. As example, weertman2 has described a model based on pile-up hardening which results in an expression similar to Eq. [2] with m = 2 and p = 2.5. A recent, seemingly more general approach suggested by McLean is to use Friedels dislocation network growth expression to calculate the stress dependence of r. This model predicts r = p 3,2 and, as h is taken to be a relatively weak function of stress, the stress dependence of i should be about proportional to p3, 2. Once again, it is required that p be a strong function of stress to yield i This recovery model is by no means complete as the stress dependence of network growth is calculated in the absence of an applied stress meaning that r should probably be a stronger function of stress than given by p3, 2 and also some recent work by Mitra and McLean8 suggests that the stress dependence of h may be as large as Because of the importance of the stress dependence of p in determining the overall stress dependence of the strain rate it seems reasonable to examine this relationship in some detail. Measurements made on dislocation densities present during high-temperature steady-state creep generally obey the following relationship a =o0 + aGVWp [5] where uo is usually called a friction stress, a is a numerical constant about equal to unity, G is the shear modulus, and b is the Burgers vector. Depending on the magnitude of uo, data obeying Eq. [5] can give rise to a range of stress dependencies of p. For example, if we assume that the expression where 6 is some constant, adequately represents the stress dependence of p over a range of o, then from Although Eq. [6] obviously breaks down when u 5uo for uo 6 can vary over a wide range of values. In particular, if u > a, > 0 then 6 will be greater than 2. As an example the data of Ishida and McLean are plotted in Fig. 1 showing excellent agreement with dynes per sq cm) and also showing good agreement with a p cc u3 dependence when plotted on a log-log basis. As oo increases 6 tends to increase and correspondingly the stress dependence of the predicted creep rate should also increase,* as-

Jan 1, 1968

By G. A. Moore

A brief review is given of methods designed to produce metallic iron of high purity, and typical results are listed. A recent method, utilized at the National Bureau of Standards, consists of the extraction of ferric chloride by ether, reduction of this ferric chloride to ferrous chloride, further purification of this chloride, and the subsequent electrolytic deposition of metallic iron. iron produced by this procedure apparently is softer than, and otherwise different in properties from, any iron previously prepared and contains appreciably smaller amounts of impurities. THE history of attempts to produce "pure" iron reaches to antiquity and it may be presumed that each ancient armorer who succeeded in making a better steel concluded, correctly, that he had done a better job of removing the "base metals," and incorrectly, that he now at last had a "pure" metal. Early metallurgical papers mentioned use of "pure iron" in making alloys—this "pure" iron in most cases being inferior to some commercial stocks of the present time. Improvement has been continuous, and usually at a sufficient rate to convince each succeeding group of workers that they, at last, were using the really pure metal (until the analysts also improved their techniques to again discover the impurities). These adventures were reviewed in some detail by Cleaves and Thompson.' Although the ores of a metal may be abundant, difficulties in extracting it may make the pure metal very rare. When impurities are restricted to a total of a few parts per million, nearly all pure metals become rarities. Lead, copper, gold, mercury, silver, zinc, aluminum, bismuth, and the six platinum metals are claimed to be available with total impurities ranging from 2 to 50 ppm. The present small and scattered world supply of so-called "pure" iron holds an unimpressive place in another group of 16 metals having approximately 100 ppm of foreign material. Of about 20 less rare metals, only the platinum metals are more costly to prepare. While the production of such rare varieties of iron may appear insignificant in the presence of thousand-ton operations with 95 to 99 pct metal, it must be emphasized that all researches on commercially interesting irons and steels are in fact studies of the modifications of the properties of iron by additional materials. Until the properties of high purity iron are directly measured, all ferrous research must operate without known base values. Traces of impurities may affect the properties of a metal in many ways. Infinitesimal traces of solutes, by disturbing the electronic configuration, greatly change the electrical properties of transistors and semiconductors2-3 and slightly larger traces might alter these quantities in iron. Soluble impurities which disturb the perfection of lattice arrangement not only may alter the magnetic constants and electric properties, but by their close association with dislocation phenomena probably control the very existence of the "yield point"; determine the value of yield stress; and perhaps control the selection of slip and cleavage planes. It has been speculated that impurities might even cause the allotropic transformation in iron, but in any case their rearrangement must contribute to the unreliability of heat capacity and other thermodynamic measurements. Impurities which do not remain in solution may cause even greater effects on the properties. Microscopically visible amounts of phases other than ferrite can be found in all high purity irons which have come to my attention. It can be calculated that from 50 to as little as 2 ppm of an insoluble material might be sufficient to completely film all grain boundaries in irons having grain sizes from ASTM Nos. 10 to 1. Should this occur, such films, even though invisible, may be very important in fracture problems, especially at extremes of temperature:' Studies of grain growth and diffusion normally imply consideration of a single-phase system, hence, in the presence of insoluble impurities they can be expected to give ambiguous data." High purity iron is also in demand for use as chemical and spectro-chemical standards; for work in classifying the lines of the iron spectrum; for biological work in nutrition; and for work in nuclear physics. where the presence of some sensitive

Jan 1, 1954

By C. G. Dunn, F. Lionetti

The energy associated with grain boundaries in polycrystalline aggregates is believed to play a major role in grain growth processes and, when growth ceases, to determine the final equilibrium grain boundary angles. Further, the energy of grain boundaries of recrystallization nuclei is a factor in nucleation processes. It is important to know, therefore, how the energy per unit area of a grain boundary, that is, the grain boundary surface tension y, depends on the difference in orientation of the two lattices of the grains producing the boundary. Although the problem is important, surprisingly little has been done toward a quantitative evaluation of the effect of orientation difference on grain boundary energies. C. S. Smith1 recently has discussed this problem and in addition to showing effects of orientation difference on equilibrium angles has shown a variety of interesting effects of surface tension on the appearance of microstructures. Fig 1 and the following relations expressed in Eq 1, which connect equilibrium grain boundary angles and surface tensions, illustrate equilibrium conditions which are believed to hold true in metals. ?l2 _ ?23 _ ?l3 [1] sin ?3 sin ?1 sin ?2 Clearly any two of these surface tensions can be expressed in terms of the third when the equilibrium angles ?1, ?2, and ?3 are known. Applied to the present problem for solid state equilibrium of three grains, the angles ?1,?2 and ?3 must be measured in a plane perpendicular to the line of junction of the three grains. Normally a direct determination of these angles from random microsections is impossible. Consequently Harker and Parker2 and Smith1 (except for some measurements on flat specimens) resorted to a statistical method to determine equilibrium grain boundary angles. Smith reported that grain boundaries meet the surface of a piece of metal nearly perpendicularly. He reported also, in connection with direct angle measurements on flat specimens with grains extending through the thickness, that angles varied appreciably from 120" and concluded that there was a measurable effect of orientation difference on surface tension. Another direct way of determining equilibrium angles and a method adaptable to studying particular configurations, recently suggested by Dunn,³ is to use a three-grain flat specimen with orientations of grains so chosen that the junction line of the three grains will be straight throughout the thickness and perpendicular to the surface of the specimen. Choice of orientations is possible when individual grains of each group can be grown to predetermined orientations through the reorienting and growth of " seed crystals " as described.³ Not only is it possible, for example, to have grains with the same crystallographic plane in the plane of the specimen, but a given orientation difference between two grains can be made a common factor to an unlimited number of three-grain groups while a series of orientation differences is investigated. Any effect of anisotropy of gas-solid surface tension due to grain orientation should be minimized by having all gains oriented the same with regard to crystallographic plane in the plane of the specimen. Another feature of the three-grain group is the notched grain boundaries as shown in Fig 2 for one specimen (S4). The notches serve to anchor the end positions of the grain boundaries (especially at high temperatures) while the central and junction point of the grains moves toward an equilibrium position. Final equilibrium should produce straight grain boundaries if the notches are very narrow and if changes in orientation* of the grain boundary do not alter the surface tension.† If one assumes the straight line condition and no change of surface tension with small changes in grain boundary orientation and finds the equilibrium configuration by a minimization of the grain boundary energy, one obtains the relations given in Eq 1. The approach to straight line boundaries or to minimum energy configurations in specimens containing large grains, such as those used in the present investigation, may be very slow compared with the approach to equilibrium conditions for the grain boundary angles. It may be desirable, as proved to be the case in the present investiga-

Jan 1, 1950

By B. R. Hollebone

The chemical action of molten anhydrous pyridinium chloride (pyridine hydrochloride) on oxy salts and ores of some Group IV and V metals are discussed-in particular zirconium, hafnium, niobium (columbium) , and tantalum. Laboratory-scale experiments are described whose results suggest that this reaction might provide a practicable means of converting ores of these metals to the anhydrous metal chlorides. Experimental results are given which provide some insight into the nature of the reactions and some of the compounds which could be present at intermediate stages. The treatment of ores of the more refractory metals is difficult and expensive and often demands the use of gaseous chlorine, hydrogen fluoride, or other reagents which are, if nothing else, expensive and dangerous to use. This situation is, of course, due to the strong metal-oxygen affinity resulting from the high charge and the small size of the metal ion which combine to produce such high lattice energy in the metal oxide as to defeat standard reduction methods. Thus, the characteristic of these metals which leads to one of their most important properties—corrosion resistance—is the main hurdle in obtaining the metal. Many common methods' for treating ores of zirconium and niobium (columbium), for example, proceed as directly as possible to the preparation of anhydrous halides. These halides are purified by now standard processes of solvent extraction, fractional distillation, and so on. This paper reports on preliminary stages in the development of a method of treating these ores—particularly of niobium—so as to prepare the anhydrous, volatile halides by the use of chemical reagents which are much more easily handled than those used at present. CHEMICAL PRINCIPLES The solvent action of aminium halides has been referred to periodically in the literature over several decades. The chemistry of pyridinium chloride has been discussed particularly by Audreith2 and Starke.3 However, since this is not familiar chemistry in its nonaqueous setting, it is perhaps well to point out some general metallurgical principles and applications. One can use, as point of departure, the fact that HC1 dissolved in pyridine is an acid very much the same as aqueous HC1. It thus gives essentially all the reactions of the HC1 with which we are familiar. However, when the ratio of HC1:pyridine reaches 1:l (a ratio far higher than is possible with H2O) the solution becomes solid C5F5NHC1, pyridinium chloride.* Inter- estingly, the acidic properties of HC1 persist in this medium, although they are manifest only in the molten state of the compound. Some typical reactions of divalent metal compounds which we have carried out in our laboratories are the following: 2PyHCl + Zn — (ZnCl2) + H2 + 2Py 2PyHCl + MnO — (MnCl2) + H2O + 2Py 2PyHCl + CuS — (CuCl2) + H2S + 2Py 2PyHCl + CaCO3 — (CaCl2) + H2O + CO2 + 2Py In these equations, the parentheses indicate a solvated compound which in water would be predominantly a hydra ted cation but which in molten PyHCl will more likely be a complex chloro-anion of the type MC14-. Some important physical properties of pyridinium chloride (PyHCl) are given in Table I. One sees from the data in Table I that at the temperature of molten pyridinium chloride both water and pyridine will boil away. Thus the system will be kept anhydrous. For this reason the reaction 2NbCl5 + 5H2O— Nb2O5 + 10HC1 has no counterpart in molten PyHCl. Instead, the chloride is made even more stable by the formation of a hexachloro complex: Nb2O5 + 12PyHC1 — 2PyHNbC16 + 5H2O + 10Py One interesting property of these complexes is their thermal instability which for the case of niobium can be illustrated as PyHNbCl6 — PyHCl + NbCl5 With a view to possible use of this chemistry in ore treatment, we have attempted to dissolve Pyrochlore (essentially FeO - Nb2O5) and recover the NbC15 from it.

Jan 1, 1968

By R. McNeill, D. E. Weiss, E. A. Swinton

In a continuous countercurrent exchange process, an alteration in any one of the operating conditions has a complex effect on the others, which can only be predicted by employing the transfer unit or the theoretical stage theory on a basis of trial and error. A simple method is described for illustrating diagrammatically the behavior of a counter-current system, the equations being simplified by means of a concept the maximum hypothetical exchange performance. An example based on a typical metallurgical system is given, in which a divalent metal is recovered from a dilute solution, the resin being regenerated continuously by a monovalent ion. Useful conclusions are drawn from a study of the theory. Practical methods for performing continuous ion exchange are discussed, and the development of equipment based on modified ore dressing jigs is described. A swinging sieve jig contactor is evaluated experimentally. DURING the last decade, the new synthetic ion exchange resins have been applied extensively in industries outside the field of water treatment, but there is no record of a continuous counter-current process operating on an industrial scale. Attempts have been made to devise a satisfactory process but many problems remain to be solved. The basic principles of continuous processes will be outlined, as well as the major problems in their operation and the progress made in the CSIRO laboratories toward the development of satisfactory industrial techniques. In the metallurgical field ion exchange resins can be used for various applications such as the recovery and concentration of valuable metals from mine waters,' the regeneration of pickling and plating liquors," the prevention of pollution by waste effluents and the recovery of the constituents from them," and the purification of valuable metals such as the rare earths by chromatographic fractionation on columns of ion exchange resins.7,8 . Turther applications undoubtedly will be found in the field of hydrometallurgy where the use of ion exchange resins would enable direct extraction of the desired metal ion from the filtered leach liquor or the leach pulp. For example, an ion exchange process has been described recently for the extraction of gold from a cyanide leach pulp." A continuous process would have advantages in many applications over the usual process employing a fixed bed and intermittent cycle. In a recovery process, it would yield a product stream of steady purity and concentration, it would waste less water in rinsing, and if the contacting apparatus were efficient less resin would be used, since each portion of the resin would be cycled as soon as it was loaded instead of lying idle until the whole bed was ready for regeneration. A very major advantage is that it would be simpler to control automatically. It is probable that continuous operation will be the key for really large scale applications of ion exchange. The flow sheet of a continuous ion exchange recovery-concentration process is illustrated diagrammatically in Fig. 1. Dilute liquor containing the valuable ion flows through the stripping section countercurrently to a moving bed of resin and leaves after a final contact with freshly regenerated resin. The resin leaves the unit almost in equilibrium with the incoming liquor and then flows to the regenerating unit where it is treated by a slow countercurrent flow of concentrated regenerant solution. The adsorbed ion is displaced from the resin and appears in the concentrated product stream. The resin then must pass through a rinse unit or section where regenerant entrained by the resin is washed back into the regeneration section by water. The regenerated and washed resin is then recycled back to the stripping section. I. Theoretical Operating Behavior of Continuous Ion Exchange Stripping System The simple theory of continuous ion exchange is analogous to that of solvent extraction and other diffusional transfer operations and is governed by the equilibrium relationship, the mass balance, the rates of mass transfer, and the contacting efficiency of the unit. Equilibrium Relationship—The relative affinity of two ions A and B, for a particular resin immersed in their solution, can be expressed by plotting compositions of the solution against compositions which exist in resin in equilibrium with those solutions, i.e. C/Co vs q/a where C, is the total normality of the solution, C is the normality of ion A in the solution, a is the total exchange capacity of the resin in gram equivalents

Jan 1, 1956