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By Frank G. Miller

This report presents developments of fundamental equations for describing the flow and thermodynamic behavior of two-phase single-component fluids moving under steady conditions through porous media. Many of the theoretical considerations upon which these equations are premised have received little or no attention in oil-reservoir fluid-flow research. The significance of the underlying flow theory in oil-producing operations is indicated. In particular, the theoretical analysis pertains to the steady, adiabatic, macroscopically linear, two-phase flow of a single-component fluid through a horizontal column of porous medium. It is considered that the test fluid enters the upstream end of the column while entirely in the liquid state, moves downstream an appreciable distance, begins to vaporize, and then moves through the remainder of the column as a gas-liquid mixture. The problem posed is to find the total weight rate of flow and the pressure distribution along the column for a given inlet pressure and temperature, a given exit pres5ure or temperature and given characteristics of the test fluid and porous medium. In developing the theory, gas-liquid interfacial phenomena are treated. phase equilibrium is assumed and previous theoretical work of other investigators of the problem is modified. Laboratory experiments performed with specially designed apparatus. in which propane is used as the test fluid, substantiate the theory. The apparatus. materials and experimental procedure are described. Comparative experimental and theoretical results are presented and discussed. It is believed that the research findings contributed in this * paper should not only lead to a better understanding of oil-reservoir behavior, but also should be suggective in regard to future research in this field of study. INTRODUCTION In recent years much time and effort has been consumed in both theoretical and experimental studies of the static and . dvnamic behavior of oil-reservoir fluids in porous rocks. Although lack of sufficient basic oil-field data, principally concerning the properties and characteristics of reservoir rocks and fluids, largely precludes quantitative application of research results to oil-field problems, qualitative application has become common practice. In effect. oil-reservoir engineering research is serving as a firm foundation for oil-field development and production practices leading to increased economic recoveries of petroleum. This province of research. however, still poses many perplexing problems. The thermodynamic behavior of two-phase fluids moving through porous media constitutes one facet of reservoir-fluid-flow research that has not received the attention it deserves. This report embodies a theoretical discussion of this subject and a description of a series of related laboratory experiments. The significance of the problem to oil field operations is indicated but in articular the report centers around a theory and method for analyzing the steady. macroscopically linear, two-phase flow of a fluid (a single molecular species) through a horizontal column of porous medium. For simplicity in showing how the thermodynamic behavior of two-phase fluids moving through porous media affects oil-reservoir performance problems, attention is focused temporarily on a particular well producing petroleum from an idealized water-free solution-gas drive reservoir, the reservoir rock being a horizontal, thin, fairly homogeneous sandstone of large areal extent confined between two impermeable strata. The flowing hydrocarbon fluid is considered to exist entirely as a Iiquid at points in the reservoir remote from the well; however. the decline in fluid pressure in the direction of the well causes vaporization of the hydrocarbon to begin at a radial distance r from the well. Upstream from r the fluid moves entirely as a liquid and downstream from r it moves either entirely as a gas or as a gas-liquid mixture depending on the properties of the hydrocarbon and on the thermodynamic process it follows during flow. The distance r would be variable under transient flow conditions. but for purposes of analysis the flow is considered to l~e steady at the particular instant of observation during the flowing life of the well of interest. If the flow were isothermal and the hydrocarbon a pure substance, the fluid would be entirely gaseous downstream from r. Thus, this isothermal flow process for a pure substance would require that the heat of vaporization be supplied at r. over zero length of porous medium, at the precise rate necessary to maintain the constant temperature. This means that the solid matrix of the porous medium (reservoir rock) and the surroundings (impermeable strata confining the reservoir rock) would have to serve as infinite heat sources. Heat-transfer requirements would be somewhat less severe for the isothermal flow of a multicorn-ponent hydrocarbon as bubble and dew points at the same temperature correspond to different pressures. In this instance isothermal conditions would be sustained without complete vaporization of the fluid over zero length of porous medium. Nevertheless. as the flow is in the direction of decreasing

Jan 1, 1951

By Frank G. Miller

This report presents developments of fundamental equations for describing the flow and thermodynamic behavior of two-phase single-component fluids moving under steady conditions through porous media. Many of the theoretical considerations upon which these equations are premised have received little or no attention in oil-reservoir fluid-flow research. The significance of the underlying flow theory in oil-producing operations is indicated. In particular, the theoretical analysis pertains to the steady, adiabatic, macroscopically linear, two-phase flow of a single-component fluid through a horizontal column of porous medium. It is considered that the test fluid enters the upstream end of the column while entirely in the liquid state, moves downstream an appreciable distance, begins to vaporize, and then moves through the remainder of the column as a gas-liquid mixture. The problem posed is to find the total weight rate of flow and the pressure distribution along the column for a given inlet pressure and temperature, a given exit pres5ure or temperature and given characteristics of the test fluid and porous medium. In developing the theory, gas-liquid interfacial phenomena are treated. phase equilibrium is assumed and previous theoretical work of other investigators of the problem is modified. Laboratory experiments performed with specially designed apparatus. in which propane is used as the test fluid, substantiate the theory. The apparatus. materials and experimental procedure are described. Comparative experimental and theoretical results are presented and discussed. It is believed that the research findings contributed in this * paper should not only lead to a better understanding of oil-reservoir behavior, but also should be suggective in regard to future research in this field of study. INTRODUCTION In recent years much time and effort has been consumed in both theoretical and experimental studies of the static and . dvnamic behavior of oil-reservoir fluids in porous rocks. Although lack of sufficient basic oil-field data, principally concerning the properties and characteristics of reservoir rocks and fluids, largely precludes quantitative application of research results to oil-field problems, qualitative application has become common practice. In effect. oil-reservoir engineering research is serving as a firm foundation for oil-field development and production practices leading to increased economic recoveries of petroleum. This province of research. however, still poses many perplexing problems. The thermodynamic behavior of two-phase fluids moving through porous media constitutes one facet of reservoir-fluid-flow research that has not received the attention it deserves. This report embodies a theoretical discussion of this subject and a description of a series of related laboratory experiments. The significance of the problem to oil field operations is indicated but in articular the report centers around a theory and method for analyzing the steady. macroscopically linear, two-phase flow of a fluid (a single molecular species) through a horizontal column of porous medium. For simplicity in showing how the thermodynamic behavior of two-phase fluids moving through porous media affects oil-reservoir performance problems, attention is focused temporarily on a particular well producing petroleum from an idealized water-free solution-gas drive reservoir, the reservoir rock being a horizontal, thin, fairly homogeneous sandstone of large areal extent confined between two impermeable strata. The flowing hydrocarbon fluid is considered to exist entirely as a Iiquid at points in the reservoir remote from the well; however. the decline in fluid pressure in the direction of the well causes vaporization of the hydrocarbon to begin at a radial distance r from the well. Upstream from r the fluid moves entirely as a liquid and downstream from r it moves either entirely as a gas or as a gas-liquid mixture depending on the properties of the hydrocarbon and on the thermodynamic process it follows during flow. The distance r would be variable under transient flow conditions. but for purposes of analysis the flow is considered to l~e steady at the particular instant of observation during the flowing life of the well of interest. If the flow were isothermal and the hydrocarbon a pure substance, the fluid would be entirely gaseous downstream from r. Thus, this isothermal flow process for a pure substance would require that the heat of vaporization be supplied at r. over zero length of porous medium, at the precise rate necessary to maintain the constant temperature. This means that the solid matrix of the porous medium (reservoir rock) and the surroundings (impermeable strata confining the reservoir rock) would have to serve as infinite heat sources. Heat-transfer requirements would be somewhat less severe for the isothermal flow of a multicorn-ponent hydrocarbon as bubble and dew points at the same temperature correspond to different pressures. In this instance isothermal conditions would be sustained without complete vaporization of the fluid over zero length of porous medium. Nevertheless. as the flow is in the direction of decreasing

Jan 1, 1951

IT is difficult to judge how much influence the success attained during its first year, 186465, by the School of Mines at Columbia had on developments in education for the mineral industry elsewhere in the immediately subsequent years. The facts are as follows: 1. The Massachusetts Institute of Technology began giving instruction in February 1865, with a mining course included in its curriculum. 2. Early in 1865 the faculty of the Department of Science, Literature and the Arts of the University of Michigan requested permission from the Regents to establish "a course of study to be called the School of Mines . . . Also that the degree of Mining Engineering be conferred on students who should complete the course of study prescribed in the same." A resolution authorizing this was adopted by the Regents on March 28, 1865. 3. Samuel Hooper endowed a Sturgis-Hooper professorship of geology at Harvard in 1865 with the intention of making it a nucleus of a new School of Practical Mining and Geology. 4. Yale appointed Alfred P. Rockwell professor of mining in 1865. 5. Lafayette College appointed Henry S. Osborn professor of mining and metallurgy in 1865. 6. Washington College (as Washington and Lee was then known), rising out of the ashes of Civil War destruction, made a fresh start in 1865, with General Lee as its president, and offered a mining course in the first catalogue thereafter published. 7. Lehigh University, founded in 1866, had a mining curriculum from its beginning. 8. Rensselaer Polytechnic began offering a curriculum in mining and metallurgical engineering in 1867. It would be natural to suppose that these events were a reaction to the success of the school at Columbia, and possibly they

Jan 1, 1941

By L. W. Pommier, F. B. Brien

The Rheological properties of pulps are non-Newtonian in character and more than one viscosity parameter is necessary to describe their behavior, therefore, the single term 'apparent viscosity' which has been used in the past may be misleading. The study reported in this paper uses a dimensional analysis based on the Ostwald-de Waele shear stress-rate of shear model for non-Newtonian liquids to develop velocity and resistance equations for falling spheres. An electronic monitoring apparatus was assembled for determining the velocity of metallic bodies as they fall through opaque liquids and suspensions. By means of this apparatus the behavior of the viscosity parameters of the Ostwald-de Waele model and the applicability of the proposed equations were examined for a number of non-Newtonian liquids. The validity of the equations for these liquids was confirmed. Preliminary data collected using solid-liquid suspensions established the validity of the form of the basic equations for these systems. The differential movement of solid particles through solid-liquid pulps and suspensions is very important LO many branches of engineering, such as minerals processing, soil mechanics, ceramic slip processing, oil well drilling-mud technology, materials-handling in pipelines, and many others. There is a dearth of fundamental knowledge on the flow resistance encountered by immersed bodies moving through solid-liquid suspensions. The resistance offered by Newtonian liquids to the movement of free settling spheres is well described for laminar and turbulent conditions by Stokes' and Newton's Laws, respectively. However, problems are encountered when attempts are made to extrapolate these simple relationships into solid liquid suspensions. The rheological properties of pulps are such that they are non-Newtonian in character;'" that is, the applied shearing stress and resulting rate-of-shear are related by non-linear functions, and thus, in the simplest case two viscosity parameters are necessary to describe their rheological properties. For this reason the single term 'apparent viscosity' which has been commonly used to explain the flow resistance of suspensions and non-Newtonian liquids may be misleading. It is realized that a rigorous analysis of the rnechanisms of momentum transport of liquid-solid systems is complex indeed. There are many variables that affect the rheological properties of the systems such as density, size, shape, and surface energy of the suspended solid and density and viscosity of suspending liquid, as well as the solid to liquid ratio. However, it was felt that a useful contribution to the knowledge of the behavior of suspensions could be made by examining the systems in terms of the basic fundamentals of nowNewtonian flow. This has led to the development, by means of dimensional analysis, of velocity and resistance equations, using two viscosity parameters to describe the velocity of penetrating bodies and the flow resistance encountered by these bodies, as they pass through non-Newtonian systems. THEORY In order to examine the effects of the rheological properties of solid-liquid suspensions on the movement of immersed bodies it is appropriate to start with non-Newtonian liquids and develop equations, analogous to those of Stokes and Newton, for laminar and turbulent flow respectively, from which quantitative information may be obtained. Further investigation would then be directed at the complex suspension systems, and the effects of the many variables on the velocity and resistance equations. Liquids are classified on a basis of viscosity which may be defined as the relationship between applied shear stress and resulting rate of shear?-'* Pure single phase liquids composed of small light molecules behave as Newtonian liquids, having a single viscosity parameter since the shearing stress and rate-of-shear are related by a linear function. Bingham plastics are similar but have a yield stress. Of particular importance in our investigation are dilatant (shear thickening) and pseudoplastic (shear thinning) non-Newtonian liquids, with and without yield values.

Jan 1, 1968

By F. A. Forward, V. N. Mackiw

The paper relates to the laboratory and pilot plant studies that have been carried out by Sherritt Gordon Mines Ltd., Metallurgical Research Div., in developing the ammonia pressure leach process for extracting copper, nickel, cobalt, and sulphur from high grade nickel concentrate produced from Lynn Lake ores, and describes in some detail the chemistry of the process. IT is well known'.' 2 that copper, nickel, cobalt, zinc, ferrous iron, and a number of other metals combine with ammonia in aqueous solution to form complex ions of the form [Me(NH,)x]"+. The stability and solubility of these ions depend on the concentration of the metal ion in solution, on the amount of NH, present, and on the amount and type of anions present, e.g., OH-, C0;-, NO,, C1-, SO;-. If ammonia is partially or completely removed from such solutions, for example by boiling, the soluble ammines tend to decompose and the metals precipitate as basic salts. These properties of metal ammines have found practical application in the commercial recovery of copper, nickel, and cobalt from a variety of ores. In an operation formerly conducted at Kennecott"" the mill tailing containing 0.80 pct Cu as copper carbonate was leached by percolation with an ammonia-ammonium carbonate solution to dissolve the copper as the ammine. At Calumet and Hecla0-" With a mill tailing containing about 0.4 pct Cu as metallic copper, it has been found necessary to aerate the ammonia-ammonium carbonate leach solutions between stages to oxidize the solubilized copper. At Nicarol"-" where nickel and cobalt occur as oxides and silicates which are not soluble in ammonia, the ore is heated to decompose silicates and to selectively reduce the nickel and cobalt to metal, leaving the iron as Fe,O,, and is then leached with ammonia-ammonium carbonate solution accompanied by aeration to dissolve nickel and cobalt as ammines. In each of these leaching operations, the anion present is CO, and the metals can be precipitated from the leach solution as oxide (copper) or hydroxide and carbonate (nickel and cobalt) by boil- ing off NH, and C02 both of which are recycled to treat a subsequent ore charge. The products-—oxide, hydroxide, or carbonate—can be treated by conventional smelting, calcining, or electrolytic methods to convert them to refined metals. Thus the procedures mentioned utilize the properties of the ammines to extract copper, nickel, and cobalt from nonsulphide ores and separate them from the leach solutions. These processes have the advantage that they can be carried out in closed vessels at atmospheric pressure, that the leaching solutions are specific for the desired metals, that the metals can be recovered as relatively pure compounds by the boiling operation, and that the NH, and CO, can be recycled. Also, as the leach solutions after boiling and filtration are substantially free of metals, NH,, and CO,, they can be discarded, thus facilitating the control of the water balance in the leaching circuit. When, as is the case with Sherritt Gordon concentrates, sulphides are treated with ammonia solution in the presence of oxygen, the leach solution contains SO,--, and an entirely different set of conditions is encountered. The ammine sulphates (of nickel, for example) are more soluble than the carbonates and can be only partially decomposed by boiling. The SO, and NH, in the solutions can not be recovered by boiling. Thus, despite the more favorable leaching conditions resulting from high solubility of the ammine sulphates, the recovery of metals, NH,, and SO, from the solutions must be effected by other means. Sherritt Gordon Nickel Concentrate Treatment The Ni-Cu-Co flotation concentrate produced at Lynn Lake'" contains 12 to 16 pct Ni, 1 to 2 pct Cu, 0.2 to 0.5 pct Co, 33 to 40 pct Fe, 28 to 34 pct S, 8 to 20 pct insoluble, and less than 0.02 oz per ton precious metals. The nickel is present chiefly as pentlandite, the copper as chalcopyrite, and the iron as pyrrhotite and pyrite. Most of the cobalt is thought to be present in pentlandite, although it is known that a small amount occurs as Co-Ni-pyrite.

Jan 1, 1956

By T. V. Philip, R. E. Lenhart

When commercial silicon iron sheets of varying magnetic quality are isothermally annealed at high temperatures, extremely large grains develop in the material having good magnetic properties. These grains are of the (110) [001] orientation and are formed by secondary recrystallization. The primary driving force for this secondary recrystallization is grain boundary free energy. For the secondary grains, activation energies of 103 kcal per mole for nucleation, and of 75.5 kcal per mole for growth, were obtained. The activation energy for nucleation of the secondary grains is consistent with a model involving redistribution of a precipitate acting as the primary grain growth inhibitor. SINGLY oriented silicon iron sheet was first produced in 1935.1 The material as commercially produced today has a very highly developed preferred orientation or texture; up to 95 pct of the grains are crystallographically oriented with their (110) planes in the plane of the sheet and their [loo] directions parallel to the rolling direction. This texture, usually written as (110) [00l], is referred to as the "GOSS" or the "cube-on-edge" texture. Because the magnetic properties of this material are superior to those of the nonoriented sheets in the direction of rolling, the oriented silicon iron has acquired tremendous industrial importance especially in the manufacture of transformer cores and other electrical equipment. The commercially produced material is essentially an iron-silicon alloy containing about 3 1/4 pct Si with minor impurities totaling less than 0.15 pct. The silicon steel heat is melted in the open hearth or electric furnace. The ingots are hot rolled, with or without being slabbed, to strips of 0.100 to 0.080 in. thickness. They are then cold reduced to an intermediate thickness, recrystallized, cold reduced to final thickness, decarburized, and finally annealed at a high temperature. During this high-temperature anneal, extremely large grains with the cube-on-edge texture are produced in the sheet. Several papers have appeared in the literature2-10 relating to the production of the Goss-textured material. Most of these describe the textures produced on cold rolling and on subsequent annealing of single crystal or polycrystalline silicon iron. May and Turnbull11,12 have recently shown the necessity of a second-phase dispersed impurity in the material for the production of the Goss texture. However, none of these papers describes in detail the nucleation and growth kinetics of the (110) [001] grains during the final high-temperature anneal.* The present work, therefore, is an attempt to understand the nucleation and growth kinetics of the cube-on-edge grains in the silicon iron sheet during the final high-temperature anneal.

Jan 1, 1962

By J. C. Melrose, W. R. Foster, J. G. Savins, E. R. Parish

Many differences can be imagined between gas-oil flow in which the gas is supplied at the face of the core and gas-oil flow in which the flowing gas was originally dissolved in the oil. If capillary pressure characteristics and flow requirements control gas saturation distribution, the gas would be expected to be located at preferred sites within the porous medium as determined by pore sizes. On the other hand, during solution gas drive the gas first appears as bubbles through a nuclea-tion process. Nothing in self-nucleation theory specifies at which sites the first bubbles should be formed. In all probability they will be randomly distributed throughout the porous medium. Furthermore, it is not at all certain that even at low rates of production the gas will redistribute itself after nucleation to the channels normally occupied by gas in simple gas flow. Stewart, et at, have shown that at least for some limestone samples, oil recoveries could not be predicted for all rates of production using any one set of relative gas and oil permeabilities. An important factor in controlling recoveries during solution gas drive was the rate of bubble formation, higher rates giving higher recoveries. Stewart, et al, attributed the increase in recovery to a better distribution of the gas phase in heterogeneous limestone samples than is obtained by simple external gas drive. Differences in recovery from these causes were not reported for sandstone cores. In the experiments to be reported here, oil recovery, pressure and producing GOR history were measured during solution gas drive for a 5-ft sandstone core. The results were compared with predictions from the Muskat method for computing solution gas-drive behavior using external gas-drive relative permeability. The effects of changing the rate of production and oil viscosity were studied. At high laboratory rates of average pressure decline, two observations were made which would not have been predicted by Muskat's depletion theory: (1) oil recovery increased with increasing rate of production for a given viscosity oil, and (2) oil recovery increased with increasing oil viscosity for a given high rate of production. Both of these observations are explained as consequences of diffusion control of gas saturations superimposed on the normal gas-oil flow requirements, Fur- thermore, discontinuous gas phase flow appears to be significant during solution gas drive. The laboratory tests were performed at rates of average pressure decline many times greater than the maximum possible rate of average pressure decline in an actual oil field. It is, therefore, not possible to draw any direct conclusions regarding the effect of rate on recovery for the solution gas-drive mechanism under actual field conditions. However, at the lower laboratory rates, recoveries were nearly independent of rate and could be predicted by the Muskat method, using external gas-drive relative permeability data. These results suggest that at normal oilfield rates the effect of rate on recovery for the solution gas-drive mechanism is negligible. EXPERIMENTAL PROCEDURES The core material for the pressure depletion studies was Bandera sandstone from an outcrop in the Mid-Continent. This sandstone was selected because of its low permeability (about 10 md), which would permit the development of substantial pressure gradients in the corn at moderate flow rates. The core was 5-ft long and 2-in. in diameter. Its properties are listed in Table 1. Relative gas-to-oil permeability ratios were measured by an external gas-drive method2. The results are shown for a short 2-in. core and for the 5-ft core in Fig. 8. Oils used in the pressure depletion experiments were kerosene and a highly refined white oil (standard white oil No. 3) with gas-free viscosities of 1.8 and 25 cp, respectively. The gas was a naturally occurring methane from Gough field, Inglewood, Calif. The oil viscosities, gas solubilities and formation volume factors are plotted as functions of pressure at 75°F in Figs. 1 and 2. Methane viscosities and compressibilities were obtained from the literature"'. A core mounting was required which could withstand up to 2,500 psi internal pressure. This was obtained by first encasing the core completely in a plastic resin (Scotch Cast, manufactured by Minnesota Mining & Manufacturing Co.) The plastic covered core was then inserted into a steel pipe equipped with screw caps so that the plastic coating could be pressured from

By W. H. Emmons

MANY mineral veins occupy faults, and movements on certain warped fault planes have resulted in openings. On normal faults the [ ] steeper parts have the widest openings, and on reverse faults the flatter parts have the widest openings. Theoretically the width of the opening is the sine of the angle of deflection times the amount of movement on the fault plane, but actually the widths of some of the openings are probably less because of readjustments of walls along joints or of other readjustments. The first treatment of the subject seems to have been in a book on mineral veins by John Leithart, published in Newcastle, England, in 1838. Later the subject was treated in various texts published in Germany, in England, and elsewhere. The subject was not given much prominence in the earlier American literature on economic geology, but has interested several workers in that field in the past decade. In this paper examples of districts showing ore shoots on warped faults, with relations noted, are described. Fault veins of the three depth classes of veins are noted. Many epithermal veins are in normal faults, and commonly the larger ore shoots are in their steeper portions. Many mesothermal veins are in reverse faults and many others are in normal faults. The flatter parts of veins in reverse faults are commonly wider than the steeper parts, although they are not always as rich as the steeper segments of the veins. There are not many hypothermal veins in faults of measured displacement.

Jan 1, 1943

By John W. Gabelman

Uranium exploration technology historically has followed the economic cycle of demand, exploration spurt, and trailing supply; but with a greater lag. Greatest progress was made during the wane of demand as geological investigation caught up with the flood of new discoveries made during relatively short periods of peak demand. Updating brought technology to a new level based on the deposits which were discovered and not on the total range of deposit types which might exist. The technology was seldom able to predict new deposit types or new districts, which have consistently been surprises. Yet each new cycle of increased demand was at a new higher level, occasioned by a new use, which required the discovery of previously unrecognized larger types of deposits. Hindsight shows that data sufficient to have predicted most discoveries were available. The predicted growth of uranium demand far in excess of estimated resources is an incentive to examine current technology for data or promising techniques that might foster discovery by technical prediction rather than by systematic drilling. The world could well be reexamined systematically with new geophysical techniques including gamma spectrometry, radon emanometry, and magnetometry. Known occurrences could well be reevaluated in the light of new data on mineralization process and supergene leaching. Less-leachable extrinsic elements associated with uranium might he sought as clues to unleached uranium at depth. Uranium is increasingly being noted in environments containing coal and petroleum which might become targets. High-temperature replacement disseminations are increasingly reported and particularly attractive as exemplified by the Rossing district. The number of formations containing uranium occurrences is growing so that new, not necessarily fluvial, formations might be productive. Enough drilling has been done to indicate that uranium is selectively distributed regionally under some control yet to be determined. Exploration should address those environments and areas where uranium could occur rather than only those where it is already known.

Jan 1, 1976

By Edmund C. Pechin

I REGRET that I am unable to present this subject in definite form and detail. All I shall attempt at this meeting is to lay before you some curious facts, the bearings and explanations of which must be reserved for future consideration. I hope before the next meeting to have carried experiments far enough to furnish a more important contribution to the science of iron metallurgy. The Wickersham process consists in the introduction into the molten metal, as it runs from the furnace, of air from the hot blast. Mr. Samuel Wickersham is the originator of the plan, as applied in practice, although Mr. Martien had the idea a long time ago, and, I believe, .went to England about it. But at that time Mr. Bessemer was coming before the public with his invention, which engrossed the attention of iron-masters, and Mr. Martien accomplished nothing. The principal difficulty in our experiments at Dunbar was to get a practicable runner or trough, through which the molten metal should pass, and in which it should be exposed to the action of the blast. The runner we used was ten feet long, and perforated on the sides to permit the entrance of the air-currents. When we used a cast-iron and fire-clay runner, the heat was so great that before we were more than half done with a run, the lower part of the runner was melted, and we had a magnificent Fourth of July display of fireworks until the blast was shut off. We had to abandon fire clay. The runner with which we have had the best success ,is made of wrought-iron tubes, 2 1/2 inches in diameter, attached to a wrought-iron frame, and lined with a mixture of crushed conglomerate (quartz) and a little fire clay to give it cohesion. The wrought-iron shell curves inward over the upper edges, so as to catch and throw back into the current the flying sparks and particles of metal thrown out by ebullition. With this we have been able to run 12 to 14 tons at a heat with great ease. Mr. Wickersham has since prepared this material (pounded quartz) into a shaped brick or tile, with the necessary perforations for the passage of the air, which promises to answer every requirement for steady working. As regards the improvement in the quality of the iron, there seems to be no question. A large number of practical tests were made in

Jan 1, 1873

By Charles F. Hickey, Eric B. Kula

Thermomechanical treatments applied to the maraging steels include a) cold working in the austenitic condition at 650°F, followed by transformation to martensite and aging, b) cold working in the murtensitic condition and aging, and c) cold working in the aged condition with and without subsequent reaging. The strength increases in these steels are very small compared to the increases observed in conventional carbon and alloy steels. The changes that are observed are compatible with the strengthening mechanisms operative during thermomechanical treatment of conventional steels, however. Differences are caused by the absence of a carbide precipitate and the low work-hardening rate in both the solution-treated and the aged conditions. ThE 18 pct Ni maraging steels represent a class of steels which are finding great interest for high-strength applications.1~2 They are essentially carbon-free, and contain 7 to 9 pct Co, 3 to 5 pct Mo, and 0.2 to 0.8 pct Ti. Although austenitic at elevated temperatures, they can be air-cooled to room temperature to form a martensite, which because of the absence of carbon is relatively soft. On subsequent reheating age hardening occurs and strength levels of 250 to 300 ksi yield strength can be attained. These steels appear to be particularly suitable for studying the response to various thermome-chanical treatments for additional reasons other than the obvious one of attempting to improve their already attractive properties. Thermomechanical treatments can be defined as treatments whereby plastic deformation, generally below the recrystal-lization temperature, is introduced into the heat-treatment cycle of a steel in order to improve the properties. With an absence of intermediate transformation products on air cooling the maraging steels have good hardenability and hence can readily be cold-worked in the austenitic condition prior to transformation to martensite. Further, they can be worked in the martensitic condition prior to aging, and even can be deformed in the fully aged condition. Finally, it is of interest to compare their re- sponse to that of the more conventional alloy and carbon steels, where the role of carbides is important in the strength increase by thermomechani-cal treatments. The thermomechanical treatment of conventional steels has been the subject of a recent review.' I) MATERIALS AND PROCEDURE The steel used in this investigation was a commercially produced vacuum-melt heat, which had been rolled to 0.090 in. and mill-annealed. The composition of the alloy was as follows: 0.02 C, 0.08 Mn, 0.10 Si, 0.009 P, 0.009 S, 18.96 Ni, 7.34 Co, 5.04 Mo, 0.29 Ti, 0.05 Al, 0.004 B, 0.01 Zr, and 0.05 Ca. Unless otherwise stated the heat treatments used were the standai-d solution treatment at 1500°F for 1 hr, air cool, followed by a 900°F, 3 hr age. In this condition, the material exhibited 232 ksi yield strength and 239 ksi tensile strength. Mechanical properties were determined by Vicker's hardness measurement (20 kg) and by tensile tests on standard 1/2-in.-wide, 2-in.-gage-length sheet tensile specimens. Notch tensile tests were run using the 1-in.-wide NASA type, edge-notched specimen.4 Fracture-toughness determinations were made on 3-in.-wide, center-notched, fatigue-cracked specimens, following the recommendations of the ASTM Committee on Fracture-Toughness Testing.4 An electric-potential technique was used for measuring the crack size at the onset of rapid crack propagation5 which is necessary for calculations of Kc, the critical stress-intensity factor under plane-stress conditions. The critical stress-intensity factor under plane-strain conditions KI, was also calculated, using the stress at which the first observable crack growth occurred. 11) RESULTS A) Cold-Worked in the Austenitic Condition. The reported M, temperature for the 18 pct Ni maraging steel is about 310°F.1 Therefore, a temperature of 650°F was selected as suitable for rolling in the austenitic condition. Specimens were solution-treated at 1500°F for 1 hr, air-cooled to 650°F, and rolled varying percentages from 0 to 60 pct, at 20 pct reduction per pass. Tensile and hardness properties after aging at 900°F for 3 hr are shown in Fig. 1. The tensile strength increases from 253 to 271 ksi and the yield strength from 247 to 265 ksi as a result of a reduc-

Jan 1, 1964

By E. P. Dahlberg, R. E. Reed-Hill

On the assumption that stress or strain relaxation occurs as the result of a thermally activated process, equations are derived relating to tensile experiments that give the strain as a function of the time under the condition of constant stress, and the stress as a function of the time for constant strain. It is demonstrated that if the strain-rate equation i = previously proPosed by Kuhlmann., is used as a starting point, then the relaxation of strain at constant stress may be expressed by the equation c = (-RT/(Y) 1tz tanh (t + is the strain capable of being relaxed at any given instant. Similarly, it is shown that the relaxation of stress at constant strain may be given by a = (-RT/B) In tanh (t + t0)/27, where a is the instantaneois value of the relaxable stress. The fact that these relationships reduce to well-known empirical equations at both large and small values of the stress Or strain is also shozcn. The present theory is shown to agree well with experimental data obtained from tensile elastic aftereffect experiments on a zirconium specimen prestrained at 77 k as to make it strongly anelastic. It is also demonstrated that elastic aftereffect data obtained using torsional specimens ?,Lay agree reasonably well with the equation derived for the case of tension. RELAXATION experiments are often employed as a means of studying metallic deformation mechanisms.' The simplest and most commonly employed techniques involve stress relaxation at constant strain and strain relaxation at constant stress. In general, however, investigations of this nature have been seriously handicapped in the past by a lack of suitable equations giving the time dependence of the relaxing variable over an interval that extends from small strains up into the region where internal-friction experiments become strain-amplitude dependent. This paper presents a derivation of such a set of equations for the case where the time-dependent part of the strain is anelastic or recoverable and the specimens are loaded in simple tension. The relaxation of strain under the condition of constant stress will be considered first. Let us assume that strain relaxation occurs as the result of a reversible thermally activated process that occurs at a number of relaxation centers lying in an elastic matrix. Then, following Kuhlmann,2 we may express the rate of strain relaxation as follows: where C is the strain rate, AFx the free energy of activation of the process controlling strain relaxation, a, the effective or average resolved stress at the relaxation centers, u an activation volume, R the universal gas constant, T the absolute temperature, > a factor with dimensions of a volume that accounts for the strain contribution of a successful operation of a unit process, N the number of relaxation centers per unit volume, and v the Debye frequency. The first term on the right of Eq. [I] represents a strain rate in the direction favored by the stress, while the second term represents the rate in the opposite direction. It is implied in Eq. [I.] that both F and v are symmetrical with respect to the two basic directions of operation of a relaxation process. Eq. [I] may also be written where and S and Q are the activation entropy and activation energy, respectively, of the relaxation process. In the following, A will be considered a constant. This is compatible with a set of experimental conditions where the relaxation rate is controlled by a single basic reversible process in which it may be assumed that the temperature dependence of the product ?Nv is negligible in comparison with the temperature variation of the exponential term. It is also implied that v, 7, and N do not depend strongly on a, . In deriving a relationship for the strain as a function of the time from her equation, equivalent to Eq. [2], Kuhlmann2 chose to consider only the limiting cases where the time was either very small or very large. It will now be shown that it is possible to integrate Eq. [2] to obtain a single equation valid over a wide range of strains if the concept of relaxable strain is introduced. The use of this quantity, which is the difference between the instantaneous value of the strain and the value of the strain at complete relaxation, represents the primary point of departure of the present theory from that of earlier workers. Let us express the effective stress at the relaxation centers in terms of strain. For this purpose we may use the following equation derived by zener3 for the case of strain relaxation at slip bands: where M? and M are the relaxed and unrelaxed moduli respectively, go the applied constant tensile stress, and m an average orientation factor that takes account of the fact that a,, the effective stress at the relaxation center, may not be a tensile stress (i.e., a

Jan 1, 1967

By C. L. Magee, H. W. Paxton

PREVIOUS workersl'% ave found that as-quenched ferrous martensites can be plastically deformed at low stresses. They have also found that the stress to obtain small strains can be significantly increased by aging at temperatures up to 150°C. This behavior has been interpreted in two ways: 1) that the deformation at low applied stress is due to internal stresses and thus the aging phenomenon is due to relaxation of the internal stresses;' 2) that the microdeformation arises through the motion of unpinned dislocations and the aging process is the diffusion of carbon to the dislocations to pin them.293 In a recent paper,4 we have shown that under certain conditions the dominant microdeformation mechanism of as-quenched Fe-31Ni marten-site-austenite aggregates is the transformation of retained austenite. Our results on resistance changes during deformation and temperature dependence of the deformation also established that, at temperatures above 300° K, the microdeformation was not due to this transformation. The purpose of this note is to report results of experiments which indicate that explanation 1 is appropriate for this deformation. All results presented here are from conditions where transformation does not make a measurable contribution to the microplastic deformation, in Fe-31Ni-0.002C, or in Fe-29Ni-0.02C-0.25Ti. The experimental techniques that were used for measurement of the plastic deformation are described4 and analyzed5 elsewhere. Fig. 1 shows the microplastic response of 100 pct austenite at 300" and 350° K. The microplastic response of an austenite-martensite aggregate is also given in Fig. 1 and it is seen that, after formation of martensite, the initial plastic deformation occurs at lower stresses. Thus, the softness is not entirely due to retained austenite—the quenched structure can be deformed at lower stresses despite the fact that the macroscopic strength is significantly higher. A result which allows a distinction to be drawn between the alternative explanations for this behavior is derived from aging experiments on the low-carbon alloy containing titanium. We have previously shown4 that the presence of titanium in this alloy reduced the free carbon to a sufficiently low level that thermal stabilization of the austenite-martensite transformation was not detected. Despite this, Fig. 2 shows that the microplastic response is decreased by aging treatments. A similar aging effect in Fe-ZONi, with some titanium, has previously been reported by . Thus, carbon is not necessary for the aging process and explanation 2 is at best incomplete. Since internal stress relief can occur independently of carbon (any temperature dependence of the flow stress can result in decreased internal

Jan 1, 1969

By W. A. Riggs

In a single year the total transportation cost equals nearly 30 pct of the value of mineral commodities, the largest single cost from the deposit to consumer. The magnitude of this economic factor calls for more complete understanding of cost and operational problems between producer and carrier than now exists. Details are given of the costs of providing transportation as well as freight rates for selling transportation. In 1958, transportation of mineral commodities in the United States required 600 billion ton-miles to move 1 3/4 billion tons of products of mines comprising solid fuels, crude oil, industrial minerals and rocks, and ores. Possibly 17 pct was handled by more than one mode of transport, since combinations of several modes of transport may, at times, achieve better service/cost results than any single mode. Total transportation cost of nearly $5 billion equaled roughly 30 pct of the value of the mineral commodities, the largest single cost from the mineral deposit to the consumer. The tremendous magnitude of this transportation undertaking demands much more complete understanding than now exists between mineral producers and carriers about the economic and operational problems of each other. A substantial portion of the daily work of the writer is spent in trying to act as a combination interpreter and catalyst between potential shippers and carriers, hoping to direct both to points of mutual understanding and advantage. For the purpose of this paper, it is necessary to ask mining people to accept some terminology and to try to appreciate the mental approach of the freight rate making people of the carriers. This paper will consider costs of providing transportation as well as freight rates for selling transportation—although these are fields of limited certainty. There are no accurate statistical breakdowns for all modes of transport and types of carriers indicating commodities, volume of traffic, distances, costs, and rates. Much information is available for railroads, and some for the regulated portions of air, motor, pipeline, and water transportation. Unregulated carriers, handling about half of the transportation of products of mines, are not required to report, and very little is known of their activities. Figures used herein are national in scope, unless otherwise indicated, and have generally been derived from Interstate Commerce Commission reports and files. Tonnage figures have been reduced to net tons of 2000 lb. The very generalized comparison of average mileage freight rate levels for various modes of transport provided by Fig. 1 affords advantageous perspective for the entire field of transportation costs. Dashed guide lines show cents per ton-mile, and dotted guide lines show percentage of first class railroad freight rate. While costs of other than railroad transportation more nearly follow constant cents per ton-mile functions, costs of railroad transportation show characteristic taper, or decrease in cents per-ton mile with increasing length of haul. This fundamental difference in cost is due largely to the fact that railroads and pipelines provide their own fully taxed roadway facilities while highway, waterway, and air carriers use government-provided tax-free roadway at no cost other than fuel, license, and certain excise taxes. Thus railroad and pipeline transportation might be said to carry heavy threshold costs in addition to those transportation costs which are directly variable with ton miles of transportation produced. The original basis of railroad freight rate structures lies in the classification of all articles of commerce into railroad class ralings ranging from 7 to 40 pct of first class (100 pct) rate level, dependent on value, hazard, loading characteristics, service requirements, and whether carload or less than carload. Classification tables and mileage-based (but arbitrarily grouped), rate scales are published as tariffs subject to approval by regulatory bodies. Used together, these determine class rates in cents per 100 lb between points in the U. S. Where local commercial or operating conditions render it advantageous for carriers to depart from

Jan 1, 1961

By D. G. Westlake

Polycrystalline tensile specimens of various Zr-0-H alloys have been tested at 298°, 178°, and 77°K. Solute oxygen and hydride precipitates in quenched alloys made individual contributions to the yield strength at 0.2 pct strain which combined to produce a resultant strength increment, a,., Ductility changes which were ohserved can he interpreted in terms of the various oxygen and hydrogen concentrations, testing tem -peratures, and dispositions of the hydride. ADDITIONS of oxygen in solid solution were known to increase the yield and tensile strengths of polycrystalline zirconium as early as 1951.' More recently, the critical resolved shear stress (CRSS) for prism slip in zirconium single crystals was also shown to be affected by the solute oxygen impurity.' This latter work also demonstrated that large increments of strength could be contributed by the finely dispersed zirconium hydride precipitates that are present in quenched Zr-H alloys.3 It was concluded that the combined strengthening due to alloying could be expressed by where to is the increase in the CRSS due to solute oxygen alone and TH is the increase due to finely dispersed hydride precipitates. Eq. [I] is analogous to one used to express the combined strengthening effects of work hardening and neutron radiation damage.4 Eq. [1] was verified only indirectly and for only small amounts of the impurities—up to 0.14 at. pct 0 and 0.63 at. pct H. The present investigation was undertaken to obtain a more direct verification of the validity of the form of Eq. [1] for this system and also to determine the combined effects of oxygen and finely dispersed hydride precipitates on the tensile strength and ductility of polycrystalline zirconium. EXPERIMENTAL PROCEDURE Tensile specimens were machined from the same rolled billet of Kroll zirconium used in the earlier study.' These measured 38 by 4.7 by 0.5 mm and had 10-mm gage lengths which were 2.8 by 0.5 mm. Each specimen was ß-annealed in vacuo at 1173°K for 15.5 hr and a-annealed at 1073°K for 4 hr to D. G. WESTLAKE, Member AIME, is Associate Metal l ur-gist, Metallurgy Division, Argonne National Laboratory, Argonne, III. Manuscript submitted July 17, 1964. IMD______________ give an equiaxed structure with grain diameters averaging 0.06 mm. Oxygen was added by allowing the metal to react with a known quantity of oxygen during the 0 anneal and known quantities of hydrogen were added during the a anneal. Each alloy was encapsulated in Pyrex under vacuum, annealed at 873°K for 4 hr, quenched into ice water, and polished by immersion in a solution of 46.75 vol pct H2O, 46.75 vol pct concentrated HNO3, and 6.5 vol pct HF (49 pct) at 298°K. Special heat treatments given to a few specimens are described in the results below. Tensile tests were done on an Instron machine and were begun within 20 min after the quench, except where specified otherwise. Tests at 298°K were in air, at 178°K in acetone, and at 77°K in liquid nitrogen. All tests were at a strain rate of 8x sec-1. RESULTS AND DISCUSSION Yield Stress at 298°K. The compositions of alloys and the corresponding yield stresses (0.2 pct strain) are given in Table I. A plot of the yield stresses of the oxygen alloys, A, B, C, and D, indicates that varies linearly with CO1/2, where Co is the oxygen concentration, Fig. 1. This is in accord with Fleischer's6 theory for solution strengthening if the oxygen atoms do not cluster, or the cluster size remains constant with increasing oxygen concentration. In Fig. 1, it appears that if one could prepare some oxygen-free zirconium its yield stress would be very low. Therefore, we shall assume that for the oxygen alloys is equivalent to O0, the strength increment contributed by the presence of oxygen. The relationship between0.2and Co is expressed by 0.2 = 31.3 CO1/2, when the yield stress is in kg per sq mm and the concentration is in at. pct. Each of the hydrogen alloys, Al, A2, A3, and A4, contained 0.081 at. pct 0 as an impurity. In Fig. 1, it appears that this small amount of oxygen makes a significant contribution to the strength which cannot be ignored when we evaluate the contribution of the finely dispersed hydride. Let us assume the validity of the following equation: a0.2 = (a2o+a2R)1/2 [2] which is analogous to Eq. [I] for single crystals, and calculate values of UH for the hydrogen alloys by using the experimental values of 0.2 and o (0.081 at. pct) = 8.9 kg per sq mm. For 0.36 at. pct H, oH = 6.47; for 0.72 at. pct H, OH = 11.30; for 2.16 at. pct H, OH = 19.4; and for 3.60 at. pct H,

Jan 1, 1965

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

The stability of a 70/30 Mn-Cu alloy aged to peak damping has been investigated using electron microscopy, X-ray diffraction, and torsional pendulum measurements. Storage at room temperature or at 100" C causes a reduction in damping capacity. This is shown to be due to the formation of subdomains which "lock" the main domain structure and so hinder their movement. After storage the damping capacity can be restored by a retransformation treatment, which generates structures identical to those found in newly aged specimens. Plastic deformation by rolling also causes a decrease in damping capacity. In this case the damping capacity can only be restored by retransformation if the amount of deformation is less than about 5 pct. THE general metallography and structure of these high damping capacity alloys has been discussed in Part I of this work.1 Part II deals with some of the variables that affect the damping capacity. In particular, the stability of the damping capacity of a 70/30 alloy aged for 2 hr at 425° C and quenched has been investigated. The temperature sensitivity of the damping capacity of a 70/30 alloy aged for 2 hr at 450° C has been reported by Birchon.2 The damping capacity begins to decrease with increasing temperature, and is very low above the M, temperature of 125°C. The cubic — tetragonal transformation is completely reversible and there is no apparent thermal hysteresis associated with the change in damping capacity. Another important effect was first reported by Dean and his coworkers.3 They noticed a decrease in the damping capacity with time for specimens of a quenched tetragonal alloy. More recently workers at the Admiralty Materials Laboratory 4 have studied the stability of an aged 70/30 alloy. They found that the damping capacity decreased to half its original value after about 1000 hr at room temperature. EXPERIMENTAL The techniques used for electron microscopy and X-ray diffraction have been described in Part I. The damping capacity was measured by means of a torsional pendulum, using rectangular specimens, 3 by 0.3 mm with a 6 cm gage length. The specific damping capacity, S.D.C., was calculated as a percent amplitude decay in free vibrations over 10 cycles, starting at an amplitude which corresponded to a 700 psi surface shear stress. Because of the stress dependence of the damping,' the values obtained were about a third those reported for a 5000 psi surface shear stress.' RESULTS a) Effect of Aging Temperature. The effect of aging temperature on the damping capacity is shown in Fig. 1. The damping capacity reaches a peak of 12 pct after aging at 400° to 425°C) then begins to decrease as the volume fraction of a Mn increases. At higher aging temperatures the structure becomes cubic again with a low damping capacity. b) Stability of the Aged Structure. The damping capacity of the aged alloy decreases with time at room temperature. This process could be accelerated by storing at 100°C, when about 100 hr were required for the damping to fall to half its original value. The results of room temperature and 100°C storage, for times up to 1000 hr, are shown in Fig. 2. The damping capacity starts to decrease after about 24 hr at 18° C and 1 to 2 hr at 100°C. It was found, however, that the damping could be almost completely restored by retransformation. The specimens were held at a temperature above the M, for a short time, 250° C for 5 min, and then quenched. The values of damping capacity for specimens that were aged, stored, and then retransformed are shown by the full points in Fig. 2. X-ray measurements of the c/a ratio and hardness readings on the specimens did

Jan 1, 1969

By Mark J. Klein

An internal-friction profile induced by nitrogen in Cr-35 at. pet Re was studied as a function of nitrogen concentration and heat treatment. From these studies, the solubility of nitrogen in this alloy was deduced. The equilibrium solubility of nitrogen in chromium does not appear to be substantially changed by the addition of 35 at. pet Re to chromium. However the precipitation kinetics of nitrogen from solution are significantly decreased. IT has been found that rhenium has a beneficial effect on the low-temperature ductility of Group VI-A metals. As part of a study to investigate the mechanism of this increased ductility, it was of interest to compare the concentration of interstitials retained in solution in one of these ductile bee alloys with the concentration retained in solution in its base metal. In this regard, a study of the solubility of nitrogen in ductile Cr-35 at. pet Re was selected for this phase of the investigation because the solubility of nitrogen in the base metal, chromium, has been determined over a fairly large temperature span.1-3 In addition, nitrogen is known to have an embrittling effect on chromium,4 but does not appear to have a comparable embrittling effect on Cr-35 at. pet Re.5 The experimental method selected for this study was the measurement of internal friction. This technique allows interstitial-concentration measurements to be made in bee metals that are sensitive to small changes in the concentration of a particular interstitial, even when other interstitials are present. When subjected to a cyclic stress, interstitial atoms in solid solution give rise to an internal-friction peak whose origin is the stress-induced ordering of interstitials into preferred lat- tice sites. These internal-friction peaks signify a dissipation of elastic energy which is greatest when the period of oscillation is comparable with the relaxation time for the attainment of an equilibrium interstitial distribution. For dilute interstitial binary alloys, the height of the internal-friction peak is proportional to the concentration of interstitial atoms in solid solutions. snoek8 has shown that the internal friction, Q-1, may be expressed by the equation where A is the relaxation strength, ? is the angular frequency, and 7 is the relaxation time. The relaxation strength, A, is proportional to the concentration of interstitials taking part in the relaxation if no interaction occurs between solute atoms. Thus values of peak height, which can be determined as a function of temperature, give a measure of the relative concentration of interstitial atoms in solution at various temperatures. If equilibrium has been attained, the peak heights will be proportional to the interstitial solubilities. The constant that relates A to the interstitial concentration can be determined experimentally from peak-height measurements as a function of concentration for specimens of constant crystallographic orientation. When this has been done, Q-1 measurements can be used to determine solubilities according to the equation C - KQ-1 where C is the soluble interstitial concentration and K is a constant that can be experimentally determined. It is possible, however, that lattice imperfections may bind interstitials to certain lattice sites. Internal friction does not measure these interstitial~, but does measure interstitials which are free to move in the normal lattice sites when subjected to an applied oscillating stress. On alloying the pure metal with a substitutional

Jan 1, 1965

By Ralph H. Kress

Haulage trucks designed expressly for mine service were introduced about 35 years ago. The first models to arrive on the scene hauled about 15 tons and easily outperformed the modified highway trucks that had been used for mine haulage up to that time. The specialized trucks obviously had a greater potential for mining operations, and once this fact was recognized, competitive pressures in both the mining and truck-manufacturing industries drove the new vehicles toward ever more efficient performance. Many changes in truck design resulted, but not all were accepted for a variety of reasons. Often poor design was the reason, but in many cases progressive and promising designs were abandoned only because the truck manufacturer lacked the courage, tenacity, or vision to capitalize on them. There were also many cases where a promising new design was abandoned because the prototypes were initiated in a mine where personnel lacked the patience to prove them. Truck Startup Takes A Team Ally new truck that is to succeed and contribute to lower mine haulage costs must be well conceived and launched with good teamwork on the part of all concerned. Naturally, it is essential to have a good overall truck design at the outset to make this teamwork worthwhile. The design must include the selection of the right components manufactured by suppliers that can each do justice to their particular part of the new truck. Last, but by no means least, the mine operator where the truck is to be launched must be enthusiastic in his efforts to see the new vehicle through to successful operation.

Jan 1, 1971

By P. A. Laxen, H. R. Spedden, A. M. Gaudin

WHEN a mineral particle is fractured, bonds between the atoms are broken. The unsatisfied forces that appear at the newly formed surface1 are considered to be responsible for the adsorption of ions at the mineral surface. A knowledge of the mechanism and extent of ion sorption from solution onto a mineral surface is of interest in the development of the theory of flotation.2,3 Study of the adsorption of sodium from an aqueous solution on quartz offers a simple approach to this complicated problem. The availability of a radioisotope as a tracer element meant that accurate data could be obtained.4,5 Three main factors which appeared likely to affect the adsorption of sodium are: 1-concentration of sodium in the solution, 2-concentration of other cations in the solution, and 3-anions present in the solution. Hydrogen and hydroxyl ions are always present in an aqueous solution. By controlling the pH, the concentration of these two ions was kept constant. The variation in the amount of sodium adsorbed with variation in sodium concentration was then determined under conditions standardized in regard to hydrogen ion. The effect of concentration of hydrogen ions and of other cations was also measured. A few experiments were made to get a preliminary idea on the effect of anions. The active isotope of sodium was available as sodium nitrate. Standard sodium nitrate solutions were used throughout these experiments except when the effects of other anions were studied. It was found that sodium adsorption increased with sodium-ion concentration, but less rapidly than in proportion to it. Increasing hydrogen-ion concentration, or conversely decreasing hydroxylion, brings about a comparatively slight decrease in sodium-ion adsorption. Increasing the concentration of cations other than hydrogen or sodium decreases somewhat the adsorption of sodium ion. It would appear as if the kind of anion is a secondary factor in guiding the amount of sodium ion that is adsorbed. Materials and Methods Quartz The quartz was prepared as in previous work in the Robert H. Richards Mineral Engineering Laboratory4 except for the refinement of using de-ionized distilled water for the final washing of the sized quartz, prior to drying5 To minimize the laborious preparation of quartz, experiments were made to determine whether the sodium-covered quartz could be washed free of sodium and re-used. The experiments were successful as indicated by lack of Na' activity on the repurified material and by its characteristic sodium adsorption. Table I gives the spectrographic analyses of the quartz used. The quartz ranged from 16 to 40 microns in size, averaging about 23 microns (microscope measurement), and had a surface of 1850 sq cm per g (lot I), 2210 (lot II) and 2000 (lot III) as determined by the Bloecher method.6 Radioactive Sodium Method of Beta Counting for Adsorbed Sodium: Na22, the radioisotope of sodium, possesses convenient properties.7 It has a half-life of 3 years, thus requiring no allowance for decay during an experiment. On decay it emits a 0.575 mev ß radiation and a 1.30 mev ? radiation. The decay scheme is illustrated in the following equation: [Y Nam S. - 'Net 3 years] The ß radiation is sufficiently strong to penetrate an end-window type of Geiger-Mueller counting tube. This, in turn, makes it possible to use external counting, a great advantage in technique. Furthermore, it permits the assaying of solids arranged in infinite thickness, while assaying evaporated liquors on standardized planchets. The equipment used was standard and similar to that employed by Chang8 The original active material was 1 ml of solution containing 1 millicurie of Na22 as nitrate. This active solution was diluted to 1000 ml. Five milliliters of this diluted active solution was found to give a quartz sample a sufficiently high activity for accurate evaluation of the sodium partition in the adsorption measurements. Also, 1 ml of final solution gave a sufficiently high count for precision on the liquor analyses. The sodium concentration of the diluted active solution was 1.2 mg per liter, so that 6 mg of sodium for 60 ml of test solution and 12 g of quartz was the minimum amount used. The active solution was stored in a Saftepak bottle. Procedure for Adsorption Tests: The method consisted of agitating 12 g of quartz with 60 ml of solution of known sodium concentration for enough time to establish equilibrium between the solution and the quartz surface. The quartz was separated as completely as possible from the solution by filtering and centrifuging. The activity on the quartz and in the equilibrium solution was measured and the partition of the sodium was calculated from the resulting data. The detailed procedure for the adsorption test is set forth in a thesis by Laxen5 In brief, it included the following steps: 1-Ascertainment of linearity between concentration of Na22 and activity measured. 2-Evaluation of factor to translate activity on solid of infinite thickness in terms of activity on an evaporated active film of minute thickness, on the various shelves of the counter shield. 3-Taking precautions to avoid evaporation of water during centrifuging.

Jan 1, 1952

By C. Y. Cheng

THE purpose of this note is to show that the dislocation mechanism controlling the creep of Fe-4 pet Si alloy1 may equally account for the behavior of a-Fe2 over the same temperature range. A recent study of the creep behavior of a-Fe has been made by Ishida et al.2 Their results were in agreement with the mechanism of nonconservative motion of jogged screw dislocations over the entire range of temperatures investigated, from 480° to 1045°K. However, the observed creep rate was much higher than that which could be accounted for by the above model unless the authors assumed that pipe diffusion became significant below 775°K. More recently, Cheng et al.1 inves-gated the creep of Fe-4 pet Si alloy over about the same temperature range and found that the results could be correlated fairly well with a dislocation climb mechanism as represented by Eq. [l]. Proceeding as shown previously,1 if creep is controlled by a single climb mechanism, at intermediate stresses, the shear creep rate, y, can be represented by where n and K are material constants {K is independent of the temperature but dependent on the structure, that is, K decreases during the primary stage and reaches a steady-state value over the secondary stage of creep), t is the applied shear stress, G is the shear modulus, gc is the free energy of activation for creep (usually equal to that for self-diffusion, gd), and RT has the usual meaning. By solving for y, the apparent activation energy for creep, Q which can be determined experimentally, is given by where hc is the enthalpy of activation for creep which usually is also equal to that for self-diffusion, h^. By using Eq. [2], the data in Fig. 2 of Ref. 2 can be re-plotted as shown in Fig. 1. By comparing the two figures, it is seen that the slight increase in the apparent activation for creep over Region II, as noted in Fig. 2 of Ref. 2, is due to the influence of temperature on the shear modulus rather than of the stress on the

Jan 1, 1969