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By T. O. Massalski, J. D. Ayers

A massive transformation, 0 —am, takes place in a number of copper-based systems where the ß phase field at high temperatures extends to compositions that are slightly less solute-rich than the limits of the a phase field that exists at lower temperatures. Consequently a solid-state transformation becomes possible that does not involve a change of composition. Within this narrow range of composition the massive am phase can be usually produced in two ways: by a fast quench from the ß phase through the a phase field, or by pulse heating into the a phase field of an undecomposed ß phase retained at room temperature by a prior quench. In the Cu-Ga system the occurrence of a massive am phase has been also observed in alloys whose composition falls outside the equilibrium a phase field1 but not in the Cu-Zn system.2 We have recently observed the occurrence of the ß — am transformation also in two silver-based systems, Ag-Zn and Ag-Cd. The a and 0 phase fields in these systems again slightly "overlap" in a narrow composition range. In the Ag-Zn system this range falls between 36.7 and 40.2 at. pct Zn, and in the Ag-Cd system between approximately 41 and 42.5 at. pct Cd. Alloys were prepared from high-purity materials and cast in quartz tubes under inert atmosphere. No significant change of composition occurred during casting. After homogenizing in the 0 phase field, small pieces of each alloy were reheated at the homogenizing temperatures for a few minutes and quenched into various media. There were examined metallographic-ally after removal of surface layers that may have suffered from contamination or from the loss of the solute element. In the Ag-Zn system extensive areas of the am phase (identified by selective etching, observation of the slip trace variants, and occurrence of twinning) were observed in a comparatively low-zinc alloy (37.8 at. pct Zn) for all quenching media employed: iced

Jan 1, 1969

By M. R. Geer, H. F. Yancey

Although the use of dense suspensions for coal cleaning was pioneered in the United States with the Chance sand flotation process, and during the past year a pilot plant using a magnetite suspension has started operation in this country, the more recent developments in this field of coal cleaning have occurred principally in the Netherlands. During the thirties the Dutch developed the Barvoys process, in which a medium of barite and clay is employed, the Tromp process, which utilizes a magnetite suspension, and the Loess process, in which is used the air-borne earth or soil known as loess.1-3 All these processes are finding increasing use in European coal-cleaning practice. Now a fourth process, the cyclone cleaner, is under development by the Netherlands State Mines. A cyclone thickener for reclaiming and thickening the dense suspension is a novel feature of the Loess process. Through accident, the discovery was made that the cyclone could be utilized as a cleaning device for fine coal. When the cyclone thickener at the Maurits mine plugged, the overflow was found filled with clean coal free of refuse, and from this observation developed the concept of the cyclone as a coal cleaner. In June 1945 the cyclone cleaner was observed by one of the authors,' and in September 1945 it was described by Dries-sen6 in a paper presented in London before the Institute of Fuel. As the cyclone seemed to offer unusual promise as a means of extending heavy-medium cleaning to the finer sizes of coal that cannot readily be treated in existing heavy-medium processes, the Bureau of Mines, following Driessen's, presentation, launched an investigation of the cyclone as a coal cleaner. Added impetus was given to this study by the present increased interest in heavy-medium cleaning in this country. Object and Scope of Investigation Driessen's report, although comprehensive in many respects, did not include a detailed description of the cyclone cleaner, and contained almost no information on the influence of the various operating variables of the cyclone. It was necessary, therefore, to investigate the influence of the cyclone adjustments on its performance before studying the application of the cyclone to various coal-washing problems. The present report is confined entirely to these preliminary tests, designed to demonstrate the operating characteristics of the cyclone. The investigation has been in progress

Jan 1, 1949

By Lloyd R. Jackson

In the past 15 years there has been a great deal of interest in the fundamentals of plastic flow and rupture in metals and a number of papers have presented substantial advances toward a fundamental insight into the mechanism of these two processes. This paper is an appraisal of the present position with respect to the following: 1. The relative importance of shear and hydrostatic stresses in controlling the plastic flow of metals. 2. The relative importance of shear and hydrostatic stresses in determining the amount of flow before rupture in metals. 3. The use of generalized strains in determining the effect of plastic flow on the work-hardening of metals. FundamentalS Involved in Plastic Flow In attempting to devise a quantitative description of plastic flow in metals, it has been customary to assume that metals are homogeneous and isotropic. The fact that neither of these assumptions is correct complicates the experimental appraisal of relations developed. Nevertheless, as will be shown, metals are close enough '0 being isotropic and homogeneous so that considerable insight into the mechanism of plastic flow can be obtained. The assumptions of isotropy and homogeneity allow both the elastic and plastic behavior of metals to be described in terms of 12 variables—six being stress variables, and six being strain variables. From this viewpoint, it should be possible to represent the stress-strain relations in the plastic range for metals by a surface in 12 dimensions. One boundary of this surface would be the surface of transition from elastic to plastic behavior; the other would be the surface of rupture. These two surfaces would be joined by the surface of plastic flow. The shape of this composite surface would depend on the test temperature and speed of straining This paper is concerned only with results obtained at constant temperature and constant speed of straining. While such a representation is conceivable, the demonstration of such a surface would present almost insurmountable obstacles. The most fruitful simplification of this concept has been the recognition that the behavior of metals in the plastic region is primarily a result of shear stresses and strains. Based on this viewpoint, it is possible to utilize stress and strain invariants that are independent of hydrostatic components to define an effective stress and strain. In effect, this amounts to reducing the task of representing stresses and strains in 12 dimensions to one of representation in two dimensions. The two invariants (one for stresses and one for strains) that have received most attention are the following: q2 = ½[(Txx= - Tyy)2 + (Tyy - Tzz)2 + (Tzz - Txx)2 + 3(Txy2 + Tyz2 + 7xx2) [1]

Jan 1, 1947

By Lloyd R. Jackson

In the past 15 years there has been a great deal of interest in the fundamentals of plastic flow and rupture in metals and a number of papers have presented substantial advances toward a fundamental insight into the mechanism of these two processes. This paper is an appraisal of the present position with respect to the following: 1. The relative importance of shear and hydrostatic stresses in controlling the plastic flow of metals. 2. The relative importance of shear and hydrostatic stresses in determining the amount of flow before rupture in metals. 3. The use of generalized strains in determining the effect of plastic flow on the work-hardening of metals. FundamentalS Involved in Plastic Flow In attempting to devise a quantitative description of plastic flow in metals, it has been customary to assume that metals are homogeneous and isotropic. The fact that neither of these assumptions is correct complicates the experimental appraisal of relations developed. Nevertheless, as will be shown, metals are close enough '0 being isotropic and homogeneous so that considerable insight into the mechanism of plastic flow can be obtained. The assumptions of isotropy and homogeneity allow both the elastic and plastic behavior of metals to be described in terms of 12 variables—six being stress variables, and six being strain variables. From this viewpoint, it should be possible to represent the stress-strain relations in the plastic range for metals by a surface in 12 dimensions. One boundary of this surface would be the surface of transition from elastic to plastic behavior; the other would be the surface of rupture. These two surfaces would be joined by the surface of plastic flow. The shape of this composite surface would depend on the test temperature and speed of straining This paper is concerned only with results obtained at constant temperature and constant speed of straining. While such a representation is conceivable, the demonstration of such a surface would present almost insurmountable obstacles. The most fruitful simplification of this concept has been the recognition that the behavior of metals in the plastic region is primarily a result of shear stresses and strains. Based on this viewpoint, it is possible to utilize stress and strain invariants that are independent of hydrostatic components to define an effective stress and strain. In effect, this amounts to reducing the task of representing stresses and strains in 12 dimensions to one of representation in two dimensions. The two invariants (one for stresses and one for strains) that have received most attention are the following: q2 = ½[(Txx= - Tyy)2 + (Tyy - Tzz)2 + (Tzz - Txx)2 + 3(Txy2 + Tyz2 + 7xx2) [1]

Jan 1, 1947

By I. Lowthian Bell

THERE has been probably no improvement introduced into the manufacture of iron which created more surprise in the minds of practical smelters and of scientific men than Neilson's discovery of the hot blast. In 1829, Messrs. Dunlop & Co. consumed at the Clyde Works, near Glasgow, nearly 79 tons of coal to make a ton of pig iron, of which about 20 cwts. was employed under the boilers of the blowing engines, leaving nearly 7 tons for the consumption of the furnace itself. In the year 1833, by heating the air to 612' F. (322' C.), they redoccd the 79 tons to 3 tons by the mere burning of 8 cwts. of coal in the apparatus for raising the blast to this temperature. The statenlent just given is strictly true in a commercial sense, but when we come to consider the question as one of physical science, it is necessary to eliminate some of the conditions which conduced to so extraordinary a result. Anterior to Neilson's time the fuel employed in smelting iron was coke, and it was supposed at that period, erroneously, however, that coal in its raw state, when burned with cold air, was totsally unfit for the purpose in question. This mineral, as it was obtained from the Lanarkshire coal-field, contained about 35 per cent. of volatile matter, but the process of charring it was performed in so unskilful a manner that instead of receiving 88 cwts. of coke from 135 cwts. of coal, 60 cwts. only was the product of the operation. Again, the reduced colisumption of carbon in the furnace itself was accompanied by a corresponding diminution of blast, and this was followed by an economy of half a ton in engine coal. After making a proper allowance, however, for all these collateral circumstances, we are within the mark when we admit that in actual coke, which is really the form the fuel has to assume before it is burnt in the blast-furnace, not less than 30 cwts. was saved by heating the blast to 615° F. (322° C.). This unexpected economy, be it remembered, was obtained by the combustion of the 8 cwts. of coal, somewhat wastefully applied in the hot-air apparatus. Numerous have been the opirlions advanced by different authorities in the scientific world to account for the apparent anomaly, bat none,

By R. F. Steigerwald

The effects of heat transfer on the corrosion behavior of type 304 stainless steel in boiling water have been studied. Heat transfer conditions increase the tendencies of the stainless steel toward stress-corrosion mucking when the water is contaminated with Cl-. Surface preparation is the most important variable in determining the severity of the stress-corrosion problem in water with a given Cl- content. Heat treatment, chemical cleaning, and degree of wet film boiling also affect the corrosion of stainless steels used as heat transfer surfaces in boiling water. An up-paratus for corrosion testing under controlled heat transfer conditions is described. THE principal objective of this investigation was to study the corrosion behavior of AISI Type 304 stainless steel in boiling high-purity water under conditions of heat transfer. The principal variables in the study were: a) boiling conditions: limited boil, agitated boil; b) metallurgical structure: annealed or sensitized; c) surface condition: rolled, pickled, or ground. The results of the study should elucidate the role of heat transfer in the corrosion of stainless steel in boiling high-purity water and provide a base line from which to assess the severity of this type of corrosion. Although there has been an investigation of the effect of heat transfer on the corrosion behavior of stainless steels in alkaline waters,' work on the corrosion of stainless steels under heat transfer has been largely confined to various acid solutions.'-4 Furthermore, the study of the corrosion of stainless steels in high-purity water has been generally restricted to auto-clave and instream testing in superheated (e.g., 300°C) water and steam.5'6 Cooling water problems led to this study of the corrosion behavior of type 304 stainless steel in high-purity water at its atmospheric boiling point. In addition to the effects of heat transfer, this study also considered the influences of the type of boiling,7 metallurgical structure, and surface condition on the corrosion behavior of stainless steel in high-purity water. Two boiling conditions were investigated in this study: a) limiting boiling, i.e., when the heat-transfer surface had just reached the boiling point and boiling nucleated randomly over the specimen surface and b) agitated boiling, i.e., when a mild degree of superheat had been achieved on the specimen surface and boiling occurred generally over the specimen surface. Both boiling conditions are broadly classified as wet-film boiling. Originally, this program included the study of a third type of boiling, dry-film conditions. At dry-film boiling the temperature of the heat transfer surface is high enough so that it is covered with a continuous film of steam. Experimental difficulties made it impossible to study this kind of boiling with the available apparatus. Since surface condition affects heat transfer rates, three typical surfaces were chosen for study: a) as-rolled, the 2B finish received from the supplier, b) as-pickled, 30 min in 8 pct HNO3-1 pct HF, and c) as-ground on 120 grit paper. In order to evaluate the effect of improper heat treatment or welding on hot wall corrosion, both annealed and sensitized mi-crostructure were included in this study. EXPERIMENTAL Test Apparatus. The particular problems of interest in this investigation required a knowledge of the thermal gradient through the test specimen. From this gradient, the heat flux to the surface and the surface temperature could be determined. In order to satisfy this need, an apparatus similar to the boiling-disk apparatus of Fisher and whitney2 was designed. The solution is contained in a thermally-insulated, steel pipe lined with TEFLON resin. A stainless steel _______;________________________________________

Jan 1, 1970

By Richard V. Hughes, Rudolf J. Pfister

The necessity for getting more water into sands of low permeability in any secondary-recovery water-flood operation in order to recover all the available oil always has been a major problem. In the early days of water-flooding the addition of soda ash and caustic soda to fresh input waters was recommended and tried without success in the Bradford field. The most frequent difficulty was sand plugging. The use of natural and artificial brines often has been suggested for water-flooding, in the belief that laboratory observations of decreasing fresh-water throughput rates in measuring water permeabilities of consolidated sand cores might be partially explained by swelling of clays. A review of available literature bearing on the subject and related laboratory experiments are presented herein, offering an explanation for failure in use of soda ash and caustic soda waters and supporting the recent concept that every water used for input purposes in the secondary recovery of oil should possess such physical and chemical characteristics as to keep the clay content of the producing sands in a permanently flocculated condition. Produced brines meet this requirement. Their use is recommended as a means of increasing intake rates of tight sands and oil recoveries, as a solution to brine-disposal problems, and as a means of conserving a natural resource. Introduction There is a general belief among those engaged in the secondary recovery of oil by water-flooding that one of the most important requirements for the success of any such project is an adequate supply of good, fresh water. Fresh waters have the advantages of being more easily stabilized than salt waters and of being usable about the lease for all purposes. The use of brines for water-flooding never has been given much consideration in the Pennsylvania Grade area. The use of brines in Mid-Continent operations has been considered largely as a substitute for fresh waters, which were economically unobtainable for many operations. Estimated recoveries for some water-drive fields indicate that less of the original oil in place will be left upon abandonment than with the above-average practices used in Pennsylvania Grade water-flood operations. Lower residual oil saturations than 25 pct of the pore space following the water-flooding of Third Bradford sand cores in the laboratory are unusual. In comparison, water-flushed sands surrounding any virgin oil pool are found to be practically devoid of oil. Such lower natural residual oil saturations may be the result of a time factor much longer than economic under artificial water-flood operations, but neither the producer of primary oil nor the producer of oil by secondary recovery can obtain maximum recoveries unless full advantage is taken of all natural forces and

Jan 1, 1947

By Richard V. Hughes, Rudolf J. Pfister

The necessity for getting more water into sands of low permeability in any secondary-recovery water-flood operation in order to recover all the available oil always has been a major problem. In the early days of water-flooding the addition of soda ash and caustic soda to fresh input waters was recommended and tried without success in the Bradford field. The most frequent difficulty was sand plugging. The use of natural and artificial brines often has been suggested for water-flooding, in the belief that laboratory observations of decreasing fresh-water throughput rates in measuring water permeabilities of consolidated sand cores might be partially explained by swelling of clays. A review of available literature bearing on the subject and related laboratory experiments are presented herein, offering an explanation for failure in use of soda ash and caustic soda waters and supporting the recent concept that every water used for input purposes in the secondary recovery of oil should possess such physical and chemical characteristics as to keep the clay content of the producing sands in a permanently flocculated condition. Produced brines meet this requirement. Their use is recommended as a means of increasing intake rates of tight sands and oil recoveries, as a solution to brine-disposal problems, and as a means of conserving a natural resource. Introduction There is a general belief among those engaged in the secondary recovery of oil by water-flooding that one of the most important requirements for the success of any such project is an adequate supply of good, fresh water. Fresh waters have the advantages of being more easily stabilized than salt waters and of being usable about the lease for all purposes. The use of brines for water-flooding never has been given much consideration in the Pennsylvania Grade area. The use of brines in Mid-Continent operations has been considered largely as a substitute for fresh waters, which were economically unobtainable for many operations. Estimated recoveries for some water-drive fields indicate that less of the original oil in place will be left upon abandonment than with the above-average practices used in Pennsylvania Grade water-flood operations. Lower residual oil saturations than 25 pct of the pore space following the water-flooding of Third Bradford sand cores in the laboratory are unusual. In comparison, water-flushed sands surrounding any virgin oil pool are found to be practically devoid of oil. Such lower natural residual oil saturations may be the result of a time factor much longer than economic under artificial water-flood operations, but neither the producer of primary oil nor the producer of oil by secondary recovery can obtain maximum recoveries unless full advantage is taken of all natural forces and

Jan 1, 1947

By C.R. Taylor, John Chipman

The study of chemical reactions of liquid steel and basic open-hearth slag involves a complex slag system of at least eight important components, and often a number of others. In initiating an experimental program on the equilibrium relationship of slag and metal, it became evident that but little progress could be expected in the interpretation of the complex slags until an understanding had been gained of the simpler liquid systems composed of a limited number of slag constituents. The simplest system that in any way resembles open-hearth slag must contain lime, silica and iron oxide. Attempts to produce in an induction furnace slags containing only these constituents have met with serious limitations because of the solubility of refractories in the slag. Thus in acid-lined furnaces the slag is always saturated with silica and consequently contains between 48 and 63 per cent of this component. In basic-lined furnaces an undesired additional component, magnesia, is introduced to the extent of some 3 to 15 per cent, depending upon the acidity, sometimes with disastrous results to the furnace. Thus in a magnesia-lined furnace, Fetters and Chipman1 found it impossible to prepare slags in which the ratio (CaO + MgO)/SiO2 was less than that corresponding to the metasilicate (approximately 0.8:I). Between this composition and that of the true acid slags lies a field of composition about which very little is known and which cannot be explored by any ordinary means. This circumstance, as well as the desire to study the more basic slags in the absence of magnesia, calls for the development of a method by which slags may be brought into equilibrium with molten metal without coming in contact with refractory. Such a technic has been provided by the rotating induction furnace developed by Barrett, Holbrook and Wood.2 Three modifications of the rotating furnace were described by these authors. The first was essentially a rotating refractory cylinder containing the magnesia crucible, which was itself heated by a graphite crucible. In the second, only the magnesia crucible rotated, the cylindrical graphite heater being stationary. In the third, the coil and crucible revolved, and the metal was heated directly by induction. Experimental Method Furnace The furnace used in this investigation differed from previous designs and may be Sci- a fourth modification of the original rotating furnace. Its essential fea tures are shown in Fig. I' The Outer case A is a fire-clay flue liner for control of the atmosphere. The top B and base 6 are alberene stone. The coil supports D are of ""Formica," a material formed from phe-

Jan 1, 1943

By C. R. Taylor, John Chipman

The study of chemical reactions of liquid steel and basic open-hearth slag involves a complex slag system of at least eight important components, and often a number of others. In initiating an experimental program on the equilibrium relationship of slag and metal, it became evident that but little progress could be expected in the interpretation of the complex slags until an understanding had been gained of the simpler liquid systems composed of a limited number of slag constituents. The simplest system that in any way resembles open-hearth slag must contain lime, silica and iron oxide. Attempts to produce in an induction furnace slags containing only these constituents have met with serious limitations because of the solubility of refractories in the slag. Thus in acid-lined furnaces the slag is always saturated with silica and consequently contains between 48 and 63 per cent of this component. In basic-lined furnaces an undesired additional component, magnesia, is introduced to the extent of some 3 to 15 per cent, depending upon the acidity, sometimes with disastrous results to the furnace. Thus in a magnesia-lined furnace, Fetters and Chipman1 found it impossible to prepare slags in which the ratio (CaO + MgO)/SiO2 was less than that corresponding to the metasilicate (approximately 0.8:I). Between this composition and that of the true acid slags lies a field of composition about which very little is known and which cannot be explored by any ordinary means. This circumstance, as well as the desire to study the more basic slags in the absence of magnesia, calls for the development of a method by which slags may be brought into equilibrium with molten metal without coming in contact with refractory. Such a technic has been provided by the rotating induction furnace developed by Barrett, Holbrook and Wood.2 Three modifications of the rotating furnace were described by these authors. The first was essentially a rotating refractory cylinder containing the magnesia crucible, which was itself heated by a graphite crucible. In the second, only the magnesia crucible rotated, the cylindrical graphite heater being stationary. In the third, the coil and crucible revolved, and the metal was heated directly by induction. Experimental Method Furnace The furnace used in this investigation differed from previous designs and may be Sci- a fourth modification of the original rotating furnace. Its essential fea tures are shown in Fig. I' The Outer case A is a fire-clay flue liner for control of the atmosphere. The top B and base 6 are alberene stone. The coil supports D are of ""Formica," a material formed from phe-

Jan 1, 1943

By H. H. Podgurski, J. C. M. Li, Y. T. Chou, F. N. Davis, R. A. Oriani

When an Fe-2 pct A1 alloy is nitrogemted at 500ºC with a gus tnixture (NH3-H2) in which the nitrogen activity has been kept Lou] enough to avoid the formation of iron nitride, a two-phase alloy is generuled which consists of AlN particles and a ferrite phase cotaining a heavy network of dislocations. The amount of nitrogen contained in such an alloy, when equilibrated with the nitrogenating atmosphere, far exceeds both that needed to satisfy the normal solution requirements of a Fe and that needed to convert all of the aluninuwi to AlN. This excess nitrogen is accounted for as being trapped on dislocations, adsorbed at the ferrite -AlN interface, and as an en-Iuznced lattice solubility in strained ferrite. This excessive uptake of nitrogen had previously been attribuled by other investigators to the formation of a nonstoichiornetric aluminum nitride. Isotope exchange experiments revealed various amomts of exchargeable N14 present in the originally nitrided samples that could not be removed by reduction with HS at 500ºC. This exchangeable nitrogen has been identified us that bound to the AlN -ferrite interface. Estimates of inter facial areas in alloys containing -3 pct by weight of A1N are as high as 10 sq m per g of alloy. ThE first1 of this series of papers described the experiments forming the basis for the elucidation of the mechanism of the formation of aluminum nitride particles within an Fe-A1 alloy. It was found that not only are dislocations necessary for the nucleation of the AlN particles but also the nitriding reaction in turn produces a dense network of dislocations in the ferrite matrix. It was also observed that nitrogen in excess of that needed for the formation of stoichiometric AIN is taken up by the alloy without the formation of an iron nitride. The present paper is an analysis of the excess nitrogen sorbed by the nitrided Fe-A1 alloy which considers the structure generated by the formation of the aluminum nitride particles. Because of the high density of dislocations, this system has proved to be quite useful in studying nitrogen-dislocation interactions. Wriedt and Darken2 have already reported such studies in a cold-worked ferritic steel. EXPERIMENTAL Nitrogen Sorption. The specimens of this alloy were cold worked (50 pct reduction) to 0.011 in. thickness and chemically cleaned in a 2:1 concentrated phosphoric acid-50 pct hydrogen peroxide solution before nitrogenation. The flowing nitrogenating atmosphere (11 pct NH3-89 pct H2) was established before the ni- trogenating temperature was reached. The same gravimetric and gas-flow equipment described in an earlier paper1 was also used in this investigation. Changes in nitrogen concentration were followed gravimetrically when establishing the isotherms. In the isotope exchange experiments, concentration changes were followed volumetrically. In some instances chemical analyses (Kjeldahl method) were used to check for material balances in both the gravimetric and volumetric procedures. Our objective was to obtain reversible nitrogen sorption isotherms for alloys equilibrated with NH3-H2 gas mixtures over a large range of nitrogen activity* and temperature. The *Defined as equal to PN H /P3/2 ,where P corresponds to partial pressure in atmospheres. Actually the nitrogen activity, aN, in the alloy equals K PNH3 /p3/2H2, where K is the equilibrium constant for the reaction NH3 = N + 3/2H2. upper limit for nitrogen activity was below that which would produce iron nitride; for reasons which will become apparent later, most of the sorption studies were made in the temperature range between 400" and 500'C. The alloy sample studied most extensively in this investigation was given a series of successive reductions (100 pct H2) and nitrogenating treatments at 500°C to attain a stabilized structure. Presumably some dislocations were lost during these treatments. Throughout most of the sorption studies, temperature was held at ± 1°C and the gas-phase composition was held to k0.2 pet NH3. Based upon the results of numerous diffusion experiments with this alloy* the 'Results to be published in a third paper of this series. times chosen for equilibration were considered more than adequate, Nitrogen Isotope Exchange. The first exchange experiments were carried out by circulating a measured quantity of H2 and NH3* (with a predetermined isotopic *The NH3 was synthesized over a synthetic ammonia iron catalyst using H2, and N2, enriched with N15. AS the NH3 was formed it was removed continuously from the gas phase by circulating the mixture through a refrigerated (78ºK) trap. When most of the nitrogen had been converted to NH3, it was distilled from the trap into a glass storage vessel. composition, N15/N14) over a nitrided specimen at 450°C in a closed glass system. Attempts to reach the exchange limit isothermally, i.e., an isotopic ratio (N15/N14) in the gas phase identical with the extractable nitrogen in the nitrided alloy, were futile. The exchange rate between the gas phase and the alloy was too slow, involving many days. To circumvent the slow exchange with the gas phase, measured amounts of N15 and N14 were introduced into the alloy by nitrogenating with an NH3-H2, mixture at 500°C containing an N15/N14 ratio of 7.76; the charged specimens were then sealed by allowing an oxide film to form over them in air, and in this final condition the specimens were subjected to 500°C in vacuum for various times during which isotope exchange was allowed to proceed within the specimen. It was estab-

Jan 1, 1970

By E. R. Buchanan, R. E. Reed-Hill, F. W. Caldwell

Poly crystalline zirconium tensile specimens containing a sizable fraction of grains unfavorably oriented for slip were deformed at 77°K to strains as high as 9 pct. The contributions of the various twinning modes to the observed strain were deter~nlned quantitatively using measured twin volume fractions and Schrnid orientation factors. The results indicate that at very small strains twinning can account for almost all of the observed strain. At higher strains slip becomes the dominant means of deformation. The most significant form of twinning was {1121}. PLASTIC deformation in polycrystalline aggregates is poorly understood even today. This is primarily because slip cannot be easily observed or studied in the interior of a metal. On the other hand, twinning can be discerned inside a specimen after deformation. Twinning studies can therefore often yield quantitative information about polycrystalline deformation not otherwise obtainable. This investigation uses the above aspect of twinning in determining the contributions of twinning to the strain during tensile deformation at a cryogenic temperature (77°K). Polycrystalline zirconium was used as the object of study. There are several reasons why this information should be of value. In contrast to many metals, both the strength and ductility of zirconium increase with a corresponding decrease in temperature. This may be related to the fact that twinning becomes more profuse and complex with decreasing temperature. Secondly, it has been discovered that certain room-temperature properties of zirconium can be greatly improved by about 1 pct prestrain at 77°K. These include an increase in tensile elongation in critical directions by over 50 pctl and a large mechanical hysteresis effect.2 Both effects are believed to be related to twins formed by prestraining: plastic twin-boundary movements accounting for the increased ductility, and anelastic twin-boundary movements for the internal friction. Thirdly, hexagonal metals which twin primarily on only the (1012) mode (such as beryllium, zinc, and magnesium), unlike zirconium, are very limited in ductility at cryogenic temperatures. Therefore, the significance of the various types of twinning in zirconium at cryogenic temperatures is of more than academic interest. Three twinning mechanism-s have beenobserved in quantity at WOK, {1012), {1121), and {1122). Each must be considered as a unique deformation mechanism because of their markedly different twinning shears and basically different angles between twinning and basal planes, as shown in Table I. It is therefore necessary to separately consider the role of each of these twins during plastic deformation at 77°K. Fortunately, each twin possesses unique morphological features which makes its identification possible on a properly prepared metallographic section. The use of the polarized microscope3 can also greatly aid in identification of the various forms of twins. EXPERIMENTAL PROCEDURE Arc-melted sponge zirconium plate, previously describedY4 was machined into 1/8 by 1 1/4 in. threaded-end, round tensile test specimens. These specimens were deformed to the desired strains in a liquid-nitrogen cryostat mounted in an Instron testing machine. The tensile axis was the transverse plate direction. This specimen direction resulted in large numbers of grains in orientations unfavorable for deformation by prism or basal slip. Deformed specimens were sectioned, mounted in epoxy cold-mount resin, ground on metallographic papers, electropolished, and anodized to provide surfaces sensitive to polarized light. Standard quantitative metallographic procedures5

Jan 1, 1965

By J. S. Aronofsky

The first step in a quantitative analysis ot the mechanism of oil displacement by water in a fractured reservoir is usually conceded to be the solution of the differential equation describing the saturation distribution of two immiscible fluids flowing in a porous medium, where the capillary pressure is taken into account. In such a system the production mechanism may consist of displacement of oil both by the flow of water due to natural or artificially imposed pressure gradients and by imbibition, which implies a flow of water not due to external pressure gradients. Owing to the presence of the two oil displacement mechanisms, the mathematical model given by the differential equation intended to describe the system may not properly represent the behavior of the physical system. In fact, in the reservoir the rate of water advance may be very slow, and in the case of a fractured reservoir with a great number of large fractures, the pressure difference determining the flow of water through the matrix may be much less than 1 lb/'psi over lengths of a few feet. In such a case, imbi-bition (the exchange between oil in the matrix and water in the fractures resulting from capillary forces) may become, with time. a significant element of the production mechanism. It occurred Lo the authors, however, that without going into a physical analysis of the process of production, it might be possible by means of simple abstract reasoning to throw some light on the variation of recovery with time under conditions occurring in a highly fractured oil reservoir with rising water table. The object of this paper is to present both the reasoning and its application to a reservoir of the highly fractured type. Specifically, the analysis given here was undertaken to try to explain the increase of recovery (as defined later) with time as observed in this reservoir, without having to assume unlikely variations in the reservoir parameters with depth. This attempt has been successful as will become clear upon comparison of the computed recoveries with the actual field data. ABSTRACT MODEL Let us consider a small volume. of porous matrix saturated with oil at time, t = 0. Let the process of oil displacement by water start at time, t = t,,. At some time, t, the process will have terminated. Then a volume of oil equal to or smaller than the original oil contained in the matrix will have been produced. The first basic assumption that describes the model and guides the forthcoming reasoning is that the oil production from the small volume. dv, is a continuous monotonic function of time and that it converges to a finite limit. Such an assumption is not inconsistent with the results of laboratory waterflood tests as well as with results of imbibition tests where this is, in fact, observed. The second basic assumption is that none of the properties which determine the rate of convergence change sufficiently during the process to affect this rate or the limit. Let it be assumed that the form of the function of time relative to production from the matrix volume. dv, is given by where V,(t) is the volume of oil produced up to that time t. R is the limit toward which the recovery converges, A is a constant giving the rate of convergence, and V,(t) is the volume of oil originally in place in the volume, dv. It should be noted that recovery at time I will be understood here to he It follows that r. tends to R as t tends to infinity. CONSTRUCTION OF RESERVOIR FROM ABSTRACT MODEL Let the reservoir consist of a series of identical blocks of porous matrix stacked vertically and separated by fractures. Let each of these blocks satisfy the conditions of our abstract model. These conditions are: (1) that recovery is a continuous mono-tonic function of time converging to finite limit, and (2) none of the properties that determine the rate of convergence change sufficiently to affect the rate or the limit. Let water be rising in fractures so that oil production from any part of the block starts when the water comes in conLact with it. TOTAL RECOVERY FROM THE RESERVOIR COMPARED TO RECOVERY FROM A SINGLE MODEL ELEMENT As stipulated in Eq. 1, in the case of the abstract model,

By J. W. Goss, M. J. Coolbaugh

Most grouting has been done to stop water flaw in mines and for stabilizing foundations of various man-made structures, a survey of the U.S. literature reveals. Apparently Sun Manuel is one of the first mines in this country to use grout extensively underground for strengthening and stabilizing ground in drifts, shafts, and stations. A comparison with other procedures as well as details of the Sun Manuel program are covered. The employment of pressure grouting as a ground stabilizer at the San Manuel Copper Corp. mine reduces delays in both development and production, lowers costs, and makes possible safer working conditions. It specifically reduces delays in haulage operations and permits the maintenance of normal ventilation. In development work this grouting allows faster excavation by cementing together highly fractured or broken ground that otherwise would require extensive cribbing or spiling. In drift repair, it consolidates the loose or fractured rock over the timber or steel drift supports, thus decreasing the frequency of repair, lessening the hazards from falling rock, and curtailing delays due to blockage of drifts by muckpiles and repair operations. Pressure grouting is the process of pumping an accurately controlled mixture of cement and water into loose, fractured, or porous rock. The ratio of water to cement varies according to the nature of the rock encountered, from the thinnest mixture of 30 gal of water per sack of cement, used to fill very fine fissures, to very thick grout of 5 gal of water per sack of cement, used to fill large fissures or extensive areas of loose, broken rock. The pumping pressures at San Manuel vary from about 100 to 1000 psi, depending upon the compactness of the rock, while at other mines the pressures sometimes go as high as 5000 psi. In order to grout an area in which ground water is encountered, the pumping pressure of the grout must be increased by an amount equal to the pressure of the ground water. GROUTING IN DEVELOPMENT WORK The areas under development at San Manuel include many sections of loose, highly fractured rock. Prior to the advent of the grouting program, drifts, shafts, and stations in these areas could not be excavated without utilizing extensive support such as cribbing, spiling, and breast boarding. This slowed down the development work and increased the costs considerably over that required for excavating in more competent ground. Now, when a particularly bad area is contacted, the mining is temporarily stopped while the bad portion of drift or shaft is grouted. After the grouting is completed, the excavating is resumed with an approximate decrease of 50 pct in lost time and costs. Grouting in Drifts and Turnouts: The grouting procedures and patterns used in drifts and turnouts are very similar. The standard procedure for grouting such a turnout is shown in Fig. 1. After the ground is supported as well as possible with cribbing or lagging, the gaps between the back lagging and side lagging are plugged with empty cement sacks or additional timber, if necessary. The ground surrounding the proposed turnout is then grouted in two stages. In the first stage, the broken and caved rock is drilled and grouted to a depth of 5 to 10 ft, depending on the depth of the broken rock. This stage forms a grouted seal that allows higher pressures to be used at depths beyond 10 ft without developing excessive leaks at the face. After a grout hole is drilled, a 10-ft long pipe is wedged tightly into it with empty cement sacks. Grout is then pumped into the hole until the pressure reaches 200 to 300 psi, and the pipe is subsequently removed if it hasn't become cemented in. No more than one hole at a time is drilled and grouted because the grout has a tendency to go from one hole into another, plugging up the latter. Five or six holes are usually adequate for the first 10 ft of grouting. Experience has shown bentonite to be a useful admixture to the grout, particularly when it is indicated that the grout is being lost into large fissures or voids. Bentonite increases the plasticity of the grout enabling it to remain in place more easily until it has begun to set. In the second stage, the longer holes are drilled through the previously grouted rock, after which the

Jan 1, 1961

By C. S. Barrett, P. Coheur

AXnealing twins are common in the microstructure of copper that has been rolled and recrystallized. In such samples it follows that a twin relationship should exist between components of the re-crystallization texture,' and several examples of this have been reported. For example, twin relationships have been found in recrystallized electrolytic copper sheet, as indicated in Fig. I, from a paper by Coheur and Lejeune.2 In this pole figure the cube texture (100) [001] is indicated by the hollow squares in the lower half of the figure (the pole figure for 200 reflections) and in the upper, (III), part of the figure. The texture contains, in addition to this orientation, the first-order twins of it, shown in the figure by the filled triangles. This orientation relation has been suggested by others also, under certain annealing conditions,3'4 although pole figures have not been published to confirm it. Some orientations in recrystallized sheets are identical with their twins, because of the symmetry elements of the texture— this is true, for example, with the (113) [ZII] texture so commonly reported for brass—hence it appears impossible in such samples to decide whether the twin relationships result from twinning or merely from the symmetry of the deformation process. The present investigation of a commercial copper strip seems to yield an example in which annealing twins account unambiguously for the principal orientations present. It proves to be a case, also, for which the recrystallization texture cannot be viewed as derived from the deformation texture by a first or second-order twinning mechanism. Materials and Methods The samples investigated were of secondary copper (melted in belgium) to which 0.19 per cent iron had been added to raise the recrystallization temperature. How much the orientation characteristics of this metal can be ascribed to the iron content and how much to other impurities or to melting and pouring practice have not been investigated.* The rolling was done in one direction only, on a mill with rolls of about 20-cm diameter. A strip I. cm wide was reduced from 5 mm thickness to 0.05 mm by several cold passes at commercial speeds. The samples cut from this 99 per cent reduced strip were X-rayed throughout their entire thickness. A pole figure made soon after rolling and annealing was identical, within experimental error, with one that was made when a two-year interval occurred between rolling and annealing. X-ray patterns were made on a camera2 that traversed

Jan 1, 1947

By C. S. Barrett, P. Coheur

AXnealing twins are common in the microstructure of copper that has been rolled and recrystallized. In such samples it follows that a twin relationship should exist between components of the re-crystallization texture,' and several examples of this have been reported. For example, twin relationships have been found in recrystallized electrolytic copper sheet, as indicated in Fig. I, from a paper by Coheur and Lejeune.2 In this pole figure the cube texture (100) [001] is indicated by the hollow squares in the lower half of the figure (the pole figure for 200 reflections) and in the upper, (III), part of the figure. The texture contains, in addition to this orientation, the first-order twins of it, shown in the figure by the filled triangles. This orientation relation has been suggested by others also, under certain annealing conditions,3'4 although pole figures have not been published to confirm it. Some orientations in recrystallized sheets are identical with their twins, because of the symmetry elements of the texture— this is true, for example, with the (113) [ZII] texture so commonly reported for brass—hence it appears impossible in such samples to decide whether the twin relationships result from twinning or merely from the symmetry of the deformation process. The present investigation of a commercial copper strip seems to yield an example in which annealing twins account unambiguously for the principal orientations present. It proves to be a case, also, for which the recrystallization texture cannot be viewed as derived from the deformation texture by a first or second-order twinning mechanism. Materials and Methods The samples investigated were of secondary copper (melted in belgium) to which 0.19 per cent iron had been added to raise the recrystallization temperature. How much the orientation characteristics of this metal can be ascribed to the iron content and how much to other impurities or to melting and pouring practice have not been investigated.* The rolling was done in one direction only, on a mill with rolls of about 20-cm diameter. A strip I. cm wide was reduced from 5 mm thickness to 0.05 mm by several cold passes at commercial speeds. The samples cut from this 99 per cent reduced strip were X-rayed throughout their entire thickness. A pole figure made soon after rolling and annealing was identical, within experimental error, with one that was made when a two-year interval occurred between rolling and annealing. X-ray patterns were made on a camera2 that traversed

Jan 1, 1947

By L. J. Howell, R. C. Sommer, H. H. Kellogg

WORK described herein was undertaken with the aim of determining some of the physical-chemical properties of electrolytes suitable for the electrodeposition of pure zirconium metal. In this paper the phase diagram, vapor pressure, and activities in the melt are considered. In a companion paper,' the electrolytic conductivity of some of these melts is reported. The melts studied were mixtures of NaCl and/or KC1 with ZrC1,. Chloride melts were chosen for study because 1) if the electrolyte is to be useful for industrial electrodeposition of zirconium, the chlorides will be preferred to the relatively costly bromides and iodides; 2) fluoride melts were being studied in another laboratory (Horizons Inc., Cleveland); and 3) melts containing oxygen, in any form, are unsuitable for preparation of pure zirconium, because of the great affinity of this metal for oxygen. Unlike electrodeposition from aqueous solution, the fundamental behavior of fused-salt electrolysis is poorly understood. In most cases, such basic electrochemical information as the phase diagram of the melt system, activities in the melt, conductivity, the nature of the current-carrying ions, the equilibrium electrode potentials, and the overvoltage behavior of the electrodes is unknown to the researcher who would develop a new electrodeposition process employing a fused salt. This research project was designed to supply information about some of these basic physical-chemical properties so that an intelligent choice of electrolyte for electrodeposition studies could be made. Experimental The experimental difficulties-encountered in this work result from the properties of zirconium metal and ZrC1,. ZrC1, is a solid which sublimes at 334°C. It is rapidly hydrolyzed by moist air to HC1, ZrOCl,, and ZrO,. Unusual precautions were exercised in this work to prevent hydrolysis of ZrC1, and rigidly to exclude oxygen, nitrogen, hydrogen, and carbon from the melts under study. These elements are known to react with and contaminate zirconium metal. All melts were studied in vacuum systems, i.e., in the presence of ZrC1, vapor only. Transfer of ZrC1, to or from the melts was accomplished entirely by vacuum sublimation. In this way, neither the melts nor the ingredients thereof were permitted to

Jan 1, 1958

By M. J. Pool, C. E. Lundin

THE relative partial molar enthalpies of aluminum, gallium, and indium in liquid tin have been measured at 750°K by liquid-metal solution calorimetry. The measured heat effects and the calculated relative partial molar heats of solutions at infinite dilution are listed in Table I along with the relative heat contents of the solutes calculated from the data of Kelley. All of the values are referred to 750°K even though the calorimeter temperature fluctuated by +1°K during the entire series of experiments. The effect of this small temperature variation on the experimental values should be less than the experimental error. The limits of error given in Table I represent the standard deviations of all values from the mean. In no case was the experimental deviation greater than the listed error limits. The reported error estimates only apply to the estimated precision of experimental values and not to their accuracy. Systematic errors could be present in the calorimeter which would affect the absolute values given. Moreover the heat-content data used could also be in error and this would affect the end results. The relative enthalpies used were listed in Table I so that future corrections could be made if necessary. The relative partial molar heats of solutions of aluminum in liquid tin and dilute A1-Sn liquid solutions are large and positive. The value at infinite dilution is given in Table I. In the dilute-solution region investigated the relative partial molar heat of solution was a linear function of composition. A least-squares analysis of the data gave the following expression at 750°K: Atf^ = 6195 - 12,160 A:A1(cal/g-atom) where XA1 is the mole fraction of aluminum in the alloy. This can be compared with the data of Cohen, Howlett, and ever' who obtained the expression: 1SM = 6075 - 10,750 XM at 573°K Apparently both the partial molar heat of solution at infinite dilution and the concentration dependence increase with increasing temperature. This same

Jan 1, 1964

By W. A. Olds, H. F. Yancey, M. R. Greer

John Griffen (Consulting Engineer, Pittsburgh)— This paper presents much data offering tentative answers to many technical questions that have been raised by the employment of dense-medium processes and, particularly. by use of the drum-type vessel. It is to be hoped that the Bureau of Mines will publish complete detailed data for the 50 or more tests so that it may be studied and analyzed by everyone interested. Such study will take considerable time and effort. The writer is therefore obliged to confine his discussion to a few points he has noted as being open to question. The data in Table VI which shows the recovery efficiency for the 1 to ½-in. fraction as 100 pct raised a question concerning the accuracy of these calculated figures; washability data on the washed coal and refuse show that such a figure is impossible. When the ash content of the misplaced material in the washed coal is higher than that of the misplaced material in the refuse, recovery efficiency must be less than 100 pct. A etudy of the data In Tables 111, IV, V, and VI suggest that this error probably arose from slight errors in calculating the data in Table V and more probably from the small scale used in plotting the washability curves from the Table V data. Using the size consist data and the weight and ash percentages of individual gravity fractions of each size as given in Tables 111 and IV and the reported recovery of 80 pct of washed coal, a revised Table V was calculated, carrying weight and ash percentages to hundredths of a percent instead of rounding off at tenths. This washability data for each size of Belling-ham reconstituted feed was then plotted on large scale washability curves. From this data the new Table XIV was prepared, which agrees very closely with data shown in Table VI except for two important values, theoretical yields and recovery efficiencies. As will be noted the recovery efficiencies in Table XIV are significantly lower than those given in Table VI. A study was then made of the data showing distribution of the specific gravity fractions to washed coal and refuse. This study indicated that when this distribution was based on the fractions as tested at 0.1-sp gr intervals the number of points obtained were insufficient to establish the distribution curves with reasonable precision, which in turn would affect the accuracy of the values for the specific gravity of separation and the error areas. The data in Tables III and IV of the paper and curves prepared therefrom make it possible for the specific gravity fractions to be subdivided further. This was done using 0.05-sp gr fractions and the distribution data so obtained is given in Table XIV, with resulting values for the specific gravity of separation and the error areas. The writer believes that the derived values shown on Table XIV are more accurate than the correspond-

Jan 1, 1955

Charles H. White, Harvard University, Cambridge, Mass, (communication to the Secretary*):—In answer to Mr. Jar-man's questions I am able to say that constant use (during term-time) since 1901 has shown the new appliances in our laboratory to be very satisfactory. The draft in the hoods is sufficient to lift the fumes promptly from the baths and hotplates ; and the occasional application of stove-polish,—usually about three times a year, at the recess-periods,—so well protects all iron-work in the hoods that, up to the present time, there is very little evidence of the corroding action of acid fumes. Iron should never be used in the construction of hoods above

Jan 1, 1906