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By R. W. Gurry

When a steel in the austenitic state, with all its carbon in solution, is maintained, at constant temperature, in contact with a gas that removes the carbon from the surface, yet without otherwise altering the composition of the steel, the change in weight of the specimen, after any period of exposure, is a direct measure of the amount of carbon it has then lost. The purpose of the present paper is to show how, by application of established mathematical reasoning based on the fundamental diffusion law and on certain postulates, this loss of weight yields a complete picture of the distribution of carbon throughout a specimen of regular shape after any period of exposure, with all the accuracy required in any practical occurrence of decarburization. Precisely the same is true for the gain in weight during the reverse process of carburization, or for the gradual gain or loss of any element, so long as the steel comprises only a single phase at temperature, provided always that the experimental conditions conform to the postulates. The change in carbon content from surface to center of the specimen is always continuous, when everything is in solution, even though under the microscope the decarburized zone (or carburized rim) may appear to be sharply defined. The experimental procedure is described and some typical results are presented, which are then interpreted by application of the diffusion law. Experimental Procedure Initially an endeavor was made to follow the gain of weight during the process of carburization in a hydrogen-toluene atmosphere, but it was soon found that the specimen became coated with graphite, which could not be removed without some loss of metal; therefore it was decided to continue carburization until the steel was saturated throughout, to remove all graphite from the surface of the specimen, and then to follow the loss of weight during decarburization in a moist hydrogen atmosphere at the same temperature as that used for carburizing. The carburizing procedure has been described in an earlier paper;' it suffices to state here that the carburization lasted about I40 hr. at 760°C. (1760°F.) and 44 hr. at iiio°C. (2030°F.), these periods being long enough-—on the basis of the calculations presented later—to ensure that the specimen was about 99.9 per cent saturated at each temperature. The specimen was a cylinder about 3.8 cm. long and 0.475 cm. in diameter; the materials were carbonyl iron, a commercial low-metalloid iron, and a steel with 3.6 per cent nickel and the usual proportion of other elements. The fully carburized specimen, after cooling at the top of the furnace tube, was placed in a lathe and sandpapered to remove all graphite; then the diameter was measured with a micrometer caliper, and the initial weighing (corresponding to complete saturation) was made. By means of a

Jan 1, 1942

By L. A. Shipman

The combustion of coal in fuel beds has been practiced as an art for many years; during the last 2 7 years a scientific approach to this subject has contributed a small amount of fundamental data. The subject is a very controversial one. Opinions regarding the performance of the same coal used in the same equipment in different plants may vary from "the best coal ever used in the plant" to "the worst coal ever tired." These opinions can all be true, owing to the various conditions under which the coal was used. Because of these differences, an attempt will be made in this paper to discuss coal facts and coal characteristics as related to the use phenomena observed during the art of firing coal in fuel beds for many years. The work of Kreisinger1 and his associates in the 1,'. S. Bureau of Mines, reported in 1916, was the first scientific attempt I know of to obtain factual data explaining the mechanism of combustion of fuel beds. They gave a chart showing an ignited fuel bed. The air passing up through the fuel bed first combined with the fuel by a reaction resulting in the complete combustion of carbon to CO2, which combined with the carbon in higher levels of the fuel bed to form CO with the absorption of heat. The fundamental facts produced in those experiments proved of much value and checked with practical experiences with hand-fired fuel beds. Hand firing was the prevailing method of stoking coal at that time. The order in which these reactions occur, as shown by Kreisinger and his associates, has been amply confirmed by repetition of this work with different fuels both her? and abroad. These experiments also showed that under their conditions the rate of burning was proportional to the air flow. These data were of practical value to a fireman and were accepted as generally true in all fuel beds. In later years many observations by myself in fuel beds of underfeed stokers and other thick fuel beds such as gas producers, where channeling. increase of particle size, or both, occur. indicated that, instead of the horizontal layers we had thought were present, perhaps the layers were vertical or irregular. Later investigations in fuel beds made by Mayers2 and Barnes3 indicated that the burning takes place in some instances along the surfaces of vertical or irregular channels or cracks in the fuel bed and that under these conditions a reaction occurs that differs from that in the old horizontal-layered handfired fuel beds. Examining the data in Kreisinger'sl experiments, and the information in different charts with different fuels, different retort positions and air admissions of Barnes3 and the gas analysis arid isotherms of Mayers,2 one can check experience observation and come to a conclusion that as particle size of the fuel increases with other conditions the same, the maximum CO2 and temperature

Jan 1, 1947

By L. A. Shipman

The combustion of coal in fuel beds has been practiced as an art for many years; during the last 2 7 years a scientific approach to this subject has contributed a small amount of fundamental data. The subject is a very controversial one. Opinions regarding the performance of the same coal used in the same equipment in different plants may vary from "the best coal ever used in the plant" to "the worst coal ever tired." These opinions can all be true, owing to the various conditions under which the coal was used. Because of these differences, an attempt will be made in this paper to discuss coal facts and coal characteristics as related to the use phenomena observed during the art of firing coal in fuel beds for many years. The work of Kreisinger1 and his associates in the 1,'. S. Bureau of Mines, reported in 1916, was the first scientific attempt I know of to obtain factual data explaining the mechanism of combustion of fuel beds. They gave a chart showing an ignited fuel bed. The air passing up through the fuel bed first combined with the fuel by a reaction resulting in the complete combustion of carbon to CO2, which combined with the carbon in higher levels of the fuel bed to form CO with the absorption of heat. The fundamental facts produced in those experiments proved of much value and checked with practical experiences with hand-fired fuel beds. Hand firing was the prevailing method of stoking coal at that time. The order in which these reactions occur, as shown by Kreisinger and his associates, has been amply confirmed by repetition of this work with different fuels both her? and abroad. These experiments also showed that under their conditions the rate of burning was proportional to the air flow. These data were of practical value to a fireman and were accepted as generally true in all fuel beds. In later years many observations by myself in fuel beds of underfeed stokers and other thick fuel beds such as gas producers, where channeling. increase of particle size, or both, occur. indicated that, instead of the horizontal layers we had thought were present, perhaps the layers were vertical or irregular. Later investigations in fuel beds made by Mayers2 and Barnes3 indicated that the burning takes place in some instances along the surfaces of vertical or irregular channels or cracks in the fuel bed and that under these conditions a reaction occurs that differs from that in the old horizontal-layered handfired fuel beds. Examining the data in Kreisinger'sl experiments, and the information in different charts with different fuels, different retort positions and air admissions of Barnes3 and the gas analysis arid isotherms of Mayers,2 one can check experience observation and come to a conclusion that as particle size of the fuel increases with other conditions the same, the maximum CO2 and temperature

Jan 1, 1947

By E. E. Underwood, L. L. Marsh

Aluminum single crystals, alloyed with 0.042 atomic pet Cu and 0.11 and 1.1 atomic pct Mg, were subjected to constant stress creep tests, tensile tests, and hot hardness measurements within a temperature range of 300° to 866OK. Calculations based on Dorn's temperature-compensated time parameter, 6, gave a value of DH, = 27,000 cal per mol for the activation energy of early creep in aluminum single crystals. Correlations have been obtained for aluminum alloy single crystals with the parameter E for solid solution strengthening, as well as with the parameter F for solid solution hardening, by using a valence of three for aluminum. Limited measurements on tensile specimens show that the slip band density tends to decrease with increasing temperature and with decreasing solute concentration. INCREASING interest is being shown in the mechanisms of plastic deformation in single crystals during tensile and creep testing. The complexity of deformational processes in polycrystalline materials has led to a search for simpler experimental conditions. Numerous creep and tensile investigations have been conducted with pure, metallic single crystals. To a lesser degree, the effects of alloying elements on the tensile properties of single crystals have been determined. However: the literature dealing with the effects of alloying additions in single crystals under creep conditions is vanishingly small. This paper represents an attempt to narrow this gap in the knowledge of the subject. Previous investigations of creep behavior at the Battelle Memorial Institute1-1 have been of great value in the analysis of the present single crystal data. It is equally desirable, however, to ascertain the extent of correspondence between the behavior of single crystal and polycrystalline materials. For this purpose, correlations, similar to those developed for polycrystalline aluminum alloys by Dorn and co-workers, have been made with the single crystal data. The results from this study have tended to confirm and extend those correlations to the case of alloyed single crystals. Materials and Procedures Three dilute binary aluminum alloys were prepared for this investigation from 99.99 + wt pct Al, 99.8 wt pct Mg, and 99.92 wt pct (electrolytic) Cu. The nominal compositions of the alloys were 0.042 atomic pct Cu, and 0.11 and 1.1 atomic pet Mg. Precautions were taken to avoid contamination of the stock during melting and casting of the alloys. After a heat treatment of 8 hr at 925°F the alloys were extruded, then machined into) threaded tensile specimens with a 3 in. reduced section and a 0.505 in. diam. Spectrographic examination showed less than 47 ppm metallic impurities in each alloy. The single crystals were grown by the strain-anneal method, with a critical strain of about 11/4 pet giving the optimum results. In general, 3 in. crystals were obtained with the Al-Cu alloy, but smaller crystals in the magnesium alloys necessitated the use of 2 in. and 1 in. gage lengths with the low and high magnesium alloy specimens, respectively. After an electrolytic polish, the orientation of that portion of the specimen containing the largest single crystal was determined from Laue back-reflection photographs. Tensile tests were conducted at a constant load rate of about 2 lb per min. Creep runs were made in a constant temperature room, under constant stress at the higher creep temperatures, and constant load at the lower temperatures. The eloneation was measured to within ±5 microin. by a specially designed capacitance extensometer. The ex-tensometer arms were attached to the 3 in. specimens at the shoulders of the test piece or, where the crystals were smaller than 3 in., by knife-edge grips.

Jan 1, 1957

By Morris Muskat, J. M. McDowell

In both production and refining operations of the oil industry many processes are controlled by the gas-liquid phase relationships of the hydrocarbon mixtures of interest. The quantitative behavior of fractionating or distillation columns and stills depends on the changes in the equilibrium distributions of the hydrocarbon components between the gas and liquid phases as the pressure or temperature conditions may vary along the length of the column or as the gross operating parameters and compositions are varied. In oil producing operations the nature and amount of gas phase developed within an underground reservoir as it is being depleted and its pressure declines also involve the basic equilibrium gas-liquid phase interactions. The influence of surface conditions of temperature and pressure and various separation procedures on the nature and amount of stock tank oil and natural gas recovered from a given well stream is likewise determined by the same basic phase equilibrium characteristics of the hydrocarbon systems. Such equilibrium separation of the gas and liquid phases in a well stream is of importance both in establishing optimum separator conditions for obtaining maximum stock tank oil yields and in the general problem of crude stabilization. The phenomena involved in these problems and their quantitative aspects can, of course, be established in each individual instance by appropriate laboratory experimentation. It has been found, however, that by associating with the individual hydrocarbon components functional characteristics de- scribing their individual gas - liquid phase equilibrium behavior, the phase properties of the composite mixtures can be predicted by mathematical computation. These characteristics have been termed "equilibrium constants", or "equilibrium ratios"," and are defined by the general equation: where K, is the equilibrium ratio for the jth component, y, is the rnol fraction of that component in the gas phase, and xj is the corresponding mol fraction in the coexisting liquid phase. Considering the Kj as representing available and measurable properties of the individual components of a mixture, and as defined by Eq. (l), it is readily shown that in a coexisting gas-liquid system the rnol fraction concentrations of the individual components in the gas phase, y,, and those in the liquid phase, x,, are given by the expressions: where the nj are the corresponding rnol fraction concentrations in the composite system, and ng is the mol fraction of the whole which is in the gas phase. The basic unknown in Eq. (2) is n,: which gives the gross separation between the gas and liquid phases. This may be determined in principle by imposing the requirement that the sums of the mol fractions in both the gas and liquid phases are unity, i.e. by the equations: The solution of the equivalent Eqs. (3) lying between 0 and 1, when inserted into Eqs. (2), provides a complete description of the compositions of the coexisting gas and liquid phases. While the Eqs. (3) are essentially equivalent to polynomial equations, such transformations are of little value when dealing with multicomponent sys-

Jan 1, 1949

By J. M. McDowell, Morris Muskat

In both production and refining operations of the oil industry many processes are controlled by the gas-liquid phase relationships of the hydrocarbon mixtures of interest. The quantitative behavior of fractionating or distillation columns and stills depends on the changes in the equilibrium distributions of the hydrocarbon components between the gas and liquid phases as the pressure or temperature conditions may vary along the length of the column or as the gross operating parameters and compositions are varied. In oil producing operations the nature and amount of gas phase developed within an underground reservoir as it is being depleted and its pressure declines also involve the basic equilibrium gas-liquid phase interactions. The influence of surface conditions of temperature and pressure and various separation procedures on the nature and amount of stock tank oil and natural gas recovered from a given well stream is likewise determined by the same basic phase equilibrium characteristics of the hydrocarbon systems. Such equilibrium separation of the gas and liquid phases in a well stream is of importance both in establishing optimum separator conditions for obtaining maximum stock tank oil yields and in the general problem of crude stabilization. The phenomena involved in these problems and their quantitative aspects can, of course, be established in each individual instance by appropriate laboratory experimentation. It has been found, however, that by associating with the individual hydrocarbon components functional characteristics de- scribing their individual gas - liquid phase equilibrium behavior, the phase properties of the composite mixtures can be predicted by mathematical computation. These characteristics have been termed "equilibrium constants", or "equilibrium ratios"," and are defined by the general equation: where K, is the equilibrium ratio for the jth component, y, is the rnol fraction of that component in the gas phase, and xj is the corresponding mol fraction in the coexisting liquid phase. Considering the Kj as representing available and measurable properties of the individual components of a mixture, and as defined by Eq. (l), it is readily shown that in a coexisting gas-liquid system the rnol fraction concentrations of the individual components in the gas phase, y,, and those in the liquid phase, x,, are given by the expressions: where the nj are the corresponding rnol fraction concentrations in the composite system, and ng is the mol fraction of the whole which is in the gas phase. The basic unknown in Eq. (2) is n,: which gives the gross separation between the gas and liquid phases. This may be determined in principle by imposing the requirement that the sums of the mol fractions in both the gas and liquid phases are unity, i.e. by the equations: The solution of the equivalent Eqs. (3) lying between 0 and 1, when inserted into Eqs. (2), provides a complete description of the compositions of the coexisting gas and liquid phases. While the Eqs. (3) are essentially equivalent to polynomial equations, such transformations are of little value when dealing with multicomponent sys-

Jan 1, 1949

By K. Mukherjee

Instantaneous resistance change during martensitic transformation in Fe-30 at. pct Ni alloy has been studied using a low-noise electronic system. The smallest signals recorded in this investigation were of the order of 10 pv. These small signals did not show the initial increase reported by earlier investigators to support a double shear mechanism.&apos; A variety of pulse shapes and sizes was observed during "burst" transformations, and these signals were neither a linear function of the size of martensite plates nor of the volume fraction transformed. Even the smallest signals, presumably from single plates, showed complications resulting from elastic and/or plastic deformation, shock wave propagation, and so forth, which are inherent in the growth process of a martensite plate. The time of formation and interface velocity determined froni this experiment agree very well with the pioneering work of Bunshalz and Mehl.&apos; AN Fe-30 at. pct Ni (c0.005 pct C) alloy was used to study the time of formation of martensite plates. Martensitic transformations, unlike the nucleation and growth processes, are usually characterized by an extremely fast reaction rate. During the transformation, the crystal structure changes and this change is propagated through a finite volume of the parent crystal lattice within a very short time interval. The interface between the two phases probably consists of moving dislocations, and the time of formation of the plate depends on how fast this dislocation interface can move. Knapp and Dehlin~er or Cottrell and Bilby mechanisms, or similar dislocation models, can be used to calculate the time of formation of a martensite plate of a given size. In the past, conventional photographic technique475 as well as electrical resistivity techniques"~-" have been used to measure the time of formation of a martensite plate. The specific resistance of the martensitic phase in Fe-30 at. pct Ni alloy is lower than that of the austenite phase. Therefore if a current is passed through a small austenite sample in series with a large external resistance, then one would observe a voltage change across the sample as martensite is formed. Such dc measurements are shown in Fig. 1. The initial large voltage drop in Fig. 1, at the M, temperature, is due to a "burst" transformation where a large number of plates are formed in a cataclysmic manner within a very short interval of time. Even during the later stages of transformation as shown in Fig. 1, one can observe discontinuous voltage changes due to small bursts. In order to resolve the time scale of such discontinuous stages, the voltage signals are amplified and fed into a highspeed oscilloscope. In this investigation a low-noise amplifier was used for the first stage of amplification. The signal to noise ratio was further improved by the design of a pulse transformer. This transformer was capable of amplifying the signal by a factor of six. Voltage signals were studied over a wide time scale ranging from 2 sec to 0.1 psec. I) EXPERIMENTAL PROCEDURE A) Specimen Preparation. Specimens were cut from induction-melted Fe-30 at. pct Ni (<0.005C) alloy and cold-rolled to 0.2 by 1 mm cross section and an average length of 5 cm. During mechanical shaping, the specimens were strain-annealed at 950°C for 24 hr in vacuum. Finally the finished samples were vacuum-annealed at 1000°C for 6 hr and water-quenched to room temperature. The average grain diameter was 0.02 cm. B) Cooling System. The M, temperature of the alloy was -55°C. Fig. 2 shows the arrangement which was used to cool the specimen at a slow rate. The specimens were mounted inside a i -in.-diam hole in the 2-in.-long section of the copper specimen holder. This cavity was filled with silica gel. A dummy specimen was used under identical conditions for

Jan 1, 1969

By Ken-ichi Hirano, B. L. Averbach, Morris Cohen, N. Ujiiye

The influence of plastic deformation in compression on the self-diffisivity of a iron has been measured in the temperature range of 742º to 885°C. The diffusivity is enhanced in proportion to the strain rate, but this dependence decreases with increasing temperature. The magnitude of the strain is relatively unimportant in this connection. Strain rates from 0 to -2 x 10-3 sec-1 were investigated, with a corresponding increase in diffusivity up to 3 x 103 times. The results are analyzed in terms of vacancy diffusion and the excess vacancies introduced during dejornzntion. It is concluded that grain boundaries are the main vacancy sinks in polycrystalline iron and that the vacancy lifetime is therefore dependent on the grain size. A typical vacancy lifetime at 800°C with a nzean grain-boundary intercept of 0.3 cm is of the order of 1 sec. LATTICE imperfections are considered to be the dominant mechanism of diffusion in close-packed crystals. Vacant lattice sites are usually the most important defect, but the enhancement of diffusion along grain boundaries and other short-circuiting paths has been well documented. Inasmuch as plastic straining produces a variety of defects, it would be expected that the application of stresses sufficient to cause plastic flow during a diffusion run might result in an increase in the self-diffusivity. Enhanced self-diffusion in a iron under compressive creep has been observed by Buffington and Cohen&apos; and subsequent coworkers.2 Lee and Maddin3,4 have also found an enhancement in the self-diffusivity of silver single crystals undergoing torsional deformation. On the other hand, Darby, Tomizuka, and Balluffi5 have not observed any significant diffusion increase in single crystals of silver deformed either in tension or in compression, although the results in this case may have been affected by the occurrence of recrystallization. With poly crystalline silver, however, Forestieri and Girifalco6 have found en- hanced diffusion during compressive creep. A small decrease in the self-diffusivity of zinc single crystals under compressive loading has been reported,7 but the applied stresses in these experiments were too low to cause appreciable plastic deformation. For the cases in which enhanced diffusion has been found, a number of common effects have been noted. Usually, the ratio of the diffusivity during straining, Ds, to the diffusivity in the unstrained condition, D,, varies linearly with the strain rate, and does not seem to be a function of the plastic strain, at least up to ? = 0.2. Values of Ds/Du of the order of 100 have been reported&apos;-4 but the enhancement decreases with increasing diffusion temperature. The activation energy for diffusion decreases markedly with increasing strain rate and approaches a level of roughly one-half the unstrained value. Most of the current explanations of these observations assume that excess vacancies are generated by the deformation, but rather large concentrations of excess vacancies and/or long lifetimes are required by these theories.&apos;,&apos;,&apos;,&apos; Since the original work on iron, there has been an important improvement in the compressive-loading technique.2 The early data were also analyzed without taking into account the motion of the coordinate system in the specimens undergoing plastic deformation. This problem has now been solved by a number of investigators (see Refs. 11, 12, and the appendix of the present paper). Consequently, the strain-diffusion runs on iron for the Ds measurements were repeated and extended over wider ranges of temperature and strain rate. In addition, the original diffusivity data9 on the unstrained iron have been corrected for the divergence of the beam in the counting system and new data points have been added, resulting in somewhat different values for the self-diffusi-vities in a iron.10 The new values for Du are used in this paper. A comparison of Ds and Du confirms the large enhancement in the self-diffusivity of iron during compressive creep, as previously reported.&apos;,2

Jan 1, 1963

By L. S. Birks

The bainite transformation in a 3.5 pct Ni-1.25 pct Cr steel was studied under various conditions of cooling and stress. Several characteristics may be specified: 1) transformation in the bainite region (925° to 575°F) is very little affected by the manner of cooling from the austenitizing temperature at 1600°F to 575°F)tothe upper limit of bainite transformation at 925°F; 2) starting time for the bainite transformation is the same order of magnitude for either isothermal transformation or continuous cooling, but the rate of transformation is somewhat greater for isothermal transformation; 3) tensile stress accelerates both isothermal and continuous cooling transformation, and 32,000 psi stress changes the form of the isothermal transformation diagram to correspond in appearance to the continuous cooling diagram; 4) transformation for nonlinear, continuous cooling may not be determined directly from the linear, continuous cooling transformation diagram, but may be predicted by assuming first that the fractional amount of austenite transformed in a given small temperature interval depends on the approximate linear cooling rate during that temperature interval and then by summing stepwise over the whole temperature range. IN a previous publication&apos; an X-ray spectrometer was described with which the X-ray diffraction from a specimen could be observed continuously under controlled temperature and tensile stress. This instrument has now been applied to a study of the austenite-bainite transformation in a Ni-Cr steel for both isothermal and continuous cooling conditions, with and without stress. Certain characteristics of the transformation lead to a method of predicting the amount of transformation to be expected at a given temperature for any type of cooling curve. Material and Specimen Preparation The steel chosen for the investigation was a Ni-Cr steel having the composition in the following percentages: 0.30 C, 0.27 Mn, 0.019 P and S, 3.50 Ni, and 1.25 Cr. In order to fabricate specimens suitable for the X-ray spectrometer, a 1/4 in. plate was ground down to 0.060 in. and then cold rolled to about 0.035 in. Next it was heat treated by quenching in oil from 1650°F and tempering at 1200°F for 1 hr. Then it was etched in dilute nitric acid to reduce its thickness to 0.014 in. and cut into blanks in the shape of flat tensile specimens 3 1/4 Vi in. long, 7/16 in. wide, with a notch % in. long and 7/32 in. wide; see Fig. 1. X-Ray Technique Since the X-ray spectrometer has been described in detail elsewhere,&apos; only a brief outline of the principles will be repeated here. A focusing, pow- der-diffraction arrangement&apos; was used, as shown schematically in Fig. 1, and the specimen was mounted vertically in a vacuum furnace (not shown in the figure). The X-rays, moving in a horizontal plane, enter and leave the furnace through beryllium windows. As shown in the figure, X-rays diverging from the line source A are diffracted by the specimen B and converge at the detector slit C. The detector D and the slit C may be set at the proper angle in the horizontal plane to receive X-rays diffracted by either the face-centered phase (austenite) or the body-centered form (ferrite, bainite, martensite). The specimen is heated by electrical conduction between connectors E, and E,, and a Pt—Pt-10 pct Rh thermocouple spot-welded to the center of the notched region on the side away from the X-ray beam indicates the temperature continuously on a Brown recorder. Temperature control is exercised manually with a variable transformer on the input to E,-E,. Any desired time-temperature relationship is easily obtained by first drawing the desired curve on the temperature recorder chart and then adjusting the variable transformer during the run so that the thermocouple

Jan 1, 1957

By Richard H. Siller, Rex B. McLellan

A model for interstitial solid solutions has been considered in which a repulsive Potential exists between interstitial atoms in the solvent lattice. It has been shown that this model is consistent with the thermodynamic Properties of certain interstitial solid solutions. The model is then applied to the calculation of the variation of the diffusivity of carbon in au-tenite with composition. Although the energy levels at the saddle point, and thus the absolute values of dif-fusivity, cannot be calculated, it is shown that by taking the repulsive interactions between the diffusing atoms into account the functional form of the dependence of diffusivity on solute concentration can be derived. ThE composition dependence of the diffusivity, D, of carbon in austenite at a given temperature is well-known.&apos;-3 smith3 tried to reconcile the observed composition dependence of D at 1000°C with the previously observed4 composition dependence of carbon activity using equations for D derived by arken5 and Fisher, Hollomon, and Turnbull,6 but was unsuccessful. In this paper we shall modify the approach of Fisher et al. by considering the "blocking" model7 for interstitial solid solutions, based on concept due to Speiser and Spretnak,&apos; in which a repulsive potential exists between interstitial solute atoms in the solvent lattice, causing a certain number of interstitial sites to be "blocked" from occupancy by further solute atoms. We shall thus be able to describe the intimate relationship between the composition dependence of carbon diffusivity, a kinetic phenomenon, and the composition dependence of carbon activity in austenite. THEORY Consider for convenience one-dimensional interstitial diffusion in an fcc lattice in the [loo] direction. Fig. 1. Assume that solute atoms occupy octahedral sites only.7,9&apos;10 These octahedral sites are located on {lOO} planes a/2Å apart. A solute atom, A, occupying an octahedral site on a {100 } plane denoted by 2, has twelve nearest-neighbor octahedral sites: four on plane 1, four on plane 2, and four on plane 3. Diffusion occurs when there is a net flux of solute atoms, through an imaginary plane shown with dashed lines, from plane 2 to plane 3. Fisher et al6. use the concept of activated complexes, as given in the theory of absolute reaction rates." They show that the number of solute atoms per cubic centimeter per second which pc — Fig. 1-Diagram showing the arrangement of octahedral sites (x) in the fcc lattice. pass in the direction of diffusion from activated to new interstitial position is: ?where C is the concentration of the solute in atoms per cubic centimeter, l/m + is the fraction of new interstitial positions corresponding to motion in the forward diffusion direction (transmission coefficient), ?F* is the free-energy difference between the activated complex and the reactants when each is in its standard state at the temperature of the reaction (independent of temperature and composition in the case of carbon in austenite), y is the activity coefficient of the solute species, and, finally, ym is the activity coefficient of the activated complex (assumed constant). The flux of atoms moving in the forward direction through an area of 1 sq cm perpendicular to the direction of diffusion is therefore: m+ Ym l &apos; atoms per second where is the distance between planes. The blocking model states that a nearest-neighbor octahedral site of a given solute atom has a probability, f, of being inaccessible to other solute atoms. The number of available sites for diffusion on a given plane will, therefore, depend on f, which is constant, and Nu, the number of solute atoms on that plane. The effect is to have more available sites in the diffusion direction, thereby increasing the net flux of solute atoms. This is reflected in the transmission coefficient, l/m. To calculate the transmission coefficient for solute

Jan 1, 1970

By V. Patarini, M. Salkind

BECAUSE of its high strength and stiffness coupled with low density, continuous boron filament is showing great promise as a potential reinforcement for both metals and nonmetals. Of primary consideration for structural applications is the fatigue behavior of boron fiber composites. Composite fatigue behavior is dependent upon three factors: 1) fiber fatigue behavior, 2) matrix fatigue behavior, and 3) the effect of the interface and fiber ends. The purpose of this note is to describe the behavior of boron filament in rotating beam fatigue. The filament, described by Talley&apos; and Galasso, Salkind, Kuehl, and Patarini,&apos; was made by the hydrogen reduction of boron trichloride on a hot tungsten filament. Testing was performed using a commercial rotating beam wire fatigue tester* described by Votta.~ One end of the test sample is held in a chuck in a synchronous motor. The sample is bent around in a "U" shape, and the other end inserted into a carbide bushing. The maximum strain occurs at the bottom of the "U" where the radius of curvature is a minimum. The strain is adjusted by adjusting the length of the specimen and the location of the bushing. Samples were rotated at 3600 rpm and an automatic shutoff device used to determine the number of cycles to failure. The measurements were accurate to the nearest 360 cycles. The fatigue behavior is summarized in Fig. 1 for fifty-one samples of 4.8 x 10"3 in. diam fibers and ten samples of 3.2 X 10"3 in. diam fiber. The two sample groups represent two different filament production runs and two different nominal size groups. Both groups exhibited nominal tensile strengths of 400,000 psi. No significant difference in the fatigue behavior of the two sample groups is apparent. The scatter in the data is not unexpected for a brittle filament which exhibits a tensile strength distribution with a standard deviation of 10 to 15 pct. Because the test procedure provides a known outer fiber strain in the sample, the maximum stress was calculated assuming a Young&apos;s modulus of 58 x 10&apos; psi. This value was selected as being representative of several nominal fiber sizes.2 All of the samples which failed exhibited sudden, catastrophic fracture, and no permanent deformation. One sample was stopped after 1.66 x lo8 cycles at *200,000 psi. The fiber exhibited no apparent damage or deformation. It is apparent that the fatigue resistance of boron filament is quite good. It can therefore be speculated that the fatigue behavior of boron fiber composites would be controlled by the "weaker links", namely matrix fatigue resistance and interface behavior. In fact, preliminary investigations have revealed that this is true for boron-reinforced aluminum? It should be noted that the data presented herein may not necessarily reflect the tensile fatigue behavior of boron filament. It is well-known that boron filament has a radial residual stress pattern with the outer surface in ~om~ression.~ Because of this fact, tensile failure is normally nucleated in the interior of the filament.5 Since the data presented herein is for a rotating beam test in which only the outer surface of the fiber is stressed to the maximum value, it would be incorrect to assume that the failure mechanism and fatigue behavior would be the same if the fiber were tested in tensile fatigue. The fact that many of the data are well above the nominal 400,000 psi tensile strength would tend to support this argument. The authors would like to express their appreciation to the United Aircraft Research Laboratories for supporting this investigation and for permission to publish the results. A portion of this effort was supported by the Air Force Materials Laboratory under contract AF33(615)-2125.

Jan 1, 1968

R. Culver, Colorado School of Mines I appreciated Professor Starfield&apos;s presentation, because his approach to blasting research reflects my feelings that a lot of practical work can be done toward making short-term advances that can be used by the blasting industry. We should not forget this in our attempt to obtain solutions to such idealized problems as a mathematical theory of cratering. The blasting industry would like very much to have the efficiency of the basic blasting processes improved from the range of 20 percent up into the range of 50 percent. And many of these problems should be approached and attacked in the laboratories. Blasting research at the Colorado School of Mines for the past two or three years has been aimed at improving the pre-splitting process, because we feel it will become increasingly important to the construction industry. We have attempted to develop a unified theory of how pre-splitting works; and the more we investigate, the more variables we find. We may never obtain an entirely satisfactory theory of pre-splitting, but we have developed a tentative explanation. One of our first conclusions was that we are making very poor use of the explosive in current pre-splitting practice. But to appreciate this we must first consider how pre-splitting works. A series of parallel boreholes are loaded with low density charges which are detonated simultaneously. (Delayed detonation has been tried, but most people agree that simultaneous detonation is best, and this is what we found.) Stress waves traveling out from each borehole interact with the stress waves from the two adjacent boreholes influencing the direction of the fractures that occur and propagate from each borehole. It has been suggested in private communication with Mr. Wilbur Duvall of the U. S. Bureau of Mines, that the fracture between the adjacent boreholes is a result of the net particle velocities above and below the pre-split plane which tend to set up a net tension along the pre-split plane. Regardless of what the exact mechanism is that causes the fracture to propagate from one borehole to the next, we know that it, in general, relies upon an interaction of the stress waves. However, if there is a large compressive stress normal to the pre-split place, it can practically eliminate any possibility of obtaining the desired pre-split by preventing the desired fractures from getting started. Aside from obtaining a fracture along the pre-split plane, the other major aim of pre-splitting is to minimize the fracturing that occurs around the borehole. We do this by drilling a large hole and putting a small charge in the middle of it. This results in a badly decoupled charge which is very inefficient; most of the energy is used in compressing the air in the borehole. Out of discussions about how pre-splitting works, we decided that perhaps there was some other explosive geometry which would make more efficient use of the explosive, and result in optimizing the pre-splitting process. Starting in the laboratory with small plexiglas blocks, we found that a fully-coupled explosive charge of 5 grains/in. of PETN gave random fractures extending about I in. from the borehole. A 1/4 in. plexiglas plug fit into a 1/4 in. hole in a similar block with the same fully coupled charge gave random fractures extending out only about 1/2 in. due to the energy absorbed in fracturing the plug. If the plug was split longitudinally but otherwise using the same geometry, it was possible to drive a fracture about 2 in. in either direction from the borehole, with an even smaller amount of fracturing around the borehole.

Jan 1, 1967

By H. R. Hendricks

THE ore of the Iron King Mine, being very hard and having a very fine crystalline structure, presents many problems in milling that are not present in ordinary lead-zinc ores. This very fine crystallization causes much interlocking of minerals and is most prevalent between the gold and pyrite and the sphalerite and pyrite. The recovery of gold is extremely important in the economic value of the ore and therefore constitutes a large part of the metallurgical problem to be solved. All of the gold is free but it has not been observed in any of the mill products except under very high magnification. Some of the gold is tarnished, and this condition also makes recovery difficult. The gold values have been determined to be highest in association with chalchopyrite and arsenopyrite. The silver occurs mostly in association with galena and tennantite. A small amount of native silver has also been observed occasionally. The galena, being softer than the other minerals, frees much better in grinding. Some oxidation of galena is present in the ore, as the nonsulphide lead content amounts to approximately 10 pct of the total lead. Some oxidation of sphalerite is also present in the ore. Microscopic examination of the zinc concentrate shows many grains in the minus 325-mesh to be half pyrite, together with the fact that some of the zinc is marmatite, makes production of a high-grade zinc concentrate very difficult unless recovery is sacrificed. In the grinding, it has been determined that the flotation feed must be maintained at 85 pct minus 200-mesh to free the minerals sufficiently to make the best economic recoveries. Table I illustrates the effect of fine grinding. It shows that the bulk of the recovered minerals is in the minus 325-mesh size and is the part of the minerals that is more readily freed. The pyrite concentrate is not given in the table because it contains practically no minus 325-mesh. DEVELOPMENT OF PRESENT FLOWSHEET AND MILLING PRACTICE The first milling operation started in 1938, with a mill capacity of 140 tons daily, producing a bulk gold-silver-lead concentrate. After several stages of expansion and changes of the mill flowsheet, the mill is currently treating 380 tons of ore daily and three separate concentrates are produced. In order of their importance and value, these are: (1) lead concentrate, (2) zinc concentrate and (3) pyrite concentrate. The present average grade of mill heads is: gold 0.11 oz, silver 4.00 oz, lead 2.50 pct, zinc 7.60 pct, copper 0.22 pct, iron 22 pet and 30 pct insolubles. Specific gravity of the ore is 3.8. During the period when bulk flotation was practiced, the flowsheet was very simple. The ore was ground fine enough to liberate as much gold, silver and lead as possible. Necessary collectors and frothers were added in sufficient quantity

Jan 1, 1947

By H. Margolin, E. Ence

Two versions of the Ti-Mn binary diagram have been published recently.&apos; , -0th diagrams show two compounds in the region between 40 and 70 wt pct Mn, but disagree as to the reaction in which these compounds are involved. The investigation of the manganese-rich portion of the Ti-Mn binary diagram was undertaken at New York University as part of an investigation of ternary systems with titanium and manganese in order to determine which of the proposed diagrams is correct. A number of alloys between 31 and 70 pct Mn were prepared in a manner similar to that described by Cadoff and Nielsen; except that low currents (110 amp in argon atmosphere) and long melting times (up to 20 min) were used to prepare the alloys. Compositions were determined from weight-loss data, assuming all loss as due to manganese. Heat treatments were carried out with relatively large pieces, since there was a tendency for manganese to be lost during heat treatment. When X-ray diffraction data was to be obtained, the central parts of heat-treated specimens were used to make filings or powders which were not heat treated. Specimens were heat treated from the as-cast state. Heat-treatment times were as follows: 1150°C, 1 day; ll00°C, 2 days; 1000°C, 5 days; and 900°C, 15 days. It should be noted that equilibrium was not attained at 900°, 1000°, and in one case, at 1150°C. Metallographic specimens were electrolytically polished and strain etched by a technique described elsewhere.&apos; At least four, and possibly six, phases were found in the region investigated. On the basis of information available at this time, a completely self-consistent diagram cannot be constructed, and therefore data are presented only for those phases which have been identified by both X-ray and microstruc-ture. Of the compounds detected, the one highest in manganese is the Laves phase, TiMn,, which is hexagonal with a MgZn, type of structure.V he diffraction data for TiMn2 from a 70 pct Mn alloy annealed at 1150°C are shown in Table I. The c/a ratio and parameters of TiMn2 agree well with those of Wall-baum hnd Rostoker et al. The values obtained here are c/a = 1.641, a = 4.825A. Another compound is the y-phase which is estimated to contain about 60 pct Mn. The y-phase has a structure which is identical to that of TiMn, with c/a = 1.639, a = 4.906Å. The fact that y has a Laves-type lattice would suggest that TiMn, has a range of solubility which extends from the composition of TiMn2 (69.6 Mn) to that of y (60 pct Mn). However, this could not account for microstructures which, in the 60 to 70 pct Mn region, show several phases in both the as-cast state and after annealing at 1150°C. Fig. 1 shows a two-phase structure of a 60 pct Mn alloy annealed at 1150°C. The phases present are y (white) and e (dark). If y were TiMn, then, according to Rostoker et al.,&apos; the second phase of Fig. 1 should be P-Ti. The diffraction data for the 60 pct Mn alloy of Fig. 1 are shown in Table I. The starred d-values are from the e-phase and these lines do not correspond to those of &Ti. Comparison of as-cast and 1150°C microstructures of the 60 pct Mn alloy indicates that e precipitated from y. Since y has a

Jan 1, 1955

By Irwin Politziner F. M. Townsend, L. S. Reid

Recently published data indicate that the water vapor content of a gas, as determined by dew point measurement, is inaccurate when the gas has been dehydrated with diethylene glycol. Water vapor contents and dew point measurements of gases dehydrated with triethylene glycol have been obtained in this investigation in order to determine the magnitude of a similar error, if one exists. Experimental data show a very low concentration of triethylene glycol vapor in gases dehydrated at atmospheric ternperatures and pressures ranging from 500 to 2,500 psia and that the accuracy of dew point measurements is not impaired by the presence of triethylene glycol vapor. INTRODUCTION Nearly all natural gas transported by pipe line to northern and eastern markets must be dehydrated to a low residual moisture content in order to assure maximum transmission efficiency and continuous delivery under peak load conditions. Without dehydration, water vapor often condenses in pipe lines in quantities sufficient to restrict the flow3 and. under low atmospheric temperature conditions, gas hydrates may form and plug gathering. transmission and distribution facilities. Gas may be dehydrated to pipe line specifications by a number of methods. The most widely used methods are (1) adsorption of water vapor on a solid dessicant such as activated bauxite, alumina or silica gel,&apos; (2) by absorption of water vapor by either diethylene or triethylene glycol-water solutions of high glycol concentration,11,13 and (3) by simultaneous expansion-refrigeration of very high pressure gas in which gas hydrates are purposely formed and then quickly decomposed.&apos;"" Of these three fundamental methods, the adsorption and absorption processes provide the bulk of the dehydrated gas moving to market at the present time. The expansion-refrigeration process. a relatively new development, is gaining in favor because of its simplicity but is sharply limited in its application by available differentials between source and gathering system pressures. Where gas sale or purchase contracts contain a maximum water vapor content specification, the water vapor content is usually determined by measuring the dew point of the gas at system pressure. Knowing he dew point temperature and the system pressure, the water vapor content of the gas is determined from a graphical correlation of saturation, or dew point, temperature us the water vapor content of the gas which is customarily expressed as pounds of water vapor per million cubic feet of gas measured at 14.7 psia and 60°F. Dew points are usually measured with the U. S. Bureau of Mines Dew Point Tester. shown in Fig. 1, which is well suited for use at temperatures lower than 120°F and at pressurei; ranging from atmospheric to 3,000 psi. A number of correlations of dew point temperatures vs water vapor content are available,3,5,15 the most recent of which is that by McCarthy et al.4 Where natural gas is dehydrated by absorhing contact with concentrated diethylene glycol-water solutions. considerable difficulty is experienced in observing water dew points due to condensation of liquid hydrocarbon and glycol films on the mirrored surface of the dew point tester. Riesenfeld and Frazierl2 report that the dew point method for determining the water vapor content of a dietllylene glycol-treated natural gas is in error due to the glycol content of the condensate formed on the tester mirror, and that the water vapor content of the gas tested is actually lower than that indicated by the standard&apos; dew point-water vapor content correlation. Extensive experience in testing gases dehydrated by concentrated triethylene glycol-water solutions lias not revesled difficulties of the nature cited above for diethylene glycol. Water dew points are clear and sharp and condensation of

Jan 1, 1951

By L. S. Reid, Irwin Politziner F. M. Townsend

Recently published data indicate that the water vapor content of a gas, as determined by dew point measurement, is inaccurate when the gas has been dehydrated with diethylene glycol. Water vapor contents and dew point measurements of gases dehydrated with triethylene glycol have been obtained in this investigation in order to determine the magnitude of a similar error, if one exists. Experimental data show a very low concentration of triethylene glycol vapor in gases dehydrated at atmospheric ternperatures and pressures ranging from 500 to 2,500 psia and that the accuracy of dew point measurements is not impaired by the presence of triethylene glycol vapor. INTRODUCTION Nearly all natural gas transported by pipe line to northern and eastern markets must be dehydrated to a low residual moisture content in order to assure maximum transmission efficiency and continuous delivery under peak load conditions. Without dehydration, water vapor often condenses in pipe lines in quantities sufficient to restrict the flow3 and. under low atmospheric temperature conditions, gas hydrates may form and plug gathering. transmission and distribution facilities. Gas may be dehydrated to pipe line specifications by a number of methods. The most widely used methods are (1) adsorption of water vapor on a solid dessicant such as activated bauxite, alumina or silica gel,&apos; (2) by absorption of water vapor by either diethylene or triethylene glycol-water solutions of high glycol concentration,11,13 and (3) by simultaneous expansion-refrigeration of very high pressure gas in which gas hydrates are purposely formed and then quickly decomposed.&apos;"" Of these three fundamental methods, the adsorption and absorption processes provide the bulk of the dehydrated gas moving to market at the present time. The expansion-refrigeration process. a relatively new development, is gaining in favor because of its simplicity but is sharply limited in its application by available differentials between source and gathering system pressures. Where gas sale or purchase contracts contain a maximum water vapor content specification, the water vapor content is usually determined by measuring the dew point of the gas at system pressure. Knowing he dew point temperature and the system pressure, the water vapor content of the gas is determined from a graphical correlation of saturation, or dew point, temperature us the water vapor content of the gas which is customarily expressed as pounds of water vapor per million cubic feet of gas measured at 14.7 psia and 60°F. Dew points are usually measured with the U. S. Bureau of Mines Dew Point Tester. shown in Fig. 1, which is well suited for use at temperatures lower than 120°F and at pressurei; ranging from atmospheric to 3,000 psi. A number of correlations of dew point temperatures vs water vapor content are available,3,5,15 the most recent of which is that by McCarthy et al.4 Where natural gas is dehydrated by absorhing contact with concentrated diethylene glycol-water solutions. considerable difficulty is experienced in observing water dew points due to condensation of liquid hydrocarbon and glycol films on the mirrored surface of the dew point tester. Riesenfeld and Frazierl2 report that the dew point method for determining the water vapor content of a dietllylene glycol-treated natural gas is in error due to the glycol content of the condensate formed on the tester mirror, and that the water vapor content of the gas tested is actually lower than that indicated by the standard&apos; dew point-water vapor content correlation. Extensive experience in testing gases dehydrated by concentrated triethylene glycol-water solutions lias not revesled difficulties of the nature cited above for diethylene glycol. Water dew points are clear and sharp and condensation of

Jan 1, 1951

By Robert E. Green, Kenneth Reifsnider

A microscopic X-ray diffraction technique was employed for the simultaneous study of the behavior of several families of lattice planes, whose local orientatiotz changes are manufestations of internal distortions resulting from specimen deformation. Photographs taken using aluminum were single crystals 1/64 in. In diam are presented which illustrate the appearance of various types of deformation- or growth- induced structural variations. Slip and lattice bending were detected in tensile tests for strains as small as 0.1 pct. Evidence of deformation bands, lineage structure, and void formation wns also shown. AmONG the most important methods of studying internal stresses in metals is the utilization of various X-ray techniques. The general subject of X-ray metallography has been treated in a most excellent manner by Taylor,1 and the use of X-rays for the direct observation of imperfections in crystals has recently been reviewed in an article by Newkirk2 and in the book edited by Newkirk and Wernick.3 Since the inception of metallographic X-ray analysis, there have been numerous technological developments and refinements, each with its particular advantages and disadvantages and, acrording to these, its particular applications. X-ray diffraction techniques can be divided into two general categories, that of X-ray diffraction microscopy and that of X-ray diffraction macroscopy. In the former are included such methods as those of Berg-Barrett, Lang, and Schultz2,3 which are concerned with microscopic imperfections such as dislocations. The second category includes all work concerned with the study of the condition of a crystal lattice structure as indicated by the marroscopic detail in its diffraction patterns. An example of this is the study of the diffraction manifestations of inhomogeneous plastic deformation as manifested by formation of deformation bands and inhomogeneous lattice rotations. The method used in the present investigation was an X-ray diffraction macroscopy technique. The geometry and analytical aspects of the method were similar to those of Julien and Cullity.4,5 The source was collimated with a single slit in a manner simi- lar to the "parallel beam&apos;&apos; method of Barth and Hosemann6 except that a continuous spectrum of radiation was employed. The apparatus produced large-beam transmission Laue patterns of thin cylindrical aluminum-wire crystals, which were deformed either in tension or torsion. Although the conventional X-ray target and interposed slit were not capable of the high resolution obtainable with a fine-focus X-ray source as employed in a microfocus apparatus, resolution was a secondary consideration in our technique, and was sacrificed to obtain sufficient intensity along a sizable length of the specimen. By using a grid indexing technique similar to that of Barth,7 we were able to study several diffraction lines from various planes simultaneously. The results of these tests give additional information with regard to the inhomogeneous deformation of single crystals, and the indexing procedure used provides a correlation between portions of the test specimen and portions of a diffracted beam. EXPERIMENTAL TECHNIQUE The experimental arrangement used is shown schematically in Fig. 1. A source of continuous X radiation from a vertically mounted Machlett X-ray tube possessing a copper target and operated at 20 kv and 10 ma was passed down a horizontal lead tube 80 cm long which terminated in an adjustable vertical brass slit. The slit opening was adjusted to correspond with the diameter of the test specimen. In front of the brass slit it was possible to place a screen wire mesh, one horizontal strand of which was a lead wire which served as a fiduciary mark, the screen itself serving as an indexing system as will be described later. Behind the screen was the test specimen which consisted of an aluminum single crystal wire 1/64 in. in diameter and 3 in. long. These 3-in.-long crystals were cut from

Jan 1, 1965

By P. T. Bail, J. E. Bobek

In reservoirs containing soft shales interbedded with oil-producing sands, it is possible to have water movement from the shales into the sands during reservoir depletion. This paper presents the results of scaled flow-model tests performed to investigate the efficiency of oil displacement by this vertical influx of water into oil-producing sands. In these model tests, the effects of rate of influx and rock wettability were considered. Oil recoveries by shale-wafer influx and by water flooding were cornpared after 0.4 hydrocarbon volume of water entered the producing sand. This comparison was made for water-wet and oil-wet systems. In water-wet sand, shale-water influx produces slightly less oil than conventional water flooding; in oil-wet sand, shale-water influx produces about one-half as much oil as conventional water flooding. In another type of comparison, it was found that shale-water influx followed by water flooding recovers less oil than water flooding alone. This is true for both water-wet and oil-wet sands. A comparison of tests run at different rates of shale-water influx shows that oil recovery is insensitive to rate in water-wet sand; in oil-wet sand, oil recovery decreases with decreasing rate of influx. INTRODUCTION Localized subsidence of the earth&apos;s surface has accompanied the depletion of some oil reservoirs, particularly in California,1, 2 along the Texas Gulf Coast,3 4 and in the Bolivar Coastal fields of Venezuela. Subsidence occurs when fluid withdrawals reduce the pressure in the reservoir. The reasons for subsidence accompanying a reduction in reservoir pressure are not known with certainty.10° However, there is considerable evidence that compaction of soft shale beds adjacent to producing oil sands can be a major cause of this subsi-dence.3, 6, 10-12 When the shales compact, a limited amount of water moves from the shales into the producing sands. A schematic illustration of this oil-producing mechanism is shown in Fig. 1. As the pressure in the sand declines due to oil production, a predominantly vertical pressure gradient develops at the sand-shale boundary. This causes water to move from the shale into the sand as indicated by the solid arrows. This paper reports the results of scaled flow-model tests to investigate the efficiency of oil displacement by the vertical influx of shale water into producing sands. The model tests were not performed with the aim of duplicating the recovery behavior of any specific reservoir. The primary purpose of the tests was to obtain a better understanding of oil displacement by shale-water influx. A knowledge of the oil- and water-production characteristics of even a simplified reservoir system should be of value to engineers estimating the performance of reservoirs where shale-water influx is occurring in conjunction with other production mechanisms. The following limitations and assumptions apply to the model work. 1. The sand of the prototype reservoir is homogeneous and horizontal. 2. The shale-water influx is uniformly distributed along the top and bottom of the sand member being studied. 3. No effects of edge-water drive or dissolved-gas drive that might accompany shale-water influx are considered. PROTOTYPE RESERVOIRS Scaled-model tests were performed to study oil displacement from three prototype reservoir sections. The reservoir sections modeled consist of single sand layers out of a sequence of -sand and -shale layers, as illustrated in Fig. 1. Each prototype represents a homogeneous, high-permeability, unconsolidated sand layer. In the field, the prototype is oriented in such a manner that one end is at the radius of drainage of a producing well and the other end is pointed toward the producing well (Fig. 2). The sand and fluid properties and the dimensions of the three prototypes are given in Table 1. The capillary pressure relationships for the three prototypes are presented in Figs. 3, 4 and 5. The oil-water per-

By H. R. Ogden, A. G. Imgram, D. N. Williams

The effects of composition on the mechanical properties and aging characteristics of several alloys in the Ti-V-Cr system, with and without aluminum modifications, were evaluated. Increasing the chromium, vandium, or aluminum content increased the strength of quenched structures with chromium being the most effective strengthener. Appreciable aging response was obtained with low chromium alloys, but high chromium alloys age softened rather than. hardened. High vanadium contents had a similar effect. Aluminum additions shifted the aging behavior toward that observed in lower chromium alloys, enabling high chromium alloys to be age hardened. DURING the course of titanium alloy development many a and a-ß alloys have been evolved to commercial status. However, only one all-ß alloy has achieved this same stature. This is the Ti-13V-11Cr-3Al alloy. It is characterized by a very sluggish ß-phase decomposition reaction such that very slow cooling rates can retain the 0 phase at room temperature. In addition, very high strength levels can be obtained by long-time aging treatments. Combinations of cold or warm working followed by aging produce even further improvements in strength. This paper describes the results of a research program in which the effects of composition on the mechanical properties and aging characteristics of several alloys in the Ti-V-Cr system, with and without aluminum modifications, were evaluated. EXPERIMENTAL PROCEDURES Electrolytically refined, high-purity titanium was used as the alloy base for these studies. Iodide chromium, electrolytically refined vanadium granules, and high-purity aluminum sheet were used as alloying additions. The compositions of interest were melted as 250-g ingots in a direct current arc melting furnace under a flowing atmosphere of argon. The ingots were hot forged to 3/4-in.-diam bars, vacuum annealed for 6 hr at 1800°F to reduce residual hydrogen content, and then hot swaged to 1/4-in.-diam rods. Fabrication history, and interstitial analyses after fabrication are given in Table I. All specimens to be heat treated were sealed in Vycor capsules under a partial pressure of argon. Samples used to define the ß transus were quenched from temperatures ranging from 1350° to 1100°F after holding at temperature for 15 min. Samples for aging studies were quenched from above the ß transus temperature and then aged for up to 64 hr at 750°F and for 100 hr at 850°, 900°, and 950°F. The effects of straining prior to aging were also investigated. The results of these studies were used to select the heat treatments for the tensile specimen blanks. Heat treatments of the tensile specimens are described in Table 11. Alloys were aged after solution heat treatment or after solution heat treatment and cold swaging to 50 pct reduction in area. Standard 0.125-in.-diam tensile specimens were machined from the heat-treated blanks. All tensile tests were performed in a Baldwin-Southwark uni-

Jan 1, 1963

By R. L. Segall

AN unusual thermal etch figure in copper is described and an explanation in terms of twinning is suggested. A flat polycrystalline specimen of OFHC copper cut from a rolled sheet was electro-polished in orthophosphoric acid and annealed at 950°C in a vacuum of approximately 10-3 mm Hg for 2 hr. The specimen was found to be thermally etched, the markings on the surface being consistent with the assumption that they were the traces of the (111) planes which are developed preferentially because they have the lowest free energy. However, on one grain (the grain shown in Fig. 1) the traces formed an almost regular pentagon and at first sight it seemed unlikely that they could all be (111) traces. These traces were studied further because it was thought that they might be a type of growth spiral. A fringe pattern showed that this was not so, the grain being sensibly flat and the only features having steps were the striations and the faint curved line passing out from the center of the pentagons. To obtain some additional information, the specimen was deformed in tension. The effect of the stress was first to cause the appearance of lines running from the centers to the apexes of the pentagons and then to tilt the five segments so formed. At a much greater stress, appreciable slip appeared on the grain; these effects can be seen in Fig. 2. The micrograph was taken at a fairly late stage in the deformation and the tilting is quite marked. The magnification is the same as in Fig. 1, and although some slip can be seen it could be observed better by varying the illumination and using higher magnifications. In each segment of the grain, slip (which takes place on the (111) planes) was parallel to the side of the pentagon in that segment. The marked changes in direction of slip from segment to segment seemed to be incompatible with the presence of a regular array of subgrains. These results suggest that some of the five segments were twins. If this is so, since the twinning plane in copper is the (111) plane, the radial lines must be traces of the (111) planes on the surface. From the symmetry of the striations about the radial lines, these planes must be almost perpendicular to the surface. The angle between <III>directions in face-centered-cubic copper is 70&apos;32&apos;. If, in Fig. 3, OAB (triangle 1) is taken as matrix and OA, OB are (111) planes viewed edge on, then AB is in the correct direction to be the trace of either of the other two (111) planes on the surface. If triangle 2 is the twin (about the (111) plane perpendicular to the surface and containing OB) of triangle 1, then once again it can be shown that all lines are traces of (111) planes. Similarly, triangle 3 is the twin of triangle 2, 4 of 3, and 5 of both 4 and 1. (The sequence is, of course, quite arbitrary.) However, if this were the case there would be a discrepancy of 7&apos;20&apos; to be accounted for. It is suggested that the faint curved line passing outward from the center of the pentagon represents either a low angle boundary or a sixth small twin. The slight step shown by the fringes at this line might be an indication that the former is the case. This explanation does not account for the coincidence of obtaining a grain whose surface must be so close to (110) and obtaining the curious twinning described previously; it would be of interest to find a specific mechanism for this.

Jan 1, 1958