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By Ronald K. Linde

Metastable Ag-Cu solid solutions at two compositions beyond the maximum limits of solubility obtainable by quenching from the solid state were obtained by rapid quenching from the liquid state. The process of transformation of the metastable solid solutions into the equilibrium phases was studied by means of X-ray diffraction intensity measurements and electrical-resistance measurements; metallographic examination was also performed. Results are compared with those for an alloy quenched from the solid state at a composition which exists as a solid solution at elevated temperatures. Activation energies for the trans-formation were computed to be 33,600 * 2500 and 33,100 * 2000 cal per g mole for the 60.1 and 75.0 at. pct Ag;Cu compositions, respectively THE kinetics of precipitation in supersaturated solid solutions obtained by quenching from high temperature has been thoroughly studied in many alloys, and detailed investigations of the early stages of nucleation and subsequent growth of the equilibrium phases have been carried out. All of these studies have been made on alloys quenched from the solid state, however, and it is the purpose of this paper to present some of the results on the kinetics of transformation of metastable solid solutions in Ag-Cu binary alloys whose compositions lie outside of the solid-state limits of solubility. Limits of solubility in the solid state can be increased by rapid quenching from the liquid state. This was first demonstrated by Falkenhagen and Hofmann, who obtained appreciable increases in solubility limits of the elements of the first transition series in aluminum by rapid cooling of liquid alloys through contact with a copper mold maintained at liquid nitrogen temperature.' The same basic idea of cooling a liquid alloy by conduction onto a substrate rather than by convection of a gas or liquid (conventional quenching) has been recently revived and extended to very high rates of cooling by Duwez and his collaborators. The new technique was first applied to Ag-Cu alloys because the existence of a eutectic in this system is not predicted by the Hume-Rothery rules of alloy phase formation. Rapid quenching from the liquid state resulted in metastable solid solutions at all concentrations. The kinetics of decomposition of these metastable solid solutions containing 60.1 at. pct Ag;Cu (eutectic composition) and 75.0 at. pct Ag;Cu is the subject of the present paper. EXPERIMENTAL TECHNIQUES Alloys were made in 10- to 20-g heats using silver of purity 99.99 pet and copper of purity >99.999 pct. Components were weighed accurately to 0.1 mg and melted by induction heating in an alumina crucible under an atmosphere of hydrogen. Weight losses amounted to less than 0.02 ~ct in all cases. Rapid cooling from the liquid state was achieved in an apparatus of the type described by Pietrokowsky. 3 In this technique a freely falling drop of molten alloy is caught between a stationary anvil and a fast moving piston, both anvil and piston being lined with copper. The resulting foils were approximately circular (about 2 cm in diam) and from about 50 to 150 u in thickness, depending on the pressure driving the piston. Metallographic samples were prepared for polishing by edge-mounting foils in Quickmount. The mostef-fective etching procedure was found to be: 10 parts NH4OH (concentrated), 1 part H2O2 (30 pct), 5 parts H2O, swab for 5 to 10 sec. The transformation of the metastable alloys to equilibrium was followed by X-ray diffraction and electrical-resistivity measurements. The peak intensity and the integrated intensity of suitable Bragg reflections of the metastable and stable solid solutions were studied with a Norelco dif-fractometer, using nickel-filtered copper KO radiation. The peaks were step-scanned at intervals of 0.05 deg. Using either a Kelvin bridge or a null circuit with a Leeds and Northrup K-2 potentiometer, the changes in electrical resistance due to phase transformation were measured for specimens cut into strips about 20 mm long and 4 mm wide. All resistivity measurements were carried out at liquid-nitrogen temperature. The isothermal heat treatment was accomplished by sealing the samples in argon-filled aluminum containers with stainless-steel O-rings. Containers were then suspended in wax baths with temperatures in the

Jan 1, 1967

G. R. GOHN. l-1n Table I11 of The Sager, Brown, and Mears paper, which was presented on the screen, data were given showing the results of accelerated corrosion tests of certain magnesium alloys. Mention was made that these were carried to a certain time which was used as a measure of failure but no mention was made as to the period of time. I would like enlightenment on that. G. F. SAGER (Author).-In reply to Mr. Gohn's question regarding the times of exposure for the accelerated stress-corrosion tests referred to in Table I11 of our paper, which shows the correlation between accelerated and atmospheric stress-corrosion tests on magnesium alloys, I can say that we usually run the accelerated tests on such alloys for at least 500 hr. We feel that this is long enough to reveal any marked susceptibility to stress-corrosion cracking. In the case of the atmospheric tests on such alloys, we have not yet decided how long we should expose the specimens. Most of them are being exposed for indefinite periods and a good many of our specimens have now been exposed for several years. We may want to continue some of the tests for five or ten years. The period of six months mentioned in connection with the times of exposure for the atmospheric specimens was a rather arbitrarily selected minimum time for which specimens had to be exposed before we counted them with those that had not failed. A fairly large number of magnesium- alloy specimens have been exposed in the atmospheric stress-corrosion tests at var-

Jan 1, 1945

By H. A. Wahl, J. M. Campbell

This study extends our information on solid-liquid slurries to the flow of sand in horizontal fractures. Inasmuch as this is basically an unsteady-state process, a comprehensive photographic study was undertaken in a 10-ft windowed cell to determine if the basic flow regimes described for steady-state flow in pipes applied to the subject process. Since the number of potential variables far exceeds the capacity of a single study, emphasis has been placed on the effects of sand concentration, oil viscosity and oil flow rate. The extensive photographic evidence obtained has proven very valuable in gaining an insight into the basic flow mechanisms. Being able to follow visually the flow characteristics that accompany the quantitative data is valuable in the application of the results. Although the use of dimensionless parameters was carefully investigated. it was found that the data obtained could be more easily, and as accurately, correlated by judicious use of the dimensional variables investigated. However, a study into the feasibility of scaling slurry flow was made in the event this technique is justified in future investigations. The data presented show that the pressure behavior observed in solids transport in pipes basically applies to slurry flow in horizontal fractures. The roles of the parameters are altered but a basic equivalence exists. The most significant correlating parameter was the oil viscosity (µo) and the bulk velocity of the slurry (vn), expressed as ''µv" product. The most significant correlation expresses the rate of advance of the sand as a function of the variables investigated. There are many practical ramifications of this phase of the investigation that should aid in better treatment design. Evaluation of sand advance rates provides a means of estimating sand placement efficiencies during a treatment and the resulting sand distribution in the fracture. The results show that sand placement efficiencies are low under typical treatment conditions. A brief description of the effects of overflushing is also included. INTRODUCTION The flow of sand-oil slurries in fractures is an area in which little basic knowledge is available. This stems to some degree from the fact that it is impossible to duplicate fractures at the surface. They occur in various shapes and sizes with an infinite combination of irregularities. Unfortunately, we can never "see" these fractures except in cores and by indirect means of measurement. In spite of this inherent difficulty, it is desirable to develop some basic concepts that will provide a better understanding of the sand transport mechanism. An insight into the problem is provided by investigations of fluid flow in rectangular conduits. Several studies on the flow of liquids in non-circular conduits1,13 show that a Reynolds number-Fanning friction factor relationship can be written if the hydraulic diameter is substituted for the regular diameter in a circular pipe. This hydraulic, or equivalent, diameter is taken as four times the cross-sectional area occupied by the flowing fluid divided by the wetted perimeter. Eq. 1 expresses an extension of this same work when applied to infinite parallel planes b distance apart.' Eq. 1 is a theoretical equation expressing the friction factor as a function of the Reynolds number for laminar single-phase fluid flow. This expression has been verified experimentally. The equivalent expression for a smooth circular conduit differs only in that the value of the constant is 16 instead of 24. Numerous studies have related friction losses to Reynolds number in both circular and non-circular conduits. These results are widely used and are not reviewed here. Huitt' investigated the effect of surface roughness on fluid flow in simulated fractures. He concluded that fluid flow in fractures may be treated similarly to fluid flow in circular conduits. This work, together with that of Nikuradse,' shows that surface roughness has no appreciative effect upon the resistance to flow in the viscous flow region. In the region of turbulent flow, surface roughness is a prominent factor. Hydraulic conveyance literature is another important source of information. Durand3 has attempted to organize systematically the variables involved in hydraulic-solid transport in pipes. He has classified the modes of flow into three types according to the size of the particles in the mixture— homogeneous mixtures, intermediary mixtures and heterogeneous mixtures. With the usual concentrations and flow rates used in hydraulic transportation, particles with diameters of less than 20 or 30 microns form eszentially homogeneous mixtures with water. The data show, however, that even small materials will tend to settle out under laminar flow conditions. Mixtures containing solids over 50 microns in diameter do not achieve total homogeneity even under turbulent flow conditions. Particles from 50 microns to 0.2 mm in diameter may be transported in fully suspended flow at normal transport velocities although the concentration in the vertical plane is not uniform. Above 2 mm in diameter solid materials are transported along the bottom of the conduit at a velocity substantially less than that of the liquid itself. Between 0.2 and 2 mm in diameter, the particles tend to be in a transition zone between heterogeneous suspended flow and deposit flow at normal hydraulic transport velocities. The sand sizes used in fracturing usually fall in this size range. It is interesting to note that the grain size range designated by Durand for this transition zone corresponds closely to the transition zone between

By A. L. Barnes, A. M. Rowe

A heat transfer study was made of hot gas injection into oil shale through wells interconnected by vertical fractures. This analysis involved the simultaneous numerical solution of a nonlinear, second-order partial differential equation that describes two-dimensional conduction heat transfer in oil shale and a nonlinear first-order partial differential equation that describes convection heat transfer in the fractures. Three nonlinear, temperature-dependent coefficients were used in this work; they are thermal conductivity, thermal capacity and retorting endothermic heat losses of oil shale. Vertical fractures were considered to be of finite height. Although vertical conduction heat transfer was not considered, an estimate of the error resulting from this limitation was made. The effects of injected gas temperature, injection rate, system geometry, cyclic injection and time upon retorting efficiency were investigated. Results from this study show that the rate of retorting oil shale is a direct function of both injection temperature and rate, and the theoretical producing air-oil ratio:(AOR) is an inverse function of temperature. Retorting rates are constant until "breakthrough" of the 700 F isotherm at the producing well, assuming constant injection parameters. Retorting rates for bounded systems are higher than the analogous unbounded systems and likewise AOR's are less. The use of an alternating injection-soak routine with high injection rates is less efficient than continuous injection at lower rates. These results indicate that injection temperatures on the order of 2000F or greater may give theoretical AOR's in the economic range. INTRODUCTION Over half of the known oil shale reserves are located in the U.S., and most of them lie in the Piceance Creek basin of Western Colorado. The Colorado oil shale outcrops on the edges of the Piceance Creek Basin. At the outcrops the shale beds are relatively thin, from 25 to 50 ft thick. In the center of the basin the oil shale is as great as 2,000 ft thick and is covered with 1,000 ft of overburden. It has been estimated that there are over 1,000 billion bbl of oil in shales having an oil content over 15 gal/ton in this basin. Oil shale does not contain free oil but an organic matter called kerogen. Kerogen yields petroleum hydrocarbons by destructive distillation. It must be heated to approximately 700F, at which temperature it decomposes into shale oil, gases and coke. The U.S. Bureau of Mines and, more recently, oil companies have conducted considerable research on surface retorting methods to economically recover oil from this shale. Another approach to exploit the oil shale deposits, in particular that portion having 1,000 ft of overburden, is to retort the oil shale in place and produce the liquid and gaseous hydrocarbons through wells drilled into the shale. Some research has been done on this approach.l,2 There are several variations to the in situ retorting approach. These variations fall into one of two groups, depending upon the geometry of the system: (1) retorting in a highly fractured or broken up matrix; (2) retorting from single fractures between production and injection wells. The latter is the group studied. Several investigators,3-6 using various assumptions, have studied flow of heat through horizontal systems. The objective of this work was to make a heat transfer study of in situ retorting oil shale by hot gas injection through wells interconnected by single vertical fractures of finite height. The oil shale thermal conductivity, thermal capacity and retorting endothermic heat losses were considered to be functions of temperature. A knowledge of the

Jan 1, 1969

By W. C. Leslie

The textures of cold-rolled and of annealed iron are compared with those of an iron-0.8 pct copper alloy in which the amount of precipitation after cold rolling was controlled. Previously published pole figures -for cold-rolled and for annealed iron are confirmed. The effects of precipztatiotz after cold rolling are to retain the cold-rolled texture after annealing, to inhibit the formation of the usual allnealing texture, and to produce elongated recrys-tallized ferrite grains. It is suggested that the inhibition of new textures by precipitation after cold rolling is a general phenomenon. A great deal of attention has been paid to the development of texture during the secondary or tertiary recrystallization of ferritic alloys, but very little work seems to have been done on the control of texture during primary recrystallization. If such control were attained, it might be possible to simplify the processing of oriented materials or to change the characteristics of current cold-rolled and an-nealed products. From previous experience, it seemed likely that texture could be controlled by recrystallizing a supersaturated solid solution. Green, Liebmann, and Yoshidal found that the formation of preferred orientation in aluminum (40 deg rotation about <111> relative to the deformed matrix) was inhibited when iron was retained in supersaturated solid solution in the strained aluminum. The authors attributed this inhibition to iron atoms in solid solution. There is, however, an alternative explanation. Green et al, took a highly supersaturated solution of iron in strained aluminum and heated it to an unspecified temperature for recrystallization. It is probable that precipitation occurred prior to and during recrystallization, and it is proposed that the inhibiting agent is this precipitate, rather than the iron atoms in solid solution. It is important to note that precipitation before cold work is ineffective; the effective precipitate is that formed after cold working and either before or during recrystallization. The location and distribution of the precipitate are critical. Precipitation in such a manner has been found to have profound effects upon kinetics of recrystallization and the microstruc-ture of the recrystallized alloys.2-4 It would be surprising, indeed, if this were accomplished with no change in texture. Because of the relative simplicity of the system, and because of previous experience,4-7 it was decided to determine the effect of precipitation on texture in an alloy of iron and copper. Bush and Lindsay5 found an unspecified change in texture in cold-rolled and annealed low-carbon rimmed steel sheets when the copper content exceeded 0.1 pct. MATERIALS In earlier work, the rate of recrystallization of a low-carbon steel was greatly decreased by 0.80 pct copper, and, after the proper treatment, the recrystallized ferrite grains were greatly elongated.4 Accordingly, it was decided to investigate the effect of precipitation on texture at this level of copper content. The iron and the iron-copper alloy were made from high-quality electrolytic iron and OFHC copper, vacuum-melted in MgO crucibles, cast, hot-rolled to 0.2 in., then machined to 0.150 in. The compositions are given in Table I. The plates were heated to 925°C and brine quenched, twice. This produced a ferrite grain size of ASTM 0 in the iron and ASTM 1 in the Fe-Cu alloy. Disk specimens were cut from the heat-treated plates, repeatedly polished and etched, then used to determine (110) and (200) pole figures by reflection. Despite the complication of large grain size, these pole figures strongly indicated a random texture. PROCEDURES The copper content in solid solution in ferrite before cold rolling and recrystallization, and hence, the amount that could precipitate during the recrys-tallization anneal, was controlled at three levels by heat treatment. The specimens as quenched from 925° C were presumed to have all the copper, 0.80 pct, in solid solution. Other samples of the quenched alloy were aged 5 hr at 700°C to retain about 0.5 pct Cu in solid solution.6 A third set of quenched specimens was reheated to 700°C, then slowly cooled in steps, to reduce the amount of copper in solid solution to a very low level. All specimens were cold-rolled 90 pct, from 0.150 to 0.015 in. thick. The rolling was done in one direction only, i.e., the strip was not reversed between passes, with a jig on the table of the mill to keep the short specimens at 90 deg to the rolls. The rolls were 5 in. in diameter and speed was 35 ft. per min. Machine oil was used as a lubricant. In a supersaturated alloy, the maximum effect of the copper precipitate on microstructure and on recrystallization can be developed by a treatment at 500°C, after cold rolling and before recrystallization.&apos;

Jan 1, 1962

By U. F. Kocks

The flow stress in some latent slip systems of aluminum and silver crystals after various deformations in single slip was investigated by transverse compression and supplemented by experiments on overshoot of the compression axis and the stability of corner orientations. Work hardening was found to be remarkably isotropic, the ratio of the flow stress in the latent system to that in the primary system being between 1.0 and 1.3. The strain-rate dependence was not significantly larger in the latent system. This low anisotropy suggests that specific dislocation interactions are not the direct cause of work hardening. Either the obstacles are essentially impenetrable so that only their distance enters, or a fairly random distribution of dislocations of all systems is. in fact. formed during single slip. The latter seems to he excluded by the observations on the strain-mte dependence and on the amount of secondary strain. The amount of seconzdary strains occurring in single slip was determined by shape-change mensurements and by a new method connected with the latent-hardening experiments. It is definitely less than 1/300 times the strain in the primary svstem. WORK hardening is due to dislocation interactions; this is a hypothesis, and possibly the only one, on which all present work-harden ing theories agree. About a dozen specific interactions have been considered, and it is unlikely that any essential one has been missed. Different work-hardening theories differ to a large extent in the specific interactions which are deemed most important. The presence or absence of any particular interaction, and its degree, depend on the geometrical relationships between the two dislocations interacting. Let us enumerate some examples. Two dislocations may react, with a varying reaction energy, to form a third dislocation, and this reaction product may be sessile or glissile. Two dislocations may intersect and a jog may be formed on both, on one of them, or on neither; this jog may be sessile17Z or glissile and it may, if moved nonconservatively, lead to the production of vacancies or interstitials. Finally, a dislocation may bypass another one and thus interact only with its stress field. All these interactions depend on the specific relation between the Burgers vectors and line directions of the two dislocations. Any dislocation generated during plastic deformation of fcc crystals belongs to one of twelve slip systems. Taking any one dislocation, its relationship to each of the other eleven can fall, by symmetry, into one of only five classes. These relationships are enumerated in Fig. 1 and Table I. Each slip system is represented in the stereo-graphic projection by two triangles, namely those in one of which the specimen axis would have to lie if the specimen were to deform in single slip on this slip system in a given sense, in a tension test. Let us represent the primary slip system by the shaded triangles. The other slip systems are classified only with respect to their relationship to this primary system. The code letters (initials of established names* in German) are explained in Table I. Three specific interactions are also listed in cases where they may be strong: the product of a reaction, the formation of jogs in either system, and the elastic bypass stress. The last column relates to the types of experiments reported in this paper and summarizes their results. To decide experimentally between the relative importance of the various interactions one would like to produce a group of dislocations in one slip system and then measure the stress necessary to force another group of dislocations of a specific second system through them. Hopefully, one can produce the first set of dislocations by plastically deforming the specimen in single slip. Then one can try to achieve single slip in a specific, previously latent system and measure its flow stress. If it is different from the virgin flow stress, there has been "latent hardening". Some types of latent-hardening experiments will be discussed in the next section. The strain-rate and temperature dependence of the flow stress is an indication of the importance of dislocation intersections. By extending an investigation of this dependence to the latent systems, one can determine how much more important forest contributions are here. seeger3 has used the as-

Jan 1, 1964

By M. Nicholas, D. M. Poole

The diameters of sessile drops have been found to increase linearly with time in five reacting binary metal systems. The spreading rates of the drops are markedly dependent on temperature and on prior alloying of the solid with the lower melting point metal, hut are independent of the drop volume, wetting atruosphere , solid-surface roughness, and prior alloying of the drop with the substrate metal. A mechanism has been suggested that relates the linear-spreading rate to lateral diffusion of the liquid-metal atoms into the solid at the drop edge. An Arrhenius- type equation has been derived that describes the temperature dependence 0) the spreading rate, and although the agreement between the actual and the predicted pre-exponen-tial terms is poor that between the activation energies is excellent and the variation in the spreading rate of copper on Ni-Cu alloys produced by different extents of alloying can be predicted with considerable accuracy. CHEMICAL interactions frequently change the wetting behavior of solid-liquid systems causing, for example, "secondary spreading1 of sessile drops beyond the size defined by the surface and interfacial tensions of the unreacted components. The kinetics of the contact-angle decreases associated with this spreading are similar for many systems, but few studies have been made with the objective of determining whether the similarities are a reflection of a common mechanism. Some workers2,3 have assumed the secondary spreading is controlled by changes in the liquid surface and liquid-solid interfacial tensions and hence by the composition of the liquid, and contact-angle changes measured by the vertical-plate technique have been used to follow the course of liquid-solid chemical reactions.4 Other processes that have been invoked to explain these time-dependent changes in specific systems include the removal of adsorbed gas from the liquid-solid interface.5 penetration of containment layers on the solid Surface,6 interdiffusion,1,7 reori-entation of the solid surface into a wettable configuration: vapor-phase transport of the liquid onto the solid in advance of the drop,9 and, from vertical-plate studies. capillary flow between oxide layers and the solid surface.10 One of the reasons for the profuseness of these suggestions may be the complexity of the contact-angle change kinetics. However, in an analysis of secondary spreading gold and copper on UC,11 it was found that the diameter of the contact area between the sessile drop and the solid surface showed a simple linear increase with time although contact-angle changes were more complex. To check whether the linearity was merely fortuitous! additional exploratory work was conducted with four reacting metal-metal systems: Au on Ni. Cu on Ni, Cu on Fe, and Ag on Au. Linear spreading was observed in every case even though the kinetics of the contact-angle changes were complex. A further detailed study of the kinetics of linear spreading of five reacting metal-metal systems has been made with the object of determining the mechanism involved. The influence of variables such as temperature, drop volume. and the initial composition of the drop on the linear-spreading rate has been measured and compared with those predicted by a number of possible mechanisms. The systems employed in this study (Cu and Au on Ni and Pt, and Ag on Au) were selected because of the availability of potentially relevant chemical and physical property data. the simplicity of their phase diagrams at the wetting temperatures, and the ease of experimentation. EXPERIMENTAL TECHNIQUES The purities of the metals used in the study were: copper, 99.9 pct; gold. 99.96 pct; nickel, 99.2 pct; platinum 99.99 pct; and silver, 99.999 pct. The wetting tests were performed in a split tantalum tube vacuum resistance furnace of a conventional design. The furnace element was held vertically and was 1 $ in. in diam and 6 in, long. Viewing ports were provided in the water-cooled chamber to enable the specimens to be observed in both the horizontal and vertical planes. The temperature in the hot zone of the furnace could be held at 1500" i 5°C for an indefinite time. The surfaces of the solid-plaque metals were ground flat on Microcut paper and both the sessile drop and substrate metals were ultrasonically cleaned in methyl alcohol prior to their insertion in the furnace. After loading, the furnace was pumped down to a pressure of 2 x 10-5 mm of mercury and degassed for 30 min at 900° to 950°C. The temperature was then increased at more than 100°C per min to that used in the wetting test. The vacuum at the wetting temperature was better than 5 x 10-5 mm of mercury. Dewetting and retraction of the drop on cooling did not occur and the contact-area diameters, therefore, were measured after solidification with a vernier traveling microscope. The diameters quoted later are arithmetic means of ten measurements. The standard error of the mean never exceeded 3 pct and was often less than 1 pct.

Jan 1, 1967

By W. W. Anderson, S. Razi

Electroluminescetrce of single crystals of terbium-(loped ZnS prepared by vapor-transport technique shows the sharp line specirum characteristic of the 4f— 4ft,ansitiotzs of the trivalent Tb3 rotz. V-I tt~easuverr~ents give evidence of space-ellarge-lirrlited curvent but the thrveshold for trap-filled law behavior is not iu agreement with Lampert&apos;s theory for. Single injection. Variations of &apos;brightness with applied voltage, the observation of double peaks its brightness because joms, and the spatial distribution oi electroLur?zir~escerrce indicate that the accelet~atiotz-collision mechanism involving the bst lattice and/ov shallow traps is most likely to be responsible fov excitation of&apos; electrolnminescence. Efficiency rtreusuver)~etits show the quantwn efficiency to be about 10 pct and powev efficiency about 0.05 pct. Effect of anr~eallng the crystal in sulfur vapor is to enluztzce llle rare-earth emission. It rs pvoposed tlzat sulfitv anr~ealing crreates acceptorr-lvpe defects with which the donor-type vare-eavtll ion can associate more readily vesulting in enhanced rare-earth emission. A&apos;o such e~zlznr~cerr~etrt is obserued when the crystal is atztrealetl in zinc vapor. Photolianinescence of ZnS doped nith a variety of rare earths also shows tile slurvp l~rze rwve-eavtlz erriission which in sorrretirr~es accompanied by broad band, stvuctureless lattice emission. Photo-atrd electrolutr~itzesce?~ce of ZIIS:Tb slw~rj do!rlit~unt rare-earth emission in the ~ticirzity of 54(3OA corre-sporrdit~g to the transition D* — Fj. Hoz~!el)er, the detailed line structuve of the luo spectvtr is cliffevet~t, irzdicutit~g that different sites are active in the two processes. Decay of rave-eartlr fluorescence in ZnS doped with any of sei!evul vuve eurtlzs car1 be described by a single exporleritial e.scepl joy ZrlS:lIo. Tl~is exceptiotr can be explaitred it~ tevrr~s of tlre closely spaced er~evgy 1e1:els Jov the HO~&apos; iorr. Decay lime measurertzekzts jov ZnS:Tb, using pulsed elect,-ical ar~d pulsed opticcll excitutiorzs, (11-e itz goor1 agrcetrier~t. LUMINESCENCE of rare-earth-doped materials has been a subject of interest for the past 20 years. Within the past few years there has been a considerable increase in rare-earth research motivated in search of new and more efficient laser materials and also due to the use of certain-rare-earth compounds in the preparation of color television screens. The purpose of this study has been to seek an understanding of some of the basic processes involved in exciting the rare-earth luminescence which is associated with transitions within the 4f shell of the trivalent rare-earth ion. Single crystals of ZnS doped with a variety of rare-earth ions have been prepared by vapor-transport technique described elsewhere.&apos; Photoluminescence was excited by a high-pressure short-arc mercury lamp together with suitable glass and chemical filters. For electroluminescence, sinusoidal and pulse excitations were used. 1) ELECTRICAL CHARACTERISTICS 1.1) V-I Measurements. Electroluminescence experiments were performed on crystals of terbium-doped ZnS. The samples were cleaned and etched and indium or In-Ga alloy contacts were alloyed on by heating in H2 atmosphere to 600°C for times ranging up to 10 min. Static voltage-current measurements were made on several samples. Fig. 1 shows the results for a typical sample. For voltage V < 20 v, the V-I relationship is linear giving a resistivity of 2.5 x 109 ohm-cm for this particular sample at room temperature. In the range of 20 to 250 v, I varies as V "3 and at still higher voltages (when electroluminescence is visible to the scotopic eye) current varies as Vs up to 600 v, all at room temperature. At 77"K, for V > 200 v, / I vge5 up to 1000 v. The V-I characteristics at room temperature follow reasonably well the behavior predicted by Lampert&apos; for one carrier space-charge-limited current in an insulator with traps although, as shown later, the expression derived by Lampert2 for the threshold for trap-filled law behavior Vtfl yields an unrealistically low value for trap density if we use the experimental value of 300 v for VtfL. Assuming the case for shallow trapping, the transition from Ohm&apos;s law behavior to space-charge-limited behavior occurs at voltage Vtr given by where no = thermally generated free carrier density, L = length of the sample, e = static dielectric constant, 6 = ratio of free to trapped electron densities, e = electron charge. For the ZnS:Tb crystal, L = 0.5 mm, E = 8.3 €0, Vtr - 20 v, and no = 5 x 10&apos; per cu cm, calculated from the ohmic behavior assuming electron mobility of 100 sq cm per v-sec. This results in 9 = 0= As more and more electrons are injected the Fermi level moves up in the forbidden gap toward the conduction band. If we assume a single-energy level for traps (which is not strictly correct, as we will show later), the current voltage characteristic is profoundly affected when the Fermi level crosses the trap level. The traps are now filled and injected carriers can no longer be immobilized in traps. Hence, current rises sharply with voltage. The transition from space-charge-limited behavior to the trap-filled behavior occurs at voltage VTFL given by

Jan 1, 1968

By D. A. Elgillani, S. Atak, D. A. Rice, M. C. Fuerstenau, R. B. Bhappu

Quartz and feldspar cannot be floated with sulfonate at any pH; spodumene floats over a narrow acid pH range, while beryl responds moderately over a broad pH range. After wet-grinding in a steel mill, beryl, quartz, and spodumene float well with sulfonate below about pH 7, whereas the improvement in the response of feldspar is not so marked. A mechanism by which iron can be adsorbed on these minerals is presented. Also, the responses of leached, natural, and wet-ground beryl to amine, sulfonate, and oleate flotation are shown and related to the measured zero-points-of-charge of these materials. Earlier work with leached beryl showed that good flotation could be obtained with alkyl aryl sulfonate over a rather wide pH range using a Fagergren flotation cell.&apos; When a similar response was observed with leached quartz, it was decided that unintentional activation was being obtained from the metallic components of the Fagergren cell. To obviate this difficulty, a microflotation cell was designed, and an experimental technique was devised. These have been described elsewhere. Experiments conducted with the small cell showed that leached quartz could not be floated at any pH with any sulfonate addition,3 which is in agreement with the observations of Kraeber and Boppel.4 Similarly, it was also found that leached beryl responded to sulfonate flotation only over a narrow pH range rather than the broad range reported earlier.1 This early work,1 however, revealed the important effect that wet-grinding in a steel mill has on the flotation response of certain silicates. That is, it was found that quartz and especially beryl floated well over an unusually wide pH range after wet-grinding in a steel mill. Microcline, however, floated poorly below pH 4, even though wet-ground under the same conditions. The work of Eigeles6 on adsorption of oleic acid on leached quartz and iron-contaminated quartz at constant pH is in agreement with these flotation data. Other research has shown that ferric iron, added as a salt to the system, functions as an activator in the narrow pH range in which Fe +++ iron hydrolyzes to its hydroxy complexes.3,5 These phenomena indicate that iron functions differently in flotation systems depending on its method of introduction. The object of this paper is to determine the mechanism by which iron is adsorbed on certain minerals, the mechanism of collector adsorption after iron abstraction, and the role that Fe++ and Fe+++ assume in the selective separation of these minerals. EXPERIMENTAL MATERIALS AND METHODS Sodium alkyl aryl sulfonate, mol wt 450,7 pure potassium oleate, and pure dodecylamine were used as collectors. All other chemicals were reagent grade in quality, i.e., n-amyl alcohol as frother; HC1, H2SO4, and KOH for pH adjustment; and ferric chloride as activator. Conductivity water, made by passing distilled water through an ion exchange column, was used in the experimental work. All minerals used in the investigation were hand-picked specimens. Sample Preparation: Each of the minerals was crushed through 8 mesh, and the product was divided into two groups, one to be ground dry and the other wet. Dry grinding was accomplished with an alumina mortar and pestle. The product was dry-screened to 48 x 150 mesh, cleaned magnetically, deslimed in conductivity water, and dried. Preparation of the samples by wet-grinding involved grinding a 200-g charge of the mineral (-8 mesh) at 60% solids with natural water in a mild steel rod mill for four minutes. This charge was then wet-screened immediately with natural water to 48 x 150 mesh, dried, and cleaned magnetically. Some experiments were also conducted with leached beryl and quartz. These products were prepared by leaching the sized sample (48 x 150 mesh) with concentrated HC1 with a percolation technique until no iron could be detected in the leach liquor. Following this step, the sample was rinsed with conductivity

Jan 1, 1967

By R. W. Gould, B. G. LeFevre, A. G. Guy

The resistivity anomaly known as the K state was studied in Ni-Mo alloys containing 10.5 and 14.0 at. pct Mo. Both these alloys exhibit a large K effect which depends on the mechanical and thermal treatment. On the basis of X-ray diffuse scattering studies which were correlated with resistivity measurements, it appears that the K state in dilute Ni-Mo alloys can be associated with changes in the degree of short-range order within the a phase. An interesting phenomenon that has received much attention in recent years is the K state. The K state is marked by anomalous changes in some of the physical properties of certain alloys without the occurrence of observable microscopic structural changes. One of the early pieces of work in this area was by Thomas&apos; who studied alloys of Ni-Cr, Ni-Cu, Ni-Cu-Zn, Fe-A1, Fe-Si, and Ni-A1. Upon annealing specimens which had been previously cold-worked or quenched from an elevated temperature he found an anomalous increase in resistivity over a certain temperature range. He also found that specimens which had been appropriately annealed to develop the K state showed a decrease in resistivity upon subsequent cold working. These effects are opposite to those found in normal alloys. Although the resistivity anomaly has been rather arbitrarily taken as the "definition" of the K state, there are several other interesting effects which accompany the resistivity increase. In Ni-Cr alloys,2, 3 for example, it was found that the hardness increases with increasing resistivity. It was also found that specimens which have been treated to develop the K state can be cold-worked for as much as an 80 pct reduction of area without an increase in the hardness. In Fe-A1 and Fe-Si alloys4 the K state is accompanied by an increase in flow stress and by a lattice contraction. In Ni-A1 alloys,5 specimens which have been treated to develop the K state also show an increase in elastic modulus. In Ag-Pd alloys6 the increased resistivity observed on annealing a cold-worked specimen is accompanied by an increase in the thermoelectric power and an increase in the Hall coefficient. The explanations of the K state phenomena are varied and depend upon the particular alloy in question. Several theories have been advanced to explain the increased conductivity with cold work on the basis of changes in the electronic configuration of the alloy as a result of local lattice distortions.7"9 Most investigators, however, believe that some type of local order in the solid solution, either short-range order (SRO) or clustering, is responsible for this effect. Theories concerning the relationship between ordering and the K state have for the most part been speculative, since there is little direct X-ray evidence that can be correlated with the above property changes. Much of the previous work on the K state was done in the Ni-Cr system where the small difference in the X-ray atomic scattering factors of the components nickel and chromium makes it very difficult to use X-ray diffuse-scattering measurements to determine the role of local order. In the Ni-A1 system, however, Starke et al.10 succeeded in detecting a connection between local order and the K state. It was found that a small but measurable K effect correlated with increasing SRO in the nickel-rich a phase. The manner in which local order might increase the resistivity of K state alloys is not completely clear. Since most of the known K state alloys contain at least one transition element, significance has frequently been attached to the presence of an unfilled d shell. It has been suggested that during the formation of the K state the number of conduction electrons decreases as a result of the transfer of s electrons to the d shell where they are more tightly bound.1&apos;11&apos;12 Koster and Rocholl13 have proposed that SRO can cause an increase in resistivity for alloy systems in which the number and mobility of charge carriers are reduced when the percent solute is increased. According to this hypothesis, the local environment of a given solvent atom changes in the same manner with increasing percent solute as it does with an increasing degree of SRO; hence the change in physical properties should tend in the same direction. In this hypothesis, SRO is considered only in a statistical sense, and the increased resistivity of the K state is attributed to a change in the mean distribution of electrons and holes in the s and d states as a result of SRO. From the work of Chen and Nicholson on Ag-Pd alloys,6 it appears that the K state can occur in systems for which the d shell is completely filled. These investigators explained the increased resistivity by picturing the SRO as small domains of some form of long-range order (LRO). According to ~ibson,&apos;~ the number of effective electrons can be reduced by the creation of a new Brillouin zone boundary near the Fermi surface of an alloy as a result of the changing crystallographic symmetry that accompanies the formation of a superlattice. This idea may be expressed in terms of the superzone concept.15 In the present work the role of local order in the formation of the K state in Ni-Mo alloys was investigated. The principal tools used in this study were X-ray diffuse scattering and electrical resistivity measurements; however, these data were supplemented by electron microscopic and field-ion microscopic data. The purpose of the work was to determine whether or not the K state in Ni-Mo alloys can indeed be attributed to the formation of SRO as has been proposed by previous investigators.

Jan 1, 1969

By William A. Kapp

INTRODUCTION Coal is being mined from beneath residential areas, structures, bodies of water and other surface features in the coalfields to the north, south and west of Sydney. The particular problems faced by mine operators in these areas vary considerably due to differences in the overlying strata, the variation in the depths of cover and also depend on the number of seams being mined. Detailed subsidence work first commenced in the Southern Coalfield in 1965 and is now being carried out over areas of extraction at roost collieries. The analysis of the results of the early investigations and of the work which continues in other areas has shown that there is a consistent relationship between subsidence and mine geometry and has led to a reliable empirical method for the prediction of subsidence. In addition, particular aspects of each of the studies in the Southern Coalfield results in a clearer understanding of strata movements and of the resulting subsidence. The features of a subsidence trough apply generally to all areas but the magnitudes of specific features vary according to the stratigraphy of the particular coalfield. The aim of the subsidence work is to quantify the effects of subsidence for a range of mining geometries and mining conditions to enable the maximum safe recovery of coal from beneath surface features. The importance of local subsidence investigations is becoming more evident to mine operators and to authorities or organisations with surface interests. The subsidence work also provides important information on the stabilities of pillars of coal which remain unmined between panels of extracted coal. These pillars are not extracted either because of poor mining or geological conditions, or because pillar extraction is not part of the particular mining operation. Subsidence studies over these coal pillars clearly establish whether the pillars have remained stable or have failed to support the overlying strata. With subsidence studies continuing over several years, it is possible to assess the stabilities of these pillars on a long term basis. BACKGROUND TO THE STUDY OF SUBSIDENCE Geographical setting Most of the black coal production in Australia comes from the Sydney Basin. The coal seams extend for approximately 350 km along the coast of New South Wales and inland for distances up to 150 km. The City of Sydney is located near the centre of the coastal extent of the Basin where coal has been mined at a depth of 900 m. The Sydney Basin is part of the Main Coal Province of NSW and is divided into several coal- fields. The Southern Coalfield to the south of Sydney contained 15 operating mines and produced 12.7 million tonnes of raw coal during the 12 months to June 1981. The collieries discussed later are shown in Fig. 1. The prominent topographical feature of the area is the Illawarra Escarpment which rises to 400 m above sea level, or 300 m above the coastal strip along the South Pacific Ocean. The escarpment is mainly sand- stone and the weathering of the cliff line has resulted in a covering of talus material at its base. Several collieries are located near the seams which outcrop along the escarpment. The city of Wollongong is located in a scenically attractive area on the coastal plain. The suburbs of Wollongong extend north along the coastline, south to beyond Lake Illawarra and west to the lower slopes of the escarpment. The Illawarra Escarpment forms the eastern boundary of the Woronora Plateau. On a regional scale the surface dips gently to the west and thus forms a watershed for the rivers, most of which flow in a general north westerly direction, sometimes forming steep gorges in the sandstone. These rivers join the Nepean and Hawkesbury River system and flow into the Pacific Ocean north of Sydney. Seven dam have been constructed over the Southern Coalfield (Fig. 1) and with one large dam further to the west, their stored waters provide the needs of the Cities of Sydney and Wollongong and the surrounding districts. A large part of the area affected by mining is the undeveloped bushland of the associated catchment areas. In general no special precautions have been required with respect to subsidence with the exception of the dam structures and stored waters. With the increase in coal mining activities and the expanding residential development south of the City of Campbelltown in the outer Sydney Metropolitan area, subsidence is becoming an increasingly important area of research. Structures which have been affected or considered are townships and extensive residential areas, buildings of historical importance, major tollways, and a high pressure natural gas pipeline. The subsidence effects of mining beneath natural features within national parks is coming under study as mining approaches these areas. Geological setting The coal seams of the Southern Coalfield lie within the Illawarra Coal Measures. They contain high rank coking coal used in the local steel industry and for export. The Bulli Seam is mined extensively through- out the Southern Coalfield with the lower Wongawilli Seam being second in importance with regard to coal production. The top of the Bulli Seam is taken to be the marker horizon between the Permian Coal Measures

Jan 1, 1982

By E. Buehler, H. J. Levinstein

The temperature ranges in which the three inter-metallic phases in the Nb-Sn system form have been determined and the composition and structure of two of the three phases has been established. The kinetics of the formation of Nb3Sn in cored wire samples has been studied in the temperature range of 800° to 1050°C. From 800°to 950°C the rate of formation increases by four orders of magnitude. The rate-controlling step for the formation process in this temperature range appears to be the diffilsion of tin through NbSn. At higher temperatu~es a change occurs in the mechanism of the formation process such that up to a temperature of 1050°C the rate of formation of Nb3Sn does not increase above the rate observed at 950°C. For temperatures helow 950°C the current-carrying capacity of the wire increases with increased percent reaction reaching a maximum value when the formation process is 90 to 95 pct complete. The maximum current-carrying capacity obtainable in this temperature range is independent of the temperature. Above 950°C tlze current-carrying capacity obtainable in the wire decreases with increasing temperature of formation. A model is proposed which accounts for the ohserved behavior. RECENTLY, Buehler et a1.l reported the results of an investigation of the process variables which influence the superconducting properties of Nb3Sn-cored wire. These results indicated that at least four variables affect the properties of the manufactured wire. These include composition, particle size of the starting powder mix, temperature of heat treatment, and time of heat treatment. In order to understand completely the role of these variables, it is necessary to have an accurate knowledge of the phase equilibria in the Nb-Sn system. At the present time, phase-equilibrium diagrams for the Nb-Sn system have been published by a number of investigators.2-5 The diagrams differ as to the number of phases present, the composition of the phases, and the temperature range of stability of the phases. The present investigation was undertaken in order to resolve these differences. Since the investigation of Buehler et al. demon- strated that the length of time at the temperature of heat treatment affected the superconducting properties of Nb3Sn, it is apparent that it is necessary to understand the kinetics of the formation process as well as the equilibrium conditions before a complete understanding of the system is possible. As a result, the kinetics of formation of the various phases in the system were also studied in this investigation. EXPEFUMENTAL PROCEDURE Diffusion couples and sintered powdered compacts were employed in the phase-diagram investigation. The diffusion couples were made by filling 1/8-in.-ID monel-sheathed niobium tubes with tin. The monel sheath was employed to facilitate drawing.&apos; The tubes were then drawn to a tin-core diameter of 32 mils. Samples approximately 3 in. long were then cut from the drawn composite. The tin was drilled out of the ends to a depth of 1/4 in. and niobium-wire plugs were inserted into the ends and peened over. The monel was removed by etching in concentrated nitric acid, after which the samples were sealed in evacuated quartz bulbs and heat-treated in a resistance-wound tube furnace. The samples were quenched into ice water upon removal from the furnace. The diffusion couple samples were examined metallographically employing a chemical etching solution consisting of 10 ml of saturated chromic acid per g of NaF. In addition, two anodizing solutions were used for phase-identification purposes. The first was the picklesimer7 solution; the second consisted of equal parts by volume of 30 pct H2O2 and concentrated NH4OH to which 1 g of NaF was added per 25 ml of solution. The anodizing conditions for the second solution were 2 v and 100 ma with a tin cathode. The powdered compacts were made by pressing previously mixed powders of 99.9 pct pure Sn and 99.6 pct pure Nb supplied by the United Mineral Co. into cylinders 3/8 in. in diameter by 1/2 in. long. The cylinders were then sealed in quartz tubes and heat-treated in the same manner as the diffusion couples. The samples were examined metallographically and by X-ray diffraction techniques. Since it was desirable to be able to correlate the kinetic data with current-carrying capacity, the type of specimen chosen for this part of the investigation had to be a compromise between the optimum system for studying kinetics and one which was suitable for making current-carrying capacity

Jan 1, 1964

By Charles R. Stewart, William W. Owens

Reservoir performance predictions based on laboratory core test data assume that fluid flow is laminar for the laboratory test. A study has been made to determine the validity of this assumption for laboratory tests on various types of porosity found in producing limestone formation. Data are presented which show that turbulence and slippage can occur during laboratory tests on hetero-geneous-type porosity limestones, thus causing serious errors in measured single-phase permeabilities and two-phase relative permeability characteristics. In single-phase flow tests it is possible to eliminate turbulence and correct for slippage or to eliminate both factors by controlling test conditions. It is not always possible to control test conditions and thereby eliminate turbulence and slippage in two-phase .flow tests. A correction method is presented which can be used to calculate the true two-phase laminar flow relative permeability characteristic even though furbulence and slippage exist. .INTRODUCTION It is customary to make use of Darcy&apos;s law and modifications of this law, together with laboratory data on formation core samples to predict the performance of producing reservoirs. Such predictions are based on an assumption that fluid flow is in the laminar or streamline region for the laboratory test. It was the purpose of this inves- tigation to determine the extent to which turbulent flow may occur in laboratory fluid flow tests on hetero-geneous porosity limestones. Considering that turbulent flow conditions might exist in some laboratory fluid flow tests, additional emphasis was placed on the development of a method to correct for turbulence when laminar flow conditions could not be attained. FLUID FLOW CONCEPTS FOR POROUS MEDIA The Influence of Pore Geometry on Fluid Flow One of the more important factors influencing fluid flow in porous media is the geometry of the pore space which includes such characteristics of the pores as size, shape, distribution, roughness, uniformity, etc. In general, oil- and gas-producing formations can be divided into two broad types on the basis of pore geometry. One has been called sandstone-type porosity media, which is characterized by a small range in pore size, uniformity in shape of the pores, smooth pore surfaces and a regular and uniform distribution of pores. The other type has been called heterogeneous porosity media and is usually limited to the dolomites and limestones. This type is characterized by a wide variation in the size, shape, and distribution of the pores and rough, irregular pore surfaces. It is therefore apparent that conditions are much more favorable for turbulent flow* in heterogeneous-type porosity media than in sandstone-type porosity media. Interrelationship Between Turbulence and Gas Slippage In studying the problem of turbulent flow in laboratory tests on porous media, it is necessary to be aware of the interrelationship between slippage and turbulence for gas flow. As a result of slippage or the Klinken-berg effecta, apparent perrneabilities to gas are greater than the true value because there is no stationary layer of gas in contact with the walls of the flow channels. Gas slippage decreases as the mean free path of the gas molecules decreases. Since the mean free path of any gas decreases with increasing density, increases in static pressure result in lower apparent gas permeabilities. However, a reduction in gas permeability can also be due to turbulence. Therefore, in studying only turbulent flow in porous media, it is necessary to hold gas density, and slippage, constant or to reduce slippage to a negligible value by operating at high static pressures. Presentation of Laminar and Turbulent Flow Data A graphical relationship between permeability and a pseudo-Reynolds number, N,, will be used to show the two types of fluid flow, i.e., laminar and turbulent. The usual graphical method for such a description has been the use of friction factor-Reynolds number charts4. On such a logarithmic diagram, the laminar region appears as a straight line having a slope of 45 degrees. As the friction factor decreases and the Reynolds number increases, the turbulent region is reached and appears as a deviation from the 45-degree slope line. However, in petroleum engineering literature resistance of por-

By H. R. Ogden, E. S. Bartlett, A. G. Imgram

Unmodified disilicide coatirigs were applied to sheet-tensile specimens ofCb-Dg3 and Mo-TZM veJractovy- metal alloys. Coating thickness, degree of coating-substrate interdiffusion, and specimen geonzetry (notched and plain were included in the variables studied. Tensile tests were made to determine the ductile-lo-brittle transition temperature. The disilicide coating modestly increased the transition temperatlre of TZM, but had no effect on 043. Neither material condition (recrystallized or stress-velieved) nor specimen geometry (notched or unnotched) significantly altered the effects of coatings on the transilion temperatures of. the alloys. Cracks in the brittle coatings did not propagate into the substrate, and fracture modes appeared to be the same for both un-coated and coated specimens. MOST potential structural applications for refractory metals and alloys involve exposures to oxidizing environments at elevated temperatures. The general lack of oxidation resistance of these metals will require protective coatings to allow fulfillment of their potential. Currently preferred coatings for the oxidation protection of refractory metals are brittle intermetallic aluminides or silicides. These are typically formed on the surface of the refractory-metal substrate by a diffusion reaction between the substrate and a gaseous or liquid medium that is rich in aluminum or silicon. Because of the brittleness of these coatings, they will sustain no plastic deformation at low temperatures. They are frequently cracked by cooling from the coating temperature because of the thermal-expansion mismatch with the substrate alloy. Even if they survive cooling intact, they crack rather than sustain deformation under load at low temperatures. Thus, when a coated refractory metal is strained beyond the elastic limit of the coating at low temperatures, the mechanical environment of the substrate would include both static and dynamic cracks. These might be expected to influence the flow and fracture behavior of the substrate. This could be manifested in an altered fracture mode and/or an increase in the normal ductile-to-brittle transition temperature of the refractory-metal substrate. This paper presents the results of a research program that was conducted to determine the influence of the presence of a brittle surface coating on the low-strain-rate tensile behavior of typical refractory metals at low temperatures. EXPERIMENTAL PROCEDURES Material Preparation. Thirty-mil-thick sheets of molybdenum TZM alloy (Mo-0.5Ti-O.1Zr) and colum-bium D43 alloy (Cb-IOW-1Zr-O.1C) were obtained commercially. These alloys were selected as substrate materials representing two classes of materials important in current refractory-metal technology. The TZM was in the stress-relieved condition, and exhibited a heavily fibered grain structure. The D43 had been processed by the duPont "optimum" fabrication schedule,&apos; and exhibited slightly elongated grains typical of this process. Tensile specimens of two geometries were prepared from these materials: 1) plain specimens with 0.2-in.-wide 1.0-in.-long gage sections; 2) specimens similar to above, but with a 0.06-in.-diam hole drilled in the center of the gage section, providing a stress concentration factor, Kt, of 2.5. The "notch" geometry was selected to represent a typical condition of a rivet hole or other geometric discontinuities as might be encountered in various applications. Machined specimens were degreased, with a final rinse in acetone, prior to the application of coatings. Specimens of each substrate and configuration were pack-siliconizedin a particulate mixture of 80 pct A1203, 17 pct Si, and 3 pct NaF. Specimens were embedded in this mix (contained in graphite retorts) and coated in an electrically heated argon-atmosphere furnace under time-temperature conditions to effect nominal 1- and 3-mil-thick silicide coatings: Coating Thickness, mils Thermal Treatment 0.6 to 1.4 24 hr at 982°C 2.4 to 3.2 48 hr at 1093°C Coating kinetics were similar for both the TZM and D43 substrates. These treatments had little or no visible effect on the substrate microstructure as determined by optical metallography. The coatings on TZM were essentially single-phase unmodified disilicides, while those on D43 showed substantial evidence of modification by proportionate reaction with the respective substrate elements or phases, as shown in Fig. 1. It was recognized that these coatings might not be particularly desirable regarding protective capability. However, it was desired to circumvent possible inter -ferring chemical interaction with the substrate by pack additives such as chromium, titanium, boron, aluminum, and other elements that typify the better protective coatings for these materials.&apos; Thus, the results presented apply specifically to the simple silicide coatings investigated. They may not be rep-

Jan 1, 1967

By C. S. Matthews, M. Prats, R. I. Jewett, J. D. Baker

By mathematical analysis it was found that injectivity history of a uniform five-spot pattern can be calculated by rather simple formulas. These calculated injectivities were found to agree rather well with injec-tivities measured in a potentiometric analog. With this as a basis, a simple method was finally developed which allows prediction not only of rate of injection but also of rate and kind of production at the production well, for a uniform five-spot. Using this method formulas for the eflective injectivity and production behavior of a waterflooded reservoir having a wide range in permeability can be calculated by considering that the reservoir consists of several layers, each having a uniform but different permeability. Rather good agreement is shown by a comparison of the observed production history of a field in the Illinois basin and that calculated by the methods just described. INTRODUCTION The importance of being able to predict the injection rates for a water flood is well known, for upon injection rate depends the life of the flood, the size of pumping and treating facilities, and the rate of oil recovery. One method of determining rates of injection is through a pilot flood. However, it appears that even if a pilot flood is resorted to, a theoretical method for calculating injection rate will be valuable in extending field results to times after inter- ference and to locations of other five-spots. It is also important to be able to predict the production history of a flood. Such prediction must generally be done by theoretical means, since in general a small pilot flood will not furnish much quantitative information in this regard because of the distortion after oil-bank interference. Methods for predicting the behavior of five-spot water floods have been proposed by Yuster and Cal-houn&apos; and by Hurst.? However, these methods do not consider the effect of the mobility of the different fluids in the reservoir. Other investigators3,4,5,6 have determined the effect of the water-to-oil mobility ratio on the production history by means of different experimental techniques. Most of the published work applies to homogeneous sand bodies, does not provide information for determining the injection requirements of a flood, and seldom considers the rate of build-up of the oil bank as it fills up the partially depleted reservoir.* The present work was undertaken because of the lack of predictive method which takes into account mobility ratio and the rate of buildup of oil bank resulting from the void space in a partially depleted reservoir. As water is injected into the reservoir, which contains oil, water, and gas in macroscopically homogeneous saturation, it forms several banks ahead of the injection well. In each bank or region there is assumed to be only one mobile phase—water in the water bank, oil in the oil bank and gas in the gas region. The saturation in each region and a plan view of the banks are shown in Figs. 1 and 4, respectively. FACTORS AFFECTING INJECTION AND PRODUCTION RATES Results in this report are determined as functions of the three parameters, F, M, and M, , and of a fourth parameter, r,/L** which relates the size of the well to the flood spacing. The parameter F is the displacement factor defined by Hurst in Ref. 2. It determines the rate of build-up of oil bank as it fills up the partially depleted reservoir. When gravity effects are neglected, the four parameters just given are sufficient to describe the waterflood behavior for horizontal and homogeneous reservoirs having incompressible liquids. Definition of InjectIvity The dinlensionless injectivity (or injection rate) used in this report is defined by

By F. D. Hoyt, H. L. Hartman

The development of new processes and methods by The Pennsylvania State University to improve slate quarrying technology has centered in recent years on cutting and sawing stone in the quarry to eliminate a second cutting process in the mill. Two machines exhibit promise for this work: 1) a circular saw mounting diamonds or hard inserts to produce smaller sizes of stone and 2) a chain saw with insert cutting teeth to produce stone in the larger dimensions. Prototype machines have been constructed and tested in several Pennsylvania slate quarries, and one commercial installation has been operated for several months with a circular diamond saw. Other kinds of dimension stones may be cut by these saws. Research at Penn State has begun to study the fundamental cutting action of rotary tools or saws in slate and other dimension stones. A laboratory drill press is being instrumented to permit thrust-torque-rotational speed us penetration rate studies of single tooth cutting surfaces on stone. Machinability studies of slate conducted with tungsten-carbide inserts have been performed. The dimension stone industry generally accepts the rather basic premise that the larger the block removed from the quarry, the more practical and economical the operation. Thus, the concept of cutting to size any dimension stone while it remains in place in the parent bed would receive little consideration from the majority of members of the industry. However, the slate industry, which is usually considered a separate member of the dimension stone family, is pioneering in the development of an in-place sawing method. Before any final decision can be reached concerning a proposed new system, it is essential to take a long, hard look at the present method of operation in order to determine if the new system is indeed an improvement or even desirable. In the following section is a brief description of present quarry practice in the slate quarries of eastern Pennsylvania. PRESENT METHOD OF QUARRYING SLATE In the numerous slate quarries of Lehigh and Northampton Counties of Pennsylvania, the grain and cleavage of the slate are most often at right angles to each other; if a third surface is broken at right angles to these two natural planes of weakness, blocks of more or less rectangular shape can be separated.&apos; In conventional quarrying a large calyx core drill prepares holes of 36-in. diam in which wire-saw standards are positioned. By wire sawing between strategically located core-drill holes, large sinks or benches of virgin slate are opened up. The sides freed by wire sawing will vary from quarry to quarry but generally are rectangular in shape with dimensions averaging 20 ft in length and about 15 ft in depth. Some quarries are fortunate in having a joint or natural parting to work to, which of course diminishes the amount of core drilling and wire sawing required. Once the various benches have been developed either through wire sawing alone or through a combination of wire sawing and natural jointing planes, the block removal proceeds in the following manner. A plug hole is drilled in the block with a compressed-air hammer and a feathering chisel is inserted in the hole to cause a fracture of the rock either with or against the grain as indicated by the positioning of the so-called feathers. This operation is referred to as sculping. After a block has been freed with and against the grain by means of wedging from the cross fracture with long bars or levers, the block is further freed along the cleavage plane by shimming it up with small wooden pieces in an operation known as styling. A large steel loading chain is wrapped around a block thus freed and the chain is attached to the wheel of an overhead cable. The block is then hoisted vertically to the cableway and moved along this cableway laterally to the lip or edge of the quarry. From here it is unloaded onto a rail car or truck for transportation to the processing mill. Except for occasional blasting to free stubborn blocks,

Jan 1, 1961

By C. D. Stahl, S. M. Farouq Ali, W. E. Culham

One- and two-dimensional mathematical models have been developed that simulate transient, two-phase flow of hydrocarbon mixtures in porous media in a manner that accounts for interphase mass transfer. Numerical simulations of one-dimensional depletion-drive experiments using a two-component hydrucarbon fluid were used to establish the validity of the mathematical models. In addition, the experimental and numerical data were used to demonstrate that production rate had a relatively insignificant effect on the recovery of individual hydrocarbon components from the experimental system, and that attainment of equilibrium between phases is possible for a wide range of liquid and vapor velocities in reservoirs containing light hydrocarbon fluids. Results of some two-dimensional numerical simulations are also presented. INTRODUCTION This study was undertaken to develop a mathematical model that would simulate transient, two-phase flow of hydrocarbon mixtures in porous media under conditions that result in interphase mass transfer and to test the validity of the assumptions used to set up the model. In addition, the study was designed to determine if production rate influences the recovery of individual hydrocarbon components from reservoirs producing by depletion drive. Two-phase flow in porous media, with interchange of components between the two phases, is important in many petroleum recovery processes. Studiesl-5 conducted within the last 3 years have outlined methods of solving multiphase flow problems incorporating mass transfer. Some of these studies have also indicated the importance of accounting for mass transfer under various producing conditions. An earlier work6 first demonstrated the importance of combining relative permeability data with equilibrium ratios in compositional balance methods. The mathematical model presented in this paper is formulated so that a phase behavior package, as described in previous papers,5,17 is not required as an integral part of the routine employed to solve for the primary dependent variables. The finite difference formulation is designed so that all the primary variables can be solved for simultaneously. This is accomplished by utilizing one basic set of equations. These innovations, which are in contrast to other models2,3,5 but are similar in some respects to the approach used by Taylor,l render the total problem computationally simpler than any of the previously referenced formulations. The mathematical model was developed by combining Darcy&apos;s law with a continuity equation for each hydrocarbon component. The principal assumptions invoked in the formulation were (1) that capillary forces and diffusional effects are negligible, and (2) that thermodynamic equilibrium exists in the reservoir at all times. No assumption as to the type of vaporization process was made in formulating this model. Experimental data were required to complete this study. These were generated by conducting several depletion drive experiments. The experimental apparatus consisted of a sandstone core enclosed in a pressurized casing. The apparatus was designed in such a manner that the core could be charged with a liquid hydrocarbon mixture and depleted at different production rates. The experimental tests were designed to determine the effect of production rate on component recovery. In addition, direct comparison of experimental and mathematically predicted

Jan 1, 1970

By A. S. Odeh

This paper analyzes the effect of limited entry to flow at the wellbore on the steady-state productivity of a well. Wells that have been opened to flow along a fraction of their productive interval are termed wells with limited entry. Previous work treated the cases of a partially penetrating well, a well producing from the central portion of the productive interval and a well in which several intervals equally spaced were open to flow. In this paper the open interval can be located anywhere within the productive interval. Thus, in a sense, it generalizes previous work. The finite cosine transform was used to arrive at a solution for steady-state flow of a slightly compressible fluid. The solution was programmed for a CDC 1604 computer. Numerical vaIues for rd = 660 ft, r, = 1/4 ft, and range of sand thickness of 20 to 200 ft are presented in graphical form. The effect of rd and r, values on the result is shown in a table. The correct calculation of skin and damage ratio in the presence of limited entry to flow is explained and illustrated by examples. Moreover, the paper shows how to calculate the net decrease in productivity due to the combined effect of limited entry and perforations. INTRODUCTION In some wells only a fraction of the productive interval is open to flow. Location of this fraction is usually dictated by formation characteristics and reservoir behavior. For instance, if a gas cap exists, the open interval is located away from the gas-oil contact to prevent any possible gas coning. Wells that intentionally have been opened to flow along a fraction of their productive formation are tened wells with limited entry. Obviously, unintentional completions of this type also exist. Limited entry to flow decreases well productivity. Magnitude of the loss depends on the fraction of the formation open to flow, on the thickness of the sand, on the location of the open interval and on the ratio of rd /r, where r , is well radius and rd is the drainage radius of the well. The use of pressure buildup data on producing wells to calculate the condition of the formation around the wellbore is an accepted practice. van Everdingenl and Hurst2 introduced the concept of she skin factor s considered to be due to a thin layer of different permeability immediately around the wellbore. These authors dealt with the case of a well of complete radial geometry, i.e., a well with open-hole completion that completely penetrates the formation. The presence of a low-permeability skin results in a loss of productivity, as does limited entry. Therefore, if pressure buildup data obtained on a well with limited entry are used to establish the presence or absence of skin (i.e., formation damage), and a correction is not made for this loss of productivity, the calculations would result in an erroneous skin value. They might indicate the presence of formation damage when in reality there is none, or they might indicate a value larger than the true value. This could lead to an incorrect basis for planning remedial measures. Muskat3 studied the problem of partially penetrating wells for the case of incompressible flow. He presented equations and figures which allow estimation of loss in productivity. Brons and Marting,4 using equations based on Nisle&apos;s work,5 studied the loss of productivity for three cases. The first was for a partially penetrating well; the second was for a well producing from only the central portion of a productive interval; and the third was for a well in which several intervals equally spaced were open to flow. Their work was for steady-state depletion-type reservoirs wherein the well radius of drainage is established and the fluid is considered to be slightly compressible. Considered in this paper is the problem of wells with limited entry in which the open intervals are located anywhere within the productive sand. The finite cosine transform is used to arrive at a

Jan 1, 1969

By H. W. Reinhardt, J. W. Dally

A dynamic photoelastic analysis of stress waves interacting with a free surface is described. The free surface is that of a bench with a fixed bottom so common in quarry applications. The stress waves are generated by line charges of lead azide (Pb N,). Four models of identical geometry are investigated with the direction of detonation of the line charge varied between the four models. Dynamic photoelastic patterns are recorded and analyzed to indicate which method of detonating the line charge produced the largest magnitude of tension at the free surface. The mechanics of rock breakage by means of explosives has received considerable treatment by many investigators including Duvall, Obert, Broberg, Rinehart, and Langefors1-11 over the past two decades. Indeed in more recent years several texts12-15 have been written on the topic, treating a wide variety of subjects which are logically related to the modern technique of rock blasting. In rock blasting the chemical energy of a concentrated explosive contained in a relatively small diameter borehole is utilized to fragment the rock. The explosive is transformed into a gas with enormous pressures which exceed 10-5 bars18 This high pressure shatters the rock in the area adjacent to the borehole and produces dilatational and distortional stress waves which propagate radially away from the borehole. The state of stress associated with these outgoing waves produces a system of cracks which extend for a few feet from the borehole. The breakage produced in this manner is limited as the dynamic stress in the pulse attenuates markedly with distance. In the absence of a free surface, the stress wave propagates away from the source without further fracture. With a free face of rock near the drill hole, another mode of breakage occurs which is due to scabbing failure of the layer of rock adjacent to the free face. These scabbing failures are produced by the reflection of the incident waves and the conversion of compressive stresses into tensile stresses sufficiently large to fracture the rock. The detailed nature of the interaction of the stress waves with the free surface is complex and difficult to treat analytically. However, dynamic photoelasticity offers an experimental approach which gives a fullfield visual display of propagating stress waves and the reflection process. Applications of static photoelasticity to solution of problems related to mining technology have become relatively common (see, for instance, Refs. 17 and 18) with a plastic model loaded to produce a state of stress representative of that occurring in the workings of a mine. The application of dynamic photoelasticity is ex tremely limited. Tandanand and Hartman19 have used a multiple spark camera to study fracture in glass and plastic plates impacted by a chisel-shaped tool. This paper describes a dynamic photoelastic analysis of stress waves interacting with a free surface. The free surface is that of a bench with a fixed bottom so common in quarry applications. The stress waves are generated by line charges of lead azide (Pb-N6). Four models of identical geometry are investigated with the direction of detonation of the line charge varied between the four models. Dynamic photoelastic patterns are recorded and analyzed to indicate which method of detonating the line charge produced the largest magnitude of tension at the free surface. Experimental Procedure The model illustrated in [Fig. 1] was fabricated from a sheet of Columbia Resin CR-39 to represent a bench with a fixed bottom. Properties of the CR-39 pertaining to these dynamic experiments are listed in [Table 1]. Scribe lines on 1-in. centers are used to identify locations along the bench face. The bench height was 8 in., the burden was 3 in., and the overall dimensions of the sheet, 16 and 18 in., were large enough to eliminate reflections from nonessential boundaries during the period of observation of the dynamic event. To simulate a charge in a borehole, a groove 0.062 in. wide and 0.080 in. deep groove was cut into the sheet from one side. The lower end of the groove was 1 in. or 1/3 the burden distance below the bottom of the bench. The upper end of the groove was 3 in. or one times the burden distance below the upper level of the bench. The groove was packed with 60 mg of Pb No per in. of length, and ignited with a bridge wire detonator. Four different ignition procedures were used to examine the effects of detonation direction on the stress wave interaction with the free face of the bench. In Test 1 the line charge was ignited at the top and the line charge detonated downward. In Test 2 the line charge was ignited at the bottom and the charge burned upward. In Test 3 the charge was ignited in the center with the top half burning upward and the bottom half burning downward. Finally in Test 4 the line charge was ignited at both ends simultaneously. Sixteen high-speed photographs of the photoelastic fringe patterns representing the stress wave propagation were recorded for each of the tests. A Cranz-Schardin multiple spark gap camera 20,21 was operated at framing rates which were systematically varied from 110,000 to 250,000 frames per sec during each test.

Jan 1, 1972

By J. L. Walter

Extra-low carbon iron sheet, when deformed and annealed, undergoes exaggerated or abnormal grain growth in the critically deformed regions of the sheet. This exaggerated pmth occurs, for low strains (3 to 6 pct), only in sheet which has a fine dispersion of precipitates in the subsurface region of the sheet and fewer and coarser precipitates in the sheet interior. These particles have been identified as manganese sulfides. Wing the anneal, grains near the surface are gvowth-inhibited by the fine particles but the grains in the interior are free to grow normally. With the additional driving force provided by the strain energy, the interior grains first grow into the small subsurface pains. Eventually, these growing grains grow completely through the sheet. Calculations of limiting grain sizes at various values of strain indicate that a volume fraction of precipitates in excess of 10-&apos; would be required to eliminate exaggerated growth in material strained to 10 pct. OPEN-COIL annealing has made decarburization of sheet steel both efficient and economically practical. Use of such material for porcelain-enameling stock is one of many possible applications of low-carbon iron since carbon in steel is deleterious to porcelain-enameling properties.&apos; However, the extra-low carbon iron presently available presents another problem, that of exaggerated grain growth in regions where the sheet has been deformed as by bending or stretching. In exaggerated grain growth a few grains start to absorb their neighbors and these may become very much larger than the average grains of the sheet. Other names for exaggerated grain growth are coarsening, critical grain growth, secondary recrystallization, abnormal grain growth, or discontinuous grain growth. While this grain growth does not affect the enameling qualities of the low-carbon iron sheet, their presence results in a marked reduction of tensile-yield strength in the region of the sheet containing the large grains. The loss of tensile yield strength may render the material unsuitable for many applications . This report describes the results of a study undertaken to determine the cause of the exaggerated grab growth in extra-1ow carbon iron and, if possi- ble, to prescribe practical procedures for its prevention. GENERAL THEORY The driving force for exaggerated grain growth is the grain boundary free energy. This driving force is proportional to (l/rl + l/r2) where rl and r2 are the mutually perpendicular radii of curvature of the boundary between the growing grain and the grain being consumed. Thus, the greater the difference in size between the growing grain and the matrix grains, the higher the driving force for grain growth. If, however, the matrix grains are free to grow simultaneously, the driving force for exaggerated growth will be diminished. Stability toward growth of the matrix grains may be caused by a) a strong single orientation texture (texture inhibition),&apos; b) a dispersed second phase,3"5 c) the thickness effect,&apos; or d) intergranular segregation.7"9 As exaggerated growth occurs when growth of the matrix grains has been slowed by the stabilizing processes mentioned above, there must be an additional factor acting to promote growth of a few of the grains to the point where they are enough larger than the matrix grains that boundary energy driving forces are sufficient to cause continued growth. For instance, at the annealing temperature, growth-inhibiting inclusions may slowly dissolve and coalesce. Eventually, a grain boundary becomes unlocked and migration occurs at the expense of neighboring grains. Or, an additional driving force may be supplied to some of the grains if the material is strained. Then, since some grains will be strained less than others, the difference in strain energy between adjacent grains may be sufficient to overcome boundary locking and allow growth of the grains with lower strain energies. In the present study, therefore, such factors as the presence or absence of dispersed phases, the nature of the exaggerated growth, and the effect of strain have been considered. EXPERIMENTAL PROCEDURE I) Material and Processing. Three types of low-carbon iron were used in this study; types A and B were commercial grades, each from a different supplier.* The precise details of the processing of

Jan 1, 1963