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By Robert C. Johnson

Single crystal whiskers of ZrO2 and TiO2 were grown by solution and crystallization of these oxides in molten baths. Mixtures of Na2B407 and LiC1 were the most suitable growth media for zirconia. Sodium borate alone and Na2CO3 plus SiO2 were best suited for titania. The solubilities of zirconia and titania in molten sodium borate were determined, Whether zirconia whiskers were dendritic or nondendritic depended on the temperature used. The best single crystal whiskers were grown below 1,100° C. Titania whiskers always grew as single crystals. The tensile strengths of zirconia and titania whiskers were about 15,000 psi and 50,000 psi, respectively. Modulus of rupture was about 49,000 psi for zirconia whiskers and 75,000 psi for titania whiskers. Chemical analyses showed the zirconia and titania whiskers to be pure. The zirconia and titania whiskers were shown by X-ray analysis to be, respectively, baddeleyite and rutile.

Jan 1, 1965

By John G. Simmons

A tutorial account of the tunnel effect between metal electrodes separated by a thin insulating film is presented. Energy diagrams of metal-insulator -metal sandwiches are briefly discussed, and the isothermal and thermal J-V characteristics for symmetric and asymmetric tunnel junctions are derived from a generalized expression. Experimental data from tunnel junctions are presented, and it is shown how, correlation between theory and experiment permits a determination of some of the oxide properties. Finally, the barrier heights in AT-Al2O3-A1 junctions determined by various inr3estigators are discussed. The object of this paper is to give a tutorial account of the electric-tunnel effect between metal electrodes separated by a thin insulating film and to illustrate its utility in the study of metal-oxide interfaces. This paper will emphasize the theoretical aspects of the electric-tunnel effect: however, a brief account of the more recent experimental work will be presented. A more comprehensive experimental study of the tunnel effect will be presented in the following paper by Drs. Pollack and Morris, see p. 497. We will open with a discussion of the energy diagrams for metal-insulator-metal junctions and what we mean by the electric-tunnel effect. Following this is an account of the theoretical studies of Sommerfeld and Bethe, and Holm, and the recently reported calculations on symmetric and asymmetric junctions using the generalized formula. The theoretical presentation is concluded with calculations on the temperature dependence of the tunnel J-V characteristic. In the experimental section, it is shown how barrier heights and thicknesses are determined by comparing the experimental data with the theory. Finally, the results of various investigators on the determination of the barrier heights in Al-Al2O,-A1 systems are discussed. I) POTENTIAL BARRIERS BETWEEN CLOSELY SPACED ELECTRODES Since it is necessary to supply energy to a metal in order to observe electron emission from its surface, it is evident that the potential energy of an electron within a metal is lower than that of an electron at rest outside the metal. It follows, then, that the electron must undergo a change in potential as it crosses the metal-vacuum interface. In the Sommerfeld1 free-electron theory of metals it is assumed that the free electrons, the electrons responsible for the electrical characteristics of metals, move in a constant potential environment in the metal, and are contained within the metal by a potential barrier at the metal-vacuum interface. It will be evident that the idea of a constant potential environment is a very idealized model, since the potential energy of an electron is influenced by all of the atoms and the other electrons within the metal; however, its use is justified by the many excellent results it gives.2 Fig. l (a) is the energy diagram of the model envisaged by Sommerfeld; the metal is represented by a potential-energy well of depth V,; the vacuum level represents the energy of an electron at rest outside the metal. At 0°K the electrons, which exist in pairs in discrete energy levels, fill up the well to an energy ?, the Fermi level. The distance, Vo - ?, from the Fermi level to the vacuum level is known as the work function of the metal, and represents the minimum energy required to free electrons from the interior of the metal at 0°K.

Jan 1, 1965

By P. M. Robinson, M. B. Bever

THE heats of formation at 273°K of the compounds InBi, In2Bi, and TIBi2 have been determined by metal solution calorimetry with bismuth as solvent. The published information on the thermody-namic properties of these compounds is limited. The structure of the compound InBi (mp, 383°K) is tetragonal of the PbO (B10) type.1 The compounds In2Bi (mp, 362°K) and TIBi2 (mp of highest-melting composition, 486°K) are now believed to have structures of the NizIn (B8) type273 and not the A1B2 (C32) structures reported earlier.4, 5 The compounds In2Bi and TIBi2 have limited homogeneity ranges at room temperature, while the compound InBi has no detectable homogeneity range.' Samples of the compounds were prepared from 99.99 pet Bi (Mallinckrodt Chemical Works), 99.999 pet in (American Smelting and Refining Co.), and 99.99 pet Tl (Amend Drug and Chemical Co.) by melting the components in sealed, evacuated Vycor tubes. The compounds InBi and in2Bi were of the stoichiometric compositions. The compound TIBi2 contained 40 pet T1; this composition was chosen because at room temperature the alloy of stoichiometric composition does not lie within the homogeneity range.' The melts were held approximately 50°C above the liquidus for 8 hr and then quenched into iced brine. The samples were homogenized for 48 hr at temperatures 20°C below the temperature of complete solidification. Metallographic examination of sections taken from the center and the ends of the ingots did not reveal second phases or segregation . The heats of formation were determined as the difference in the heat effects on solution of a compound and of a mechanical mixture of its components added from the reference temperature of 273°K to liquid bismuth at 623°K. The details of the calori-metric procedure and method of calculation have been described elsewhere? The calorimeter was calibrated by adding bismuth at 273°K to the bismuth bath at 623°K. The calculated values of the heats of formation of the compounds, listed in Table I, are based on a value of 4.96 keal per g-atom for the difference between the heat contents of bismuth at 273" and 623oK7 No published values are available for the heats of formation of the compounds InBi and In2Bi. Hultgren et a1.7 have calculated a value of -0.50 i 0.10 keal per g-atom for the heat of formation at 423°K of the compound TIBi2 containing 40 at. pet T1 from heat-content measurements in the range from 398" to 700°K and the heats of formation of the liquid alloy. The difference between this value and the value of -0.66 * 0.01 keal per g-atom at 273°K is too large to be attributed to a difference between the heat capacities of the compound and the components over the temperature range 273o to 423oK7 However, the direct determination of the heat of formation by a calorimetric method should give a more accurate value. The heats of formation at 273°K of the compounds InBi and In2Bi lie on a straight line when plotted as a function of composition, Fig. 1. The compound In2Bi, therefore, appears to be barely stable with respect to its neighboring phases. In order for the free energy vs composition curve to be concave towards the composition axis, the entropy change on formation of In2Bi must be more positive than that on formation of InBi. As the compounds are ordered,2, 3, 8 there is no configurational entropy change on formation. The difference between the entropy changes on formation of the two compounds, therefore, is probably associated with the vibrational entropies. In view of the low heats of formation, the changes in vibrational entropy, due to changes in bond strength on formation of the two compounds, are likely to be small. Owing to the volume contractions on formation of the two compounds,5 the vibrational entropies probably decrease slightly but the decrease of the vibrational entropy of InBi is expected to be larger than that of In2Bi.

Jan 1, 1965

By Arnold B. Hubbard

Automatic control instruments were utilized by the Bureau of Mines for routine assays of large numbers of oil shale samples and other bituminous materials. The standard Fischer assay method was automated by automatically controlling the heating cycles of a battery of 12 electric heaters with electronic controllers and programmers. The condensers were cooled with a modified automatically controlled refrigeration bath. The complete assembly consisted of 12 retort units, necessary control instruments, and the refrigeration bath. This equipment was capable of producing more consistent results than those previously obtained with the gas-heated retorts and of increasing the output of assays substantially with no increase in operating personnel.

Jan 1, 1965

By C. H. Schack

Extractive metallurgy techniques currently employed to recover silver from primary ores and secondary scrap were reviewed and evaluated to identify and delineate metallurgical problems whose resolution would increase the supply of silver from domestic materials. The survey revealed that practically all primary silver is recovered by froth flotation concentration of various types of ores, followed by smelting and refining of the separate lead, copper, and zinc concentrates. Silver losses during the complex processing are, with rare exception, inconsequential. Furthermore, any silver production gain from base metal ores, which contribute about two-thirds of the total primary silver, is directly dependent no improvement in the market for the base metals. Statistical data on new and old silver scrap are wholly inadequate to make reliable conclusions about scrap processing problems and the possibility of increasing the recovery of silver from the many forms of secondary silver-bearing materials. The available information indicates (1) that efficient silver reclamation practices are employed by the larger users of silver, and (2) that recovery of additional secondary silver involves solution of problems of collection rather than of processing. Several possibilities exist for limited increases in silver production from primary ores by improvement in metallurgical practices. Specifically, research is needed to (1) solve the problem of recovering silver from the copper ores of the Copper Range district, Michigan; and (2) devise economically feasible methods for recovery of silver from presently marginal or submarginal ores char because of grade, location, and frequently complex nature cannot presently be exploited by conventional techniques.

Jan 1, 1965

By H. J. Ramey

Conventional calculation of total system isothermal compressibility for a system containing a free gas phase involves, among other things, evaluation of the change of oil and gas formation volume factors and the gas in solution with pressure. Preferably, this information should be obtained from laboratory measurements made with particular oils and gases. Often, experimental measurements are not available. In this case, it is necessary to obtain pressure-volume-temperature relationships from general correlations such as those of Standing' for California oils. In order to speed estimates of compressibility, generalized plots have been prepared of the change of both oil formation volume factors and gas in solution, with pressure from Standing's correlations. A generalized plot for estimating the change in the two-phase (oil and gas) formation volume factor with pressure is also presented. Usually, the effect of gas dissolved in reservoir water upon the total system compressibility is neglected for gas saturated systems, due to the low solubility of gas in water. Results of this study indicate that the increase in total system compressibility caused by solution of gas in water is often as large as the compressibility of wafer, and can be magnitudes larger for low pressure systems. Generalized results for estimating the change of gas in solution in water with pressure are presented in tabular and graphical form. INTRODUCTION During the past decade, pressure build-up and drawdown techniques have gained an important place in reservoir engineering. Build-up and drawdown analyses are only two special applications of the broad field of transient fluid-flow theory. All solutions of transient fluid-flow problems contain a parameter called the total system isothermal compressibility. This property of fluids and porous rock is a measure of the change in volume of the fluid content of porous rock with a change in pressure, and it may vary considerably with pressure. Evaluation of total system isothermal compressibility is not difficult, but it is tedious and time-consuming. Often compressibilities are estimated roughly, or transient flow methods are neglected completely. The benefits of using accurate system compressibility in properly-executed build-up or drawdown analyses are: 1. Better planning of pressure build-ups may be achieved to avoid unnecessary loss of revenue due to excessively long shut-in periods, or to shut-in periods too short to yield useable data. 2. Better and more reliable estimates of static formation pressures for reserves estimates and rate performance estimates. 3. Reliable information for evaluation of well completion effectiveness, and planning and interpretation of well stimulation efforts. The purpose of this paper is to clarify the nature of the total system isothermal compressibility, and to present useful methods for estimation of compressibility, particularly for systems containing a gas phase. DEVELOPMENT Numerous publications have presented solutions to transient single-phase flow of slightly compressible fluids, stressing pressure build-up applications. In transient flow, a compressibility* term arises to permit volume content of fluids in porous rock to change as pressure changes. The basic nature of the compressibility term is usually taken for granted. Problems arise in practical applications of transient fluid theory because most published works consider only one flowing fluid—in an ideal porous system containing only one fluid. In 1956, Perrine2 presented an intuitive extension of single-phase flow pressure build-up methods to multiphase flow conditions. Later, Martin- established conditions under which Perrine's multiphase build-up method had a theoretical foundation. Perrine has shown that improper use of single-phase build-up analysis in certain multiphase flow situations can lead to gross errors in estimated static formation pressure, permeability and well condition. It is likely that, much pressure build-up data for oil wells should be analyzed on the basis of multiphase flow. For both single-phase and multiphase build-up analysis, the isothermal compressibility term in dimensionless time groups often should be interpreted as the total system compressibility. All real reservoirs contain one or more compressible fluid phases. In addition, rock compressibility can contribute in an important way to the total system compressibility. The proper total system compressibility expression may contain terms for compressibility of oil, gas, water, reservoir rock and terms for the change of solubility of gas in liquid phases.

Jan 1, 1965

By R. W. Heckel, R. L. DeGregorio

The DeHoff method of determining the size distribution of ellipsoid-shaped, second-phase particles has been applied to the spheroidization of cementite in a eutectoid steel. The surface area of Precipitates determined from the various size fractions in the distribution was correlated with surface-area measurements based on the number of intersected interfaces on a random lest line. The precipitate particles were found to be oblate ellipsoids with an axial ratio of about 0.90. The size distributions were found to be log-normal. A method is proposed whereby the shrinkage of small particles and growth of large ones can be determined from the experimental data. The experimental data are compared to previously proposed mathematical models describing diffusion-controlled kinetics and various types of interface-controlled kinetics. The experimental growth and shrinkage rates are considerably slower than those predicted by diffusion-controlled kinetics. The best fit is obtained for a model describing interface-controlled kinetics limited by the rate of formation of cementite at the growing interfaces where the interfacial reaction rate is proportional to the solute thermodynamic activity gradient across the surface. THE subject of spheroidization of second-phase particles has been considered previously by other investigators. Livingston1 has studied the precipitation of the cobalt-rich phase from copper alloys containing 0.7 to 3.2 wt pet Co. His results indicate that the average particle size increases as the cube root of the heat treatment time in accord with diffusion-controlled kinetics.'-' Komatsu and rant' in their studies of the growth of SiO2 in a dispersion-strengthened copper-silica alloy found that the initial growth of SiO2 proceeded by diffusion-controlled growth and later stages were limited by interface-controlled growth. The values of the activation energy obtained for the interface- controlled process led them to the conclusion that the process was limited by the dissociation of SiO2 at the shrinking interface. The transition from diffusion-controlled growth to interface-controlled growth was characterized by a particle size which varied with the heat-treatment temperature. It is also interesting to note that the particle-size distribution as found by Komatsu and Grant exhibits log-normal behavior when replotted on log-probability coordinates. Dromsky, Lenel, and Ansell9 have observed the growth of Al2O3 particles having a mean free path of about 1.5 to 13 µ. Their photomicrographs indicate that the Al2O3 particle sizes were larger than those observed by Komatsu and Grant. Dromsky, Lenel, and Ansell concluded that the Al2O3 coarsened by an interface-controlled growth mechanism limited by the solution of A12O3 at the shrinking interfaces. Bannyh, Modin, and Modin10 have studied the spheroidization of a eutectoid steel (0.83 wt pet C). Their spheroidization (tempering) treatments were carried out in the range from 210o to 700°C for times between 1.5 sec and 20 hr. Measurements of mean particle size as a function of time indicated a cube root of time dependence of size at 700°C, in agreement with previous analyses of diffusion-controlled kinetics.2°7 At lower temperatures, the time dependence was less than the one-third power. It is important to note that, although mathematical models of growth* considering particle-size distribution have been available, measurements of only mean particle size have been carried out. DeHoff11 has presented a quantitative metallography technique which is applicable to the determination of the size distribution of ellipsoids of constant shape. This method is applicable to both oblate and prolate ellipsoids of all ratios of minor to major axis and is based upon an extension of Saltykov's analysis12 of the distribution of spheres of varying size. DeHoff's analysis is based upon measurements of the minor axis of the particles on a random plane of polish in a unit area. This method provides a measure of the number of ellipsoids in various size ranges per unit area. As pointed out by DeHoff, such measurements may be used to obtain surface area and total precipitate volume data. Thus, the accuracy of the distribution analysis may be checked by comparison of the surface and volume

Jan 1, 1965

By Edward W. Parsons

The explosive-expansion center-hole anchor was designed and developed for the specific purpose of use as a component of an instrument system that measures differential ground movement within a small drill hole in rock. Such anchors should have an unobstructed center hole, should be installed without a twisting action which could tangle connecting wires, and should be capable of being installed at depths in excess of 100 feet. The anchor has a thick-walled center tube and a thin-walled outer tube. Low-energy detonating cord, wrapped around the center tube and detonated with a mild end primer, expands the outer tube to produce anchorage. The explosive-expansion center-hole anchor can be installed easily in drill holes of any inclination but cannot be installed under water. Centering of the anchor is critical with regard to its subsequent holding power. The anchor is safe to make and handle.

Jan 1, 1965

By J. E. Harris, J. A. Whiteman, A. G. Quarrell

The graphitizing reaction has been studied in a number of Fe-C-Si alloys in the temperature range 550° to 725°C. The TTT relationships exhibit "C" curve behavior except where nuclei, either foreign or graphite itself, are present before the start of the reaction. It is suggested that the rate -controlling process is diffusion of carbon through ferrite. For the reaction to proceed at the observed rate it is calculated that the matrix surrounding the particles must deform plastically; experimental evidence for this deformation is presented. It is well-established that the decomposition of austenite to pear lite occurs at a maximum rate at an intermediate temperature.l-5 This "C curve" be- havior, which has been reported in a number of other systems,5-10 is a consequence of the relatively low rate of nucleation of the pearlite at small degrees of undercooling of the austenite. The cemen-tite phase in the pearlite is, in turn, metastable with respect to graphite and if steels are held for prolonged periods at elevated temperatures decomposition of the pearlite occurs. It is difficult to predict the shape of the subcriti-cal graphitization TTT (time, temperature, transformation) diagram for, in this case, undercooling does not occur. However, the free-energy change for the reaction does decrease with increasing temperature" (Fig. 1) and it is thus anticipated that the rate of nucleation will fall as the temperature approaches that of the eutectoid. In addition, a decreasing growth rate with increasing temperature is predicted in some circumstances with pure Fe-C alloys. However, apparently similar conditions exist for first-stage graphitization in the austenite range (malleabilization) but no evidence for C curve behavior has been presented in the extensive liter-

Jan 1, 1965

By J. P. Hansen

Wustite beds were reduced with carbon monoxide and mixtures of hydrogen and nitrogen in the temperature range 900° to 1,300° C to determine the effect of temperature, gas flow, and surface area on the rate of reduction to iron. The composition of the gas stream as it passed through the wustite bed was continuously measured with infrared absorption cells and heated-wire methods. The change in composition was used to calculate the reaction rates. Arrhenius plots of the data give heats of activation of 34 kcal for particles using CO, 27 kcal for particles using H2, 24 kcal for pellets using C8, and 6 kcal for pellets using H2. The velocity of reduction is dependent on the area of reacting interface and the driving potential of the gas (reducing gas concentration minus equilibrium concentration) as well as the exponential temperature effect. The reaction rate was independent of the gas velocity over the range of conditions studied.

Jan 1, 1965

By W. F. Chiao, R. B. Gordon

Tile sharp-yield point found in magnesium crystals in the solulion-treated and aged condition is studied by dislocation internal-friction experiments. The results show that the sharp yield is not file to the sudden release of pinned dislocations hut is movc likely due to the rapid multiplication of an initially small number of dislocations. Recovery or the dislocation internal friction after deformation is also studied. This yecovery results from the re-pinning of dislocations by a solute, presumably nitrogen, which moves with a relatively small activation energy. SHARP-yield points, when they occur, are a striking feature of the stress-strain curve generated during a tensile test. Although commonly associated with steel, sharp yielding has been found in a variety of metallic and nonmetallic crystalline materials. In particular, sharp-yield points have been found in zinc"' and cadmium3 containing nitrogen. With this background, Geiselman and Guy4 investigated the tensile properties of magnesium single crystals containing nitrogen to see if sharp yielding also occurs in this system. They found that sharp yields did indeed occur in solution-treated and aged specimens tested at elevated temperature but were not able to give conclusive proof that the sharp yield was caused by nitrogen, a yield drop being observed even in their purest crystals. Sharp-yield points have also been found in various polycrystalline magnesium alloys.7'8 In the study of the sharp-yield phenomenon it is desired to observe the behavior of dislocations in the earliest stages of the deformation process. Internal-friction experiments are useful for this purpose because dislocation damping is sensitive to the mobility of free-dislocation segments. At low strain amplitudes the damping, A, due to the the forced vibration of dislocation segments of average length L is ? =KAL4 [1] where A is the dislocation density and K, if the applied frequency is well below the resonant frequency of the dislocation segments? is a constant for the sample under observation.5 Dislocation damping, because of the fourth-power dependence on L, is particularly sensitive to the creation of free-dislocation segments during deformation. Since sharp yielding is associated with the sudden release of pinned-dislocation segments, marked changes in the dislocation damping are expected at the yield point.6 The use of the dislocation-damping observations to help elucidate the incompletely understood mechanism of yielding in magnesium is the primary objective of the experiments reported here. PROCEDURE Many investigations have shown that very marked and rapid changes occur in the dislocation damping of of a deformed material as soon as the straining is stopped.5 It was quite essential, then, for the purpose of this investigation, to make the damping measurements during the deformation of the samples. This can only be accomplished through the use of the ultrasonic-pulse method. In this method traveling sound-wave pulses are used and, in contrast to resonating-bar methods, only the sample ends are set in vibration. Thus, the sample can be gripped along its sides in the tensile-test machine without disturbing the damping measurements. In the pulse method, the decrease in the amplitude of a sound pulse is measured as it travels back and forth through the sample. If A is the amplitude after traversing a distance x and A. is the initial amplitude, A=Aoe-ax [2] and a is called the attenuation. It is commonly measured either in units of cm-I or as db per µ sec. The observed attenuation in a metal sample is due to a number of causes. These include scattering by grain boundaries and impurity particles, thermo-elastic damping, diffraction effects, stress-induced ordering of solute atoms, and dislocation damping. The total observed attenuation in a given sample usually cannot be resolved into these various components, but changes in a due solely to changes in dislocation damping can be accurately determined, provided the experiment is arranged so that all other sources of damping are held constant. It is desired to reduce the extraneous sources of attenuation to a minimum and for this reason the experiments are done on single crystals of high purity. Magnesium crystals offer the further advantage that, when properly oriented, only a single set of slip planes is active during deformation. Crystal Preparation. The method of sample preparation is similar to that of Geiselman and Guy.4 The starting material was high-purity, sublimed magnesium rod supplied by the Dow Chemical Co. Melting under Dow 310 flux was used to reduce the nitrogen content of the starting material: the fluxing was done under an argon atmosphere and the

Jan 1, 1965

By Charles L. Bauer

WHEN a single crystal is annealed following plastic deformation recrystallization usually occurs rather than polygonization. Consequently, re-crystallization has received the overwhelming amount of attention albeit the intrinsic mechanisms by which dislocations rearrange and annihilate one another are just as well revealed by crystal polygonization. It is the purpose of this note to demonstrate the usefulness of studying the polygonization process by means of an etch-pit technique in sodium chloride. Sodium chloride deforms easily (the slip system is of the [110], (110) type), readily cleaves on (100) planes, and can be chemically etched so as to reveal the intersection of dislocations with a free surface. Thus it is possible to observe the distribution of dislocations after a crystal has undergone a specific deformation and annealing cycle. Various phases of the polygonization process

Jan 1, 1965

The principal activities of the Bureau of Mines Explosives Research Center from July 1, 1962, to June 30, 1963, are described briefly in part 1. Part 2 gives short abstracts of publications that appeared during fiscal year 1963; in general, the research reported in these publications antedates the report period.

Jan 1, 1965

Of the twelve known ore zones on the Sunro property, acquired by Cowichan Copper Co., only the "B" and "C" orebodies of the "River Zone" had been explored sufficiently to indicate the grade and tonnage. The "B" zone was selected for initial production. The portion of this orebody above the main adit level was developed for horizontal-ring, longhole mining. Ore from the stope would be scraped directly to the coarse ore bin. The lack of a suitable mill site on surface, as well as the 8,000-ft. tramming distance, led naturally to the installation ground. I N November, 1960, a lease was obtained by Co-wichan Copper Co. Ltd. (N.P.L.) from Sunro Mines Ltd., covering the main ore (River) zone of the Sunro property. A total of twelve zones had been located on the property. Nine of these lay within the leased area. With the exception of the "B" and "C" orebodies of the River Zone, there had been insufficient exploration for tonnage and grade calculations. Exploration by previous companies had

Jan 1, 1965

By M. A. Torcaso, P. Raimondi

The distribution of the oil phase in Berea sandstone resulting from increasing and decreasing the water saturation by imbibition was investigated Three types of distribution were recognized: trapped, normal and lagging. The amount of oil in each of these distributions was determined as a function of saturation by carrying out a miscible displacement in the oil phase under steady-state conditions of saturation. These conditions were maintained by flowing water and oil simultaneously in given ratios and by using a displacing solvent having essentially the same density and viscosity as the oil. A correlation shows the amount of trapped oil at any saturation to be directly proportional to the conventional residual oil saturation Sor The factor of proportionality is related to the fractional permeability to the water phase. Part of the oil which was not trapped was displaced in a piston-like manner (normal part) and part was eluted gradually (lagging part). The observed phenomena are more than of mere academic importance. Oil which is trapped may well provide the fuel essential for forward combustion and thus be beneficial. On the contrary, in tertiary recovery operations, it is this trapped oil which seems to make current techniques uneconomic. INTRODUCTION A typical oilfield may initially contain connate water and oil. After a period of primary production water often enters the field either from surrounding aquifers or from surface injection. During primary production evolution and establishment of a free gas saturation usually occurs. The effect and importance of this third phase is fully recognized. However, this investigation is limited to a two-phase system, one wetting phase (water) and one non-wetting phase (oil). The increase in water content of a water-wet system is termed imbibition. In a relative permeability-saturation diagram such as the one shown in Fig. 1, the initial conditions of the field would be represented by a point below a water saturation of about 35 per cent, i.e., where the imbibition and the drainage curves to the non-wetting phase nearly coincide. When water enters the field the relative permeability to oil decreases along the imbibition curve. At watered-out conditions the relative permeability to the oil becomes zero. At this point a considerable amount of oil. called residual oil, (about 35 per cent in Fig. 1) remains unrecovered. Any attempt to produce this oil will require that its saturation be increased. In Fig. 1 this would mean retracing the imbibition curve upwards. In addition, processes like alcohol and fire flooding, which can be employed at any stage of production, involve the complete displacement of connate water and an increase, or imbibition. of water saturation ahead of the displacing front. Thus, in several types of oil production it is the imbibition-relative permeability curve which rules the flow behavior. For this reason a knowledge of the distribution of the non-wetting phase, as obtained through imbibition, whether "coming down" or "going up" on the imbibition curve, is important.

Jan 1, 1965

By R. W. Stahl

Gas accumulation and dust suspension are the major safety hazards in coal stockpiling and reclaiming operations. This report presents a schedule of safety precautions and plant design features devised by the Bureau of Mines to reduce danger from these and other sources.

Jan 1, 1965

By S. Zador, C. B. Alcock, K. Sudo

Measurements have been made of the standard free enevgies of formation of the sulfates of cobalt, Cupric copper, nickel, and ferric iron in the temperature range of 750° to 950°C. Dynamic gas-solid techniques have been employed in which oxide-sulfate and basic sulfate mixtures were placed in a stream of gas of controlled SO3 potentials. Thermal analysis and thermogvavimetry were used as detection methods, and it was found THE formation of sulfates during the roasting of sulfide ores is now considered to arise in many cases from the interaction of sulfur trioxide in the gas and the metal oxide which is formed on the sulfide as a first step.' As a preliminary to the investigation of the kinetics of sulfate formation during roasting, measurements have been made of equilibria from which the free energies of formation of cobalt, copper, nickel, and iron sulfates can be that the range of temperatures which could be investigated and the choice of method was largely controlled by the kinetics of these gas-solid reactions. The results are compared with previous results obtained from static measurements with which they agree quite well, and calculations have been made employing themal data to interrelate the present results with those for other sulfates. calculated. The method used has been to expose the solid sulfate (or basic sulfate) to a controlled flowing gas mixture of SO,, 02, and SOs and to observe the temperature of decomposition. The onset of decomposition was detected by thermal analysis or thermogravimetry. EXPERIMENTAL METHODS The thermal-analysis method was similar to that employed by Dewing and Richardson.' The sulfate was dehydrated at 250°C in air, and placed in a small alumina crucible which was held by a quartz ring in the hot zone of a horizontal furnace. The reaction tube of this furnace was made of mullite.

Jan 1, 1965

By Oliver Q. Leone

The effect of oxygen content in the anode metal on titanium electrorefining characteristics was studied. Increasing quantities of oxygen in the anode resulted in increased anode scale formation, decreased anode and cathode current efficiencies, lower titanium recovery efficiencies, and higher oxygen content of the cathode products. The titanium electrorefining process performed best when the anodes did not contain more than 0.5 percent oxygen, although anode dissolution was recorded for alloys containing up to 25 percent oxygen. Back emf affords a useful index of an alloy to electrorefining.

Jan 1, 1965

By Jr. Frank Parrish

This report describes the performance of 17 selected water-injection projects producing from Pennsylvanian-and Permian-age reservoirs. Illustrations depict reservoir structure and thickness, and production and injection history. A selected bibliography of publications pertaining to area oil recovery and geology is included. Tabulations of field and reservoir data reveal marked differences in the projects. Increased oil recovery resulted from injecting water in most cases; however, seven projects recovered less oil than the operators anticipated. Oil recovery by water injection ranged from 0.2 to 262 bbl per acre ft, or 0.1 to 22.5 pct of the initial stock-tank oil in place. Major reasons suggested for poor performance include: (1) Adverse directional horizontal permeability, (2) channeling of injected water through fractures or zones of high permeability, and (3) lack of containment of injected water. One 330-foot-deep project is among the first successful shallow water-floods in north Texas. Another project is the first successful Canyon sand-stone waterflood reported in the area. Previous gas injection in two Cisco sandstone projects did not prevent the reservoirs from responding favorably to waterflooding.

Jan 1, 1965

By Curt D. Jr. Edgerton

This study was made to determine trends in fresh water usage by California petroleum refineries, to Forecast fresh water requirements to 1975, and to evaluate water conservation practices. Statistical data used in the study were obtained largely from published sources and from records of selected companies. An adequate sampling of the State's refining capacity was obtained, and the data were extrapolated to the total California refining capacity. A breakdown of the data was then made on the basis of the following refining regions: (1) the Los Angeles Basin and Southern Coastal region, (2) the Southern San Joaquin Valley, and (3) the San Francisco Bay area. An unpublished forecast of crude oil input to refineries by a major oil company operating on the West Coast was used as a basis for predicting fresh-water usage. The 1963 fresh water intake by California petroleum refineries was 84 million gallons per day. This is expected to increase to 128 million gallons per day by 1975. The fresh-water to crude-oil ratio is increasing in all regions except the Southern San Joaquin Valley. At present, the supply of fresh water available to almost all of the State's petroleum refineries, mostly from surface sources and company-owned wells, is adequate, although shortages may develop within the foreseeable future. Present conservation methods are centered around the following four objectives: (1) minimum intake of fresh water of the lowest possible quality commensurate with sound technologic practice; (2) optimum recirculation (3) proper treatment before discharge; and (4) substitution of air cooling for water cooling.

Jan 1, 1965