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By Charles S. Barrett, Hermann F. Kaiser, Robert F. Mehl

THE copper-silver system presents several points of special interest in the study of segregate structures. The system is simple eutectic, with limited solid solutions terminal with the pure component metals. The extent of solid solubility decreases with decreasing temperature for both the copper-rich and the silver-rich alloys, thus offering a possibility for the formation of Widmanstätten figures and also a possibility for aging after quenching. In contrast to the structures studied previously the structures in this system are unique in their origin, for one terminal solid solution will precipitate the other, and vice versa. In most of the other systems for which crystallographic data on the precipitation (or transformation) process are available, either intermetallic compounds or intermediate phases partake in the decomposition process; the absence of such phases thus distinguishes this system. The lattice structures of the two solid solutions are identical in type, differing in lattice spacing by approximately 10 per cent; because of this it seems difficult if not impossible to predict on the basis of present theory either the outward form of the precipitate or the lattice orientation relationships between matrix and precipitate. The eutectic temperature in the copper-silver system1 is 779° C. At this temperature copper dissolves 4.3 atomic per cent (7.0 weight per

Jan 1, 1935

By P. A. Beck, S. Kohara, M. N. Parthasarathi

IT has been shown1,3 that many observed phenomena related to annealing textures in f.c.c. metals can be adequately accounted for, at least in a qualitative way, by considering the orientation dependence of the boundary mobility, without any hypotheses concerning preferred orientation of nuclei. It was noted1 that this approach is particularly successful in the common cases of primary recrystallization in highly cold-worked polycrys-talline metals, where nuclei occur in great abundance, and that in the other extreme case, where the number of nuclei is very limited, or even only a single crystal is grown, the orientation dependence of boundary mobility has only a small effect, or none at all, on the orientations resulting from annealing. Recently Dunn described examples3-6 where observed secondary recrystallization textures apparently cannot be accounted for on the basis of oriented growth alone, but also require oriented nuclei, or at least the absence of nuclei in certain orientation ranges. In general, the great difficulty in correlating the preferred orientation of recrystallized grains with that of nuclei is inherent in the fact that nuclei are by nature very small, and that they are usually identifiable as "nuclei" only after growth, i.e., after they have already been subject to growth selectivity. An investigation was carried out by Liebmann and Lücke,' and also a very similar one by Graham and Cahn,' to obtain quantitative information on the orientation depend- ence of boundary migration rates in the recrystallization of slightly deformed aluminum single-crystal rods or plates, in which artificially nucleated recrystallized grains of predetermined orientation were grown. Liebmann and Lücke foupd maximum boundary mobility for boundaries across which the misorientation corresponded to a rotation of 40 deg around a common [Ill] axis, in accordance with earlier conclusions.9,1 Also, they confirmed that such an orientation relationship predominates among crystals growing into slightly extended single crystals from presumably random artificial nuclei. On the other hand, Graham and Cahn found no preferred orientation among crystals grown in a similar manner. It is not as yet known how these observations may be reconciled with each other. The view has been expressed in various papers5'10,21 that selective growth based on the orientation dependence of boundary mobility is not in itself sufficient to account for the formation of sharp re-crystallization textures, such as those often observed in highly deformed polycrystalline metals after annealing. The present work was undertaken to ascertain whether or not it is possible to obtain a sharp re-crystallization texture in a case where random nuclei are assuredly present in large numbers. It was previously found1' that high-purity aluminum crystals rolled 80 pct on the (110) plane in the [1T2] direction, when suitable precautions are taken, may be annealed for periods of about 1000 sec at 350°C without recrystallization. It was also found that the reluctance to recrystallize in this case is due to the scarcity of material in sufficiently deviating orientations to serve as nuclei. By using such a matrix,

Jan 1, 1959

By L. L. Handy

The most common method of identifying hydrocarbon-bearing strata in a well that penetrates many different formations involves measurement and interpretation of the electrical properties of the formations as determined by electrical logs. Even though this method is used extensively, and even though in a great many instances it is capable of indicating presence of oil or gas, situations arise for which it is extremely difficult, if not impossible, to deduce the presence of hydrocarbons. These situations may involve the following. 1. A thin formation, bounded by highly resistive formations, in which it is impossible to obtain the actual resistivity of the uninvaded zone with existing logging devices. 2. A formation in which invasion has been so extensive that a value for the uninvaded zone resistivity cannot be obtained. 3. A very shaly formation in which the resistivity index, I, is lower than that usually associated with productive formations. 4. Laminated formations comprised of thin productive sands separated by thin shale streaks in which the individual sand and shale streaks are too thin to permit measurement of uninvaded-zone resistivity with existing logging devices. 5. Productive formations in which the water saturation is high. To extend the utility of electric log interpretation to identification of hydrocarbons in all types of formations, there is strong incentive to find a method not subject to these limitations. Some time ago, in connection with research on the wettability of reservoir rock, an investigation was conducted in which the resistivities of cores were measured shortly after they were removed from a core barrel, and again after they had been extracted and restored to their original oil and brine saturation.' The resistivities after extraction were generally lower. Other tests made on the cores indicated that they were more nearly water wet after they were extracted; thus, it was assumed that the observed changes in resistivities were due to a change in wettability of the cores. Other experiments'," have shown that resistivities of rock samples are sharply dependent on wettability. These experiments have shown that oil-wet samples are more resistive than water-wet samples. To obtain an understanding of how the wetting properties of the surfaces of core material affect electrical resistivity, a series of experiments was conducted. Two groups of core samples were prepared for testing. One group contained brine, but no residual oil. The other group was saturated with brine, flooded with oil to a low water saturation, then flooded with brine to a final residual oil saturation. Resistivity measurements were made on each group. Both groups were then flooded with the original brine to which a chemical had been added that renders sand and clay surfaces preferentially oil wet, a so-called reverse-wetting agent. very little change in resistivity was observed in cores containing only water. The group containing residual oil, however, showed resistivity increases of 100 to 200 per cent. These experiments showed that the resistivity of a core containing oil could be altered by changing wet-tability of the core. Moreover, the possibility was introduced that reverse-wetting agents might be employed as the basis for a logging method for identification of oil-bearing strata. Since behavior of a porous rock containing gas and water might be expected to be similar to that of a rock containing oil and water, such a method should also be applicable to identification of gas-bearing zones. In principle the wettability of the invaded zone could be reversed without altering conductivity of the interstitial water or the hydrocarbon saturation therein. Those strata showing significantly increased invaded-zone resistivities would, therefore, contain hydrocarbons; those with no significant change would be filled only with water. Addition of a reverse-wetting agent to a hydro carbon -bearing zone which is, by nature, already preferentially oil wet would not result in an enhancement of its resistivity. It is generally believed, however, that most hydrocarbon-bearing strata are preferentially water wet.

By K. A. Jackson, J. D. Hunt

A new classification of eutectics is proposed, based on tlze entvopies of wzelting of the tuio eutectic phases. The clnssification was used to predict suitable tvansparent analogs of the metallic systems. Experimental confir?nation loas obtained for the theovetical shape of the lamellar solid-liquid interface, fov the fault mechanisms of lanzellar spacing changes, and for the development of low-energy solid-solid boundaries between the lamellae. An explanation is presented to account jov the irvegular and coinplex regular structures zrhich are found in some eritectic systems. FrOM experimental observations, single-phase materials can be divided into two groups according to their solidification characteristics, those that grow as faceted crystals and those that do not. acksonl' showed from thermodynamic reasoning that the type of growth depended on a factor a which was almost thg entropy of melting. Most nonmetals have high entropies of melting (a greater than 2) and grow with crystalline facets. Most metals have low entropies of melting (CY less than 2) and grow almost isotropically with no facets. The authors propose that eutectics may be classified in a similar manner. There are three groups of eutectics, those in which both phases have low entropies of melting, those in which one phase has a high and the other phase has a low entropy of melting, and those in which both phases have high entropies of melting. Lamellar or rodlike structures are formed in systems in which both phases have low entropies of melting. In these alloys dendrites of either phase may be formed, when the alloy is rich in the relevant component. Examples are Pb-Sn, Sn-Cd, Pb-Cd, Sn-Zn, Al-Zn. Irregular, Fig. 14((), or complex regular, Fig. 14(b), structures are formed in alloys in which one phase has a high entropy of melting and the other has a low entropy of melting. Examples are A1-Si, Zn-MgzZnll, Pb-Bi, Sn-Bi. When the alloys are rich in the low entropy of melting phase, dendrites are formed; when the alloys are rich in the high entropy of melting phase, faceted primary crystals are produced. These crystals are sometimes called hoppers or pseudodendrites. In this work the term dendrite will only be used to describe nonfaceted primary crystals. Dendrites are not formed during solidification in high entropy of melting single-phase materials. The third group of eutectics includes alloys in which both phases have high entropies of melting. Each phase grows with a faceted solid-liquid interface. Since most metals do not have high entropies of melting, metallic examples in this eutectic group are rare. However they may occur between some intermetallics and semiconductors or semimetals such as silicon, germanium, and bismuth. Attempts have been made to study eutectic solidification visually by watching the growth process.374 Since metals are not transparent, the observations had to be made on external surfaces. This difficulty can be overcome by using transparent analogs of the metallic systems. As was mentioned earlier, most single-phase compounds have entropies of melting greater than 2 and so grow as faceted crystals. Recently organic materials with entropies of melting less than 2 were investigated.' These materials grow in exactly the same way as the low entropy of melting metals. When the materials are pure, they grow with a solid-liquid interface parallel to an isotherm; when they are impure, cells or dendrites are formed. Since these materials are transparent, have low melting points, and even have cubic structures, they should be ideal for making up transparent analogs of the metallic eutectics. The purpose of the present work was to investigate these organic eutectics and to see whether this quite different series of eutectics could be classified in the same way as the metallic systems. The observations made on the organic alloys are also discussed with reference to the current theories of lamellar growth. Explanations are proposed to account for the structures formed in the other eutectic groups. EXPERIMENTAL Thin cells containing the organic alloys were uni-direction ally solidified on a specially constructed microscope stage.' Uniform growth rates were obtained by moving the cells, with a motor drive, through a fixed temperature gradient, so that the solid-liquid interface remained stationary with respect to the microscope objective lens. The cells were made by fusing two microscope cover slides 7/8 by 7/8 by 1/100 in. together on three sides, leaving a gap of 1 to 3 mils between the slides, and these were filled by surface tension. A preliminary investigation of the phase diagram between two components could be made very rapidly. One side of the cell was filled with component A and the other side with component B. Since only a small amount of mixing could occur every composition from pure A to pure B was present in the cell. When the cell was placed in the temperature gradient a pictorial representation of the phase diagram was obtained. Eutectics, peritectics, "interorganics", and solid -solid transformations could be readily detected. Fig. 1 shows part of a eutectic phase diagram. The Sample was first grown slowly then stopped. The two

Jan 1, 1967

By J. K. Elliott, P. H. Kelly

Many engineering functions such as surface metering work and laboratory compressibility check points involve the use of liquid densities of light hydrocarbon mixtures at various pressures and temperatures. However, at the present time, no simple reliable method exists for determining density variation, particularly if the composition of the liquid is unknown. Consequently, a study was undertaken to develop and present a simple and accurate method of predicting density variation of a light hydrocarbon liquid with pressure and temperature, knowing only the density of the liquid at some condition. The experimental liquid compressibility data from API Project 37 by Sage and Lacey' have been considered to be accurate within 0.5 per cent and cover a wide range of pressure (14.7 to 10,000 psia), temperature (100" to 400°F) and molecular weight (up to 150). From these data, a set of liquid density curves, which relate density to pressure, temperature and molecular weight, was developed. These curves make it possible to predict density variation with pressure and temperature. Compared to extensive laboratory compressibility data on a complex, light hydrocarbon liquid, the use of the liquid density curves resulted in an average error of less than 0.5 per cent. Based on the results of this analysis, it is concluded that the set of liquid density curves developed from the data of Sage and Lacey provides an accurate and simple method for predicting the density variation of light hydrocarbon liquids when the density at some condition is known. These curves should be very helpful in many engineering calculations, particularly in the surface metering of light hydrocarbon liquids. INTRODUCTION Many situations arise in field and engineering laboratory work, such as reservoir engineering studies, check of experimentally determined laboratory data and orifice flow-meter formulas, where liquid density factors at various pressure-temperature conditions are required. Also, the need for accurate light hydrocarbon liquid information has become more important with the advent of miscible-type displacements for secondary recovery purposes in oilfield operations. Several reliable methods are available1 - "or determining the density of liquid hydrocarbons if the composition of the liquid is known. However, there is a definite lack of methods for accurately determining the variation of density when the composition of the liquid is unknown. The purpose of this study is to review the various methods for determining hydrocarbon liquid densities and to develop a simple and reliable method of determining variation in density of light hydrocarbon liquids with pressure and temperature when the compositio~n of the liquid is unknown. METHODS FOR DETERMINING DENSITY OF LIQUIDS OF KNOWN COMPOSITION Sage, Lacey and Hicks' have proposed a method to predict the density of light liquid hydrocarbons by using partial molal volumes. Data are available on experimentally developed partial liquid volumes of hydrocarbons over a rather limited range of temperature, pressure and composition. The partial mold volume method has proved satisfactory for determining the density of some hydrocarbon liquids when the composition is known. Within the range covered in the Sage, Lacey and Hicks1 data, the results agree within about 3 per cent of the experimental values. Hanson mentions the limitation of this method to a composition range of approximately 10 per cent by weight of methane, which will not allow this correction to cover most low molecular weight-light hydrocarbon liquids. Standing and Katz2 studied data on light hydrocarbon-liquid systems containing methane and ethane at high temperature and pressure and have presented a method for determining liquid densities, assuming additive volumes for all components less volatile than ethane and using apparent densities for methane and ethane. The compressibility and thermal-expansion curves used by Standing are based on assumptions that compressibility of a hydrocarbon liquid at temperatures below 300°F is a function of the liquid density at 60°F and that thermal expansion of the liquid is affected little by pressure. The information required to use this technique with an example problem is furnished by Standing.' Hanson eports an average error of - 0.5 per cent using the method of apparent densities in calculating liquid densities of several volatile hydrocarbon mixtures. However, as implied, the apparent density method is not applicable for liquid density calculations when the composition of the liquid is unknown. Watson- as presented a method

By Robert H. Merrill

In 1960, the Kennecott Copper Corp. and the U.S. Bureau of Mines entered into a joint research program to determine the changes in stress, strain, and displacement created by changes in slope angles. The field site was the Kimbley Pit, located near Ely, Nev. The supporting laboratory investigations were made at the Bureau's Denver Mining Research Center. Following a study to determine the rock stresses in the mining district, the strike and dip of geologic defects (fractures) in the rock, and the laboratory-determined strength of the rock, a new slope angle and pit configuration was selected, and instruments were installed to measure changes in stress, strain, displacement, microseismic noise rate, and sonic velocities at several points in the west wall of the pit. Between February and November 1966, the west slope was changed from an average angle of 45' to a slope angle that started at 45° on the south wall, and gradually increased to 575' at the center of the west wall, and to 61° on the north wall. The pit was deepened from about 500 ft to about 550 ft. About 2.55 million tons of waste and ore were removed by stripping and mining. Measurements made between November 1965 and September 1967 showed that the pit wall was stable before excavation began, that changes in the measured quantities occurred in the pit wall during the excavation, and that the wall returned to a condition of equilibrium after the mining was completed. The need for a method and the technology to pre-design a pit slope does not require elaboration. About 5 billion tons of material are excavated yearly by surface mining methods in the United States, and the economics, safety, and availability of lower grade metals, nonmetals and fuels could all be substantially improved if operators could preselect optimum slope angles. Mining companies and the Bureau of Mines have recognized the need for developing engineering methods to determine stable slope angles. In the industry, Kennecott Copper Corp. had been making an

Jan 1, 1969

By R. H. Oliver

The purposes, types, preparation, and testing of flocculants are discussed. A flocculation compendium is included, indicating choice of flocculant for a given set of conditions. An economic evaluation of the process is presented. Solid-liquid separation is a major expense in most mineral processing flowsheets today. Proper use of flocculation can often lower the overall cost of a solid-liquid separation by reducing the size of sedimentation or filtration equipment. PURPOSE OF FLOCCULATION When is use of a flocculant justified in terms of overall process economy? 1) when it results in process improvement, such as producing a clear liquor for electrolysis, precipitation, ion exchange, or solvent extraction; 2) when it results in satisfying requirements of pollution abatement ordinances; 3) when it results in increased recovery of values that would otherwise be lost; or 4) when it results in considerable savings in capital expenditure due to use of smaller equipment. When can the use of a flocculant adversely effect overall process economy? 1) when it results in increased filter cake moisture, 2) when it results in decreased filtration rates, 3) when it results in considerable bulking of sedimentation underflow, 4) when it contaminates either the supernatant or sludge, or 5) when the cost of using the flocculant is greater than the savings due to its use. First step in consideration of flocculants for a given application is establishment of desired goals in terms of increased clarity of effluent, increased recovery of solids, or decreased size of equipment. The most economical solution to a solid-liquid separation problem is that combination of equipment and flocculant costs which meets the established goals at the lowest total annual expenditure. This economic decision can be made only after technical data has been obtained as outlined in next four sections. TYPES OF FLOCCULATION Flocculation is a process wherein individual particles are united into more or less tightly bound agglomerates or flocs, thereby increasing effective particle size of solids suspended in a liquid. Degree of flocculation of a suspension of finely divided solids in a liquid is controlled by a combination of probability of collision between particles and probability of adhesion after the collision has occurred.' Probability of collision can be increased commercially through use of a paddle-type flocculator, combination flocculator, and clarifier or flocculating-type feedwell. Probability of adhesion usually can be increased by addition of a reagent known as a flocculant. Reagents act as flocculants through one or a combination of three possible mechanisms. The first is electrolytic neutralization of inter molecular repulsive force due to Zeta potential. This neutralization enables Van der Waal's cohesive force to hold the particles together after they collide.' The second is the precipitation, within a definite pH range, of voluminous metallic hydroxide flocs which entrap fine particles. This process is known as coagulation.14 Third is the bridging of two or more particles by either natural or synthetic long-chain, high-molecular-weight organic polymers. This bridging is accomplished by adsorption of two particles at different sites on the same molecule or by bonding of two molecules, each adsorbed to a different particle. Considerable effort has been expended in explaining the action of these polyelec-trolytes and detailed accounts are available in the literature. CHOICE OF FLOCCULANTS It is impossible, at the present time, to specify the optimum type or amount of flocculant for a given application from a knowledge of the material to be treated. The standard procedure is to choose reagents or combination of reagents most likely to be effective on the slurry; then test them.' The accompanying Flocculation Compendium (Table I) contains details of all currently available reagents sold as flocculants and it should be used when selecting the group of reagents for tests. This selection can be based on information listed in columns 4 and 5. Column 4 presents industries in which each floc-

Jan 1, 1961

By C. F. Cornell, R. C. Emmett, D. A. Dahlstrom

FOR many years the disk-type and cloth-covered drum filters have found widest application in liquid-solids separation, which uses continuous filters. The disk type is less expensive, occupies less floor space per square foot of filtration area, and re- quires negligible down time for filter media changing. However, because filter cloth is billowed out by the blowback in the cake discharge, it is very short-lived if the scraper blades are set too close. Consequently cake weight is very important in assisting cake discharge, which normally necessitates a minimum cake thickness of 3/8 to ½ in. Also, the vertical position of the disks eliminates the possibility of efficient cake washing for removal of soluble values. The disk-type filter is generally limited, therefore, to applications that require no cake washing and form relatively thick cakes within the normal range of filter cycle times. The conventional cloth-covered drum filter is a more flexible unit, permitting wider variation in the percentage of cycle time devoted to cake formation, dewatering, or washing, as required by the application. Thinner filter cakes can be discharged be- cause a horizontal line across the filter medium at the location of the scraper blade is equidistant from the edge of the blade at all points. The scraper blade therefore may be set a short distance from the filter medium or, where wire winding is not used, a floating scraper can be utilized so that the contour of the cloth can be followed. The drum filter is generally employed when there are difficult filtering slurries with resultant thin cakes or when cake washing to recover soluble values must be practiced.

Jan 2, 1958

By P. R. Schmidt, N. J. Themelis

A study zvas made of the deoxidation of copper at 1170°C by injecting a jet of carbon monoxide vertically upwards into the melt. The effects of submersion depth (2 to 20 cm), orifice diameter (& to 5 in.), and gas velocity (100 to 3650 ft per sec) were examined. In the oxygen range 0.1 to 1.0 pct 0, the overall rate was conlrolled by gaseoLcs mass Lransfer. The results were interpreted in terms of a rate coefficient per unit depth which was found to be constant with distance along the jet axis and nearly proportional to the orifice Reynolds number in the range 1000 < NReo < 9100. AS the gas flow rate through an orifice submerged in a liquid is progressively increased, at least three regions of bubble formation may be distinguished. At very low rates, the formation of bubbles is practically a static phenomenon, depending on the orifice diameter, the liquid surface tension, and the densities of the two phases. In this region, the bubble size is constant while the frequency of bubble formation increases with gas flow rate.&apos;-3 At higher flows (500 < NR~, < 2100), the frequency of bubble formation reaches a steady value and the bubble size increases with gas flow rate; when the bubbles issuing from the orifice become so large that they start coalescing to form larger bubbles, the turbulence induced in the liquid by the passage of previous bubbles shatters them into small bubbles of varying size. Finally, for gas velocities in the intermediate and turbulent regions of flow (NR,, > 2100) a tangential separation surface is created around the jet and momentum transfer takes place between it and the surrounding liquid medium. The entrainment of liquid and the resulting deceleration of the gas-liquid dispersion causes the jet to expand forming a characteristic jet cone. The large velocity and density differences between the jet and the liquid result in a high degree of instability and the jet envelope fluctuates rapidly.The characteristic jet cone can be observed by means of time exposure photographs such as those shown in Fig. 1 for an air jet introduced vertically upwards in a water bath. High-speed photography has showns that the gas-liquid dispersion within the cone consists of small bubbles the size of which depends mainly on the jet orifice diameter and Reynolds number. In the laminar region of flow, the following correlation was obtained by Leibson: The results of Liebson et a1.&apos; are plotted in Fig. 2. It can be seen that the region 2000 < NReo c 10,000 is not well-defined experimentally. In the entrance to the fully turbulent region of flow (NR,, = 10,000), the mean bubble diameter decreased to about 0.4 cm and varied only slightly from there on according to the correlation:

Jan 1, 1968

By L. A. Rapoport, W. J. Leas

The original Burkley-Leverett theory has been extended and a more detailed formulation of the waterflood behavior in linear horizontal systems is presented. Particular consideration has been given to the evaluation of capillary pressure effects and differential equations permitting an explicit evaluation of these effects have been derived. On the basis of the developed theory it is recognized that the flooding behavior is dependent upon the length of the system and the rate of injection. At the same time it has been determined that systems of different lengths yield the same flooding behavior if the injection rates and or the fluid viscosities are properly adjrrsted or "scaled." It has also been found that the sensitivity of the flooding behavior with respect to rate and length decreases as any one of these {actors increases in value and that for sufficiently long systems and high rate.; of water injection the flooding behavior becomes independent of rate and length. or "stabilized." To such stabilized conditions the theory formulated by Buckley and Leverett is applicable. A number of laboratory flooding tests have been made and good agreement Iraq been found between theory and experimental observations. The experimental results are discussed and it is shown that under field conditions the flooding behavior is usually stabilized. As a result of these finding; a procedure is indicated for evaluating field performances either on the basis of tests performed with commonly available core samples or by means of calculations using relative permeability data INTRODUCTION In recent years the development of methods for evaluating oil recovery by waterflooding has been the object of considerable research. A theoretical analysis of the mechanisms involved in the displacement of immiscible fluids was originally established by Buckle!- and Leverettl and experimental investipatio~~s have been made by numerons workers." Many of the experimental results are in mutual agreement and bear out several significant features of the flooding mechanism as predicted by theory. Thus it lias been generally recognized that a flood corresponds to the movement of a steep saturation hank or "front" (primary phase), followed by additional gradual oil displacement (subordinate phase). It has also been found that for any porous medium the flooding behavior is largely dependent upon the oil-water viscosity ratio and that for increasing values of this ratio the relative importance of the primary displacement phase decreases while that of the subordinate phase becomes more pronounced. Although the studies to date have clarified certain aspects of the flooding process. they have given rise to observations of a somewhat contradictory nature that cannot he explained in terms of the original theory. These observations pertain mainly to the effect of injection rate or pressure gradient upon recovery. Some investigators report laboratory tests that indicate incresing oil recoverieq with increasing rates of water injectill, others find the flooding behavior to be independent of and other. mention lower oil recoveries with increased injection rates.3 The conflicting evidence indicated above creates considerable uncertainty with respect to laboratory testing procedures and the utilization of the resulting data for field evaluations. The principal purpose of this paper, then, is to resolve these Uncertainties by means of a comprehensive theoretical and experimental investigation of the flooding meanism. THEORETICAL DEVELOPMENT Derivation of Flooding Equations The mathematical description of transient flow phenomena is based upon the consideration of the various processes occurring during an infinitesimal time interval in an infinitesimal volume element and upon the correlation of these processes with those occurring in the adjacent elements. The volume elements are defined as being infinitesimal in comparison to the overall dimensions of the porous system, yet each sufficiently large so aS to encompass the full range of pore openings encountered throughout the system. If a porous system can arbitrarily be subdivided into an infinite number of volume elements all possessing the same distribution of pore openings and if this distribution is unformly continuous. the system may be said to be homogeneous. Such a homogeneous porous medium is considered in the present studivs. It is furthermore postulatecl that only oil and water are present in the pornu wediu. that they act a- totally incompressible and immiscible fluids. and that gravity effects are negligible. In n linear flow system of unit cross sertional area. as treated here. the infinitesimal volume element.; to he considered are cylindrical ".slices" of thickness dx. oriented perpendicularly to the direction of flow. The equations applicable to any such volume element. at my time. describe the movement. of oil and water across the element:

Jan 1, 1953

By Paul Sterling

The general impression regarding the preparation of merchantable anthracite is that it is confined to a colossal, grimy structure, called a " coal-breaker." This name is a misnomer; for the desired result is not to break the coal, but to prevent its being broken. Preparation may be said to begin at the face of the chamber, with the mining and loading of the coal. Local conditions vary, not only ill the same field or basin, but also in the same mine, so that there is no fixed empirical rule governing the method of blasting or cutting coal. Tests should be made, when possible, to determine the explosive, or the mechanical coal-cutter, which will produce the largest percentage of what are locally known as " lump " and " prepared sizes " of anthracite. The prepared sizes are those mostly consumed for clomestic purposes. All other sizes might be called by-products of the anthracite industry; for they are not especially desirable, being the degradation resulting from the mining and handling of a brittle or laminated material. Being low in volatile combustible matter, anthracite burns most successfully when nearly of a uniform size, permitting the easy passage of air through the voids. This accounts for the large number of sizes into which the coal is separated. Table I. gives the various sizes, the diameter of ring over and through which each size is made, and the usual purpose for which it is employed.

Jan 1, 1912

By C. W. Lawr

The ores mined by the Santa Gertrudis Co. at Pachuca, Mexico, arc mainly silver-bearing; they also yield some gold and carry a little copper. Strong cyanide solutions are used to dissolve the silver and gold, and the mechanical loss of cyanide at the tailings filter has been considerable. Prior to the year 1923, the pulp, after agitation, was given a 35 to 37-min. wash with barren solution in a Butters-type leaf filter; the discharged slime cake was repulped and pumped into eight Merrill self-sluicing slime presses in which the slime was given a further wash with barren solution for 25 to 35 min., followed by a 10-min. water wash. At that time the barren solution titrated around 0.350 per cent. free KCN and 0.500 per cent. total KCN. (Aero brand cyanide is used.) It can readily be seen that a 10-min. water wash would leave considerable cyanide in the filter cake, which of course was a total loss. This averaged 0.522 kg. (1.15 Ib.) KCN per ton of solution. As the daily discharge to the dam was 1600 tons&apos; of slime of a 2:1 ratio of liquid to solid, the value of this mechanical loss of cyanide was an important item and it&apos;s recovery held alluring possibilities. Principle of Cyanide-recovery Process As it had acquired the patent rights to theLayng (H. R.) and Halvor-sen (A. L.) processes, also those of Mills (L. D.) and Crowe (T. B.) after considerable experimental work in its own laboratory and at Tonopah, Nev., The Merrill Company of San Francisco early in 1923 notified the Mexican Corporation and compania de Santa Gertrudis of its process for the recovery of cyanide from weak wash solutions, or for the transference of cyanide from a foul mill solution to a clean alkaline solution. This method is known as the Mills-Crowe process, the principle of which is as follows: The solution from which the cyanidc is to be removed is made acid by bringing it into contact with sulfur dioxide (SO2). The acidified solution is the; transferred to a closed tank in which air and solution are brought into intimate contact. The air leaving the tank charged with HCN is then passed to another tank in which it is mixed with an alkaline solution,

Jan 1, 1930

By E. De Goyler

Volcanic origin was among the first of the theories advanced to account for the occurrence of the salt domes of the Gulf coastal plain, northern Louisiana, and eastern Texas, and it is still being re-stated in various forms by the most recent contributors to our knowledge of the geology of such deposits. Argument has been largely by analogy and attention has repeatedly been called to the Mexican oil fields, particularly those of the Tampico-Tuxpam region, because of the occurrence of oil in close proximity to volcanic plugs in those fields, an occurrence supposed to have some resemblance to the common occurrence of oil in the salt domes of the United States. The author, having spent several months of the past year in a general study of salt domes and in a detailed study of certain domes in the United States, and having been acquainted for some time with the exploration of similar domes in the Isthmus of Tehuantepec region, Mexico, and with the general geology of the Tampico-Tuxpam region, Mexico, has reviewed the various theories of volcanic origin for salt domes which have been advanced to the present time. The purpose of this paper is to present such review and to discuss the supposed Mexican analogy. Review of Volcanic Theory R. Thomassyl who had visited the Five Islands of Louisiana between 1857 and 1859, in 1860 described them with some care, noting their distinct character, alignment, and similarity, and ascribing to them a volcanic origin. He regarded them as being akin to the mud lumps in the delta of the Mississippi and was impressed by their symmetry and by the ponds or lakes which occur on several of the islands and which he regarded

Jan 1, 1920

By Donald D. Carr, Lawrence F. Rooney

Perhaps no other mineral commodity in this volume has as many uses as limestone and dolomite. These carbonate rocks are the basic building blocks of the construction industry, the material from which aggregate, cement, lime, and building stone are made. Carbonate rocks, and their derived products, are used as fluxes, glass raw material, refractories, fillers, abrasives, soil conditioners, ingredients in a host of chemical processes, and much more. Although the use of limestone and dolomite goes back before recorded history, new uses and products are continually being found. Carbonate rocks form about 15% of the earth&apos;s sedimentary crust and are widely available for exploitation. Found extensively on all continents, they are quarried and mined from formations that range in age from Precambrian to Recent. Reserves of carbonate rock are large and will last indefinitely, although high-purity deposits may be absent or have limited avail- ability in certain areas. Limestone and dolomite are so useful and so abundant that in 1972 more than 690 million tons were produced in the United States. In fact, about 75% of all stone quarried or mined in the United States was carbonate rock. Sand and gravel was the only mineral commodity produced in greater quantity. In this chapter we have sought to provide the general reader an overview of carbonate rocks, their composition, distribution, production, and uses, with emphasis on developments since 1960. In doing so we borrowed extensively from our recent report on the applied geology of limestone and dolomite (Rooney and Carr, 1971). The literature on the limestone and dolomite resources of the United States and Canada is so vast and diverse that one can easily become mired down in print. We tried to list those references that are easily accessible and that provide the economic geologist with a starting point for more intensive study. The table listing selected references on limestone and dolomite resources in Canada and the United States reflects our attempt to be selective rather than exhaustive and to direct the reader to the best sources of detailed information.

Jan 1, 1975

By Harold W. Aldrich, Walter G. Scott

The leaching process of the Inspiration Consolidated Copper Co. is based upon the solubility of oxidized copper in sulfuric acid and the solubility of sulfide copper, largely in the form of chalcocite, in ferric sulfate solution. This necessitates the carrying of a rather large amount of iron in solution. The ferric sulfate is regenerated from ferrous sulfate by the oxygen given off at the anode during electrolytic precipitation of the copper. In September, 1924, excavation was started at Inspiration, Arizona, for the construction of a plant to treat 7500 tons of ore per day. When the plant was begun, the fact developed that by a minor change in the height of the overflow on the leaching tanks, 9000 tons could be charged into each tank and treated satisfactorily. This determined the maximum capacity of the plant as 9000 tons per day. The first ore was charged in October, 1926, and there are now available the records of five complete years of operation; namely, 1927 to 1931, inclusive. The original estimate of copper content of the ore to be mined for this plant was 1.19 per cent, of which 0.77 per cent was as oxide and 0.42 per cent as sulfide. From the metallurgical results obtained at the 35-ton pilot plant, it was estimated that a 90.0 per cent extraction of the oxide copper and a 75.0 per cent extraction of the sulfide copper could be made. It was estimated that the tailing would carry 0.182 per cent total copper, resulting in a

Jan 1, 1934

By Oren C. Baptist, Carlon S. Land

Laboratory research has been conducted to evaluute the effect of clay hydration on the permeability to gas of water-sensitive reservoir sands. Samples of a .sandstone containing trace amounts of montmorillonite and a sample of montmorillonite were .studied in the laboratory to detertnine whether swelling or dispersion was the cause of permeability reduction in these samples. Heliuin, containing various amounts of water vapor, was used to hydrate the clay minerals and to determine the gas permeability at various stages of clay hydration. The amount of water adsorbed by the samples using this method is small. The nonwetting-phase permeability at higher water saturations war investigated by saturating the with water and measuring the permeability to humid helium while decreasing the water saturation, Relative-permeability curves obtained from results of these procedures were used to estimate the effect of the swelling of trace amounts of mont/tlorillonite on the permeability of the .samples. Most of the damage to the permeability when reservoir sands containing trace amounts of montmorillonite are exposed to fresh water is due to dispersion and movement of clays. Blockage of pores by the increased volume of expanded montmorillonite is believed to result in permeability damage that is small in comparison to the observed damage to the samples tested. INTRODUCTION Studies have shown that permeability is severely damaged when sands containing only small amounts of montmorillonite are contacted by fresh water.15 When samples of sands containing large amounts of montmorillonite are placed in fresh water in the laboratory, these samples may completely disintegrate, forming an unconsolidated mass of larger volume than that occupied by the dry sample." In this case, it is apparent that the swelling of montmoril-lonite has destroyed the pore structure of the sand. If only a trace of montmorillonite is present in a sand. samples may remain intact when saturated with water, although the permeability to water is a small fraction of the gas permeability of the dry sample. Many workers in the field of water sensitivity have attributed this reduction in permeability to the blocking of pores and reduction of pore size by the increased volume occupied by expanded mont- niorillonite. if the sand contains a detectable amount of montmorill&apos;onite or mixed-layer clay containing rnontmorillonite. Logically3 the smaller amount of montmorillonite present in a sand, the smaller should he the effect of montnlorillonite swelling on permeability; however, the quantity of montmorillonite sufficient to cause severe damage by swelling is not known. Although hundreds of samples have been tested in our laboratory, no correlation has been established between the amount of montmorillonite in samples and the permeability reduction caused by fresh water. To many petroleum engineers, the phrase "clay swelling" is synonymous with "water sensitivity", or "permeability reduction" implying that any formation damage due to the hydration of clays is caused by swelling. Although all clays adsorb water on their surfaces, montmorillonite is the only clay mineral commonly found in reservoir rocks which adsorbs water between intercrystalline layers, resulting in expansion of the clay particle. As montmoril-lonite swells, the first few layers of water adsorbed between platelets are strongly held and well oriented, and the montmorillonite retains its crystalline structure, although expanded. As swelling of sodium montmorillonite continues, the platelets become farther apart and the forces orienting the platelets in the crystalline structure become weaker, resulting in a less orderly orientation of platelets. In an abundance of water, small groups of platelets may become detached from the original monl-rnorillonite particle and may be dispersed throughout the water phase. Because of its swelling properties, sodium montmorillonite is very easily dispersed in water. Particles of other clay minerals. such as illite and kaolinite may also be dispersed in water. causing water sensitivity of sands not containing montmorillonite. The presence of an immobile layer of water adsorbed on the surface of clays has been considered a possible cause of the low permeability to water of dirty sands. Grim states that the thickness of the layer of immobile water held by sodium montrnorillonite is three nlolecular layers or 7.5 A (angstroms), with some orientation of water extending to 100 A. Assuming a very thick, immobile water layer adsorbed on the surface of a pore represented by a capillary tube, the maximum effect of the water layer on permeability can be calculated. Using a pore radius of 10 &apos; cm and an immobile water layer of 50 A. the calculation shows the permeability to be reduced only 2 per cent. Similar calculations can be used to show that the effect of electro-osmotic counterflow is of the same order of magnitude as that of bound water. The reduction of the permeability to water by either an immobile water layer

Jan 1, 1966

By Kenneth A. Moon

An exact statistical treatment of a one-dimensional model is used as a basis for evoluating the reliability of certain simplified expressions for the activity of the solute in interstitial solutions, including one obtained from the exact expression by setting the repulsive interaction equal to infinity. The latter approximation is found to be satisfactory at low and moderate concentration if the repulsive interaction is large, even though not infinite. A similar expression (identical if the co-odination number is two) is derived from the quasichemical expression of Lacher, and is recommended as the best available expression for the excess configurational entropy of interstitial solutions with excluded sites. Some reasonable models are discussed, and the nature of the saturated solutions is determined by inspection. Some of the models reduce to the one -dimensional case. An analysis is given of the excess partial entropy of hydrogen in V-H; Nb-H; and To-H solutions. MOST treatments of the statistical thermodynamics of interstitial solid solutions have followed the classic paper1 of Lacher in making the simplifying assumption that the configurational entropy of the solution is ideal. However, it is becoming increasingly apparent that there are many interstitial solutions with very large so lute-solute repulsions, and for these the assumption of ideal entropy is not valid or useful. It is important to realize that with substitutional solutions large repulsions between the component atoms must lead to phase separation, whereas in interstitial solutions the free energy of the solution is not drastically increased by large solute-solute repulsions until intrinsic saturation is reached at the concentration where further solute would be forced to enter a site in which it would experience the repulsive effect of one or more solute atoms already present. In the limiting case of an infinitely large repulsive interaction, the excess free energy would be attributable entirely to excess entropy, the enthalpy of mixing being zero. AS will be shown below, even if the repulsions are less than infinite, a treatment based on an assumption of infinite repulsions may be very satisfactory up to moderately high concentrations of the interstitial component. Often in solutions where large repulsive interactions exist, there are also small interactions — often attractive—between solute atoms in configurations other than that corresponding to the large repulsion. In such cases the excess free energy will consist of an excess entropy term attributable to the large repulsive interactions, and an enthalpy term corresponding to the other small interactions. Nomenclature to differentiate succinctly between important cases would be a convenience. In this paper the nomenclature shown in Table I will be used. In Table I, and in the preceeding discussion, excess quantities are defined in terms of standard states which are pure solid solvent and pure (possibly hypothetical) solid saturated phase of the structure in question. In practice, it is more convenient to choose the interstitial element as a component, and its conventional standard state. This will add a composition-independent term to the excess entropy and the enthalpy. The earliest paper known to the present author which treats the thermodynamics of athermal interstitial solutions was given by schei12 in 1951, but the statistical derivations in that paper are open to criticism. Speiser and Spretnak were the first to give a correct statistical treatment,3 limited, however, to concentrations sufficiently low that the number of empty sites excluded from occupancy by more than one filled site is negligible. The purpose of the present paper is to extend the statistical treatment to more concentrated solutions, and to examine the magnitude of the errors introduced by assuming that the repulsive interactions are infinite when in fact they must be finite. THE QUASICHEMICAL APPROXIMATION Fortunately, a standard method already exists for taking into account the effect of large interactions upon the entropy of mixing. This is the quasi-chemical method, in which the probability of existence of a given pair of solute atoms in a certain proximate configuration is assumed to be proportional to exp(-w/kT), where w is the energy increase of the solution when the two atoms are moved from isolated locations in the solution to the configuration in question. A quasichemical treatment of interstitial solutions was given in 1937 in a widely neglected paper by Lacher.4 The result comes out

Jan 1, 1963

By John K. Berry

The handling and disposal of mine water is a much larger problem than is apparent at first glance. Many more tons of water are removed from underground coal mines in the United States each year than tons of coal. In the old anthracite region of Pennsylvania the average was around 36 tons of water for each ton of coal produced, while bituminous mines average about 5 or 6 tons. Water encountered in the mines may come from several different sources. In mines with light cover and without a firm solid roof, rain may seep directly into the workings. This is also true of deeper mines where pillar falls have broken the roof to the surface. The top under creek beds is generally faulty and broken and water comes through the roof at this point. Deeper mines are frequently overlain by water-bearing strata and pillar breaks and faulty top can admit water, while places running to the dip often accumulate water which comes up through the bottom. In all cases, except where passing under a year-round stream, the amount of water made is usually pretty closely connected with the weather-more water during the rainy season, less in the dry, although the deeper a mine is, the longer it is before changes in rainfall are felt. Another source of water, not connected with seasonal changes, is old water, accumulated over a period of time in abandoned workings of the mine, or from flooded adjacent mines. Here the water filters through the coal, the parting, or comes up through cracks in the bottom. Similarly, core holes, drilled to prospect the property, can be a source of unexpected water and modern safety requirements for dust-allaying water at the working faces can turn a pleasant working area into a soggy mess over the weekend if the system is not properly maintained and operated. Why water must be disposed is obvious. If allowed to accumulate, sooner or later the mine will fill up, or at least it will become "roofed" in low places, blocking ventilation and traffic. But it must also be controlled long before it reaches this stage. Water standing in the working faces is unpleasant for the men who have to work there and also cuts down on the amount of work they can do, as they must watch where they step all the time. It is especially unpleasant in low coal.

Jan 1, 1973

By Fred P. Dewey

IN preparing material for the exhibit of the National Museum at the New Orleans Exposition in 1881, it was decided to attempt to photograph the interior of a coal-mine, in order to get a strictly truthful representation of a thick coal-seam, and to show incidentally the methods of mining. While we have many drawings, both mechanical and artistic, illustrating the subject, they are not satisfactory for these purposes, simply because they are drawings. Aside from this, much interest attaches to pictures of inaccessible places, and the enlarged copies (30 inches by 40 inches) of the photographs we succeeded in obtaining, have attracted a large amount of attention from the visitors to the Museum. The Kohinoor colliery, Shenandoah City, Pa., was selected as most suitable for the attempt, principally on account of the fine exposure of the Mammoth bed, and the comparatively level character of the workings, in that colliery. This is one of the many anthracite-mines of the Philadelphia and Reading Coal and Iron Company. A detailed section of the fiftyfoot or Mammoth bed in this colliery is as follows: Feet. Inches. 1 0 Clod. 1 7 0 Coal. 1 0 Slate. Top Split. 8 0 Coal. 1 6 Slate divider.* 6 0 Coal. 1 0 6 Slate. 2 6 Coal. 0 5 Slate. 1 8 Coal. 1 2 Charcoal. 5 0 coal. 1 0 Bone and Coal. „ „ Coal. [ Bottom Split. 0 6 Bone and Slate. 3 0 Coal. 0 10 Bone and coal. 1 2 Coal. 0 2 Bone. 4 4 Coal. 0 1 Bone. 0 8 Coal.

Jan 1, 1888

By J. L. Lytton, J. E. Dorn, L. A. Shepard

Single aluminum crystals were subjected to creep in simple shear on the (111) planes in the slip direction. The activation energies for creep were calculated from the effect of small abrupt changes in temperature on the creep rate just before and immediately following the temperature change. The results definitely establish the fact that creep of single aluminum crystals occurs by-three unique processes, characterized by thethree distinct and isolatable activation energies: The 35,-500-cal-per-mole activation energy obtained at the highest temperatures was ascribed to a dislocativationtion climb process; the 28,000-cal-per-mole activation-energy process, occurring over the intermediate-temperature range was attributed to a cross-slip mechanism; and it was suggested thot the 3400-cal-per-mole process observed below 400°K may be the Peierls energy. THE most pertinent question regarding the phenomenon of creep in crystalline materials is concerned with the identity of the crystallographic mechanisms of deformation that control the creep rate. For many years slight progress was made in uncovering the basic mechanisms for creep. Over the past 10 years, however, two parallel lines of investigations have contributed to a more definitive understanding of the processes involved in creep. The extensive development and maturing of dislocation theories for deformation of crystalline materials&apos; proved to be of paramount importance for this progress. And second in importance was the replacement of the former prosaic methods of creep testing by new techniques&apos;." which were especially

Jan 1, 1959