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By C. D. Stahl, E. E. Templeton, R. F. Nielsen

It has been customary, in predicting saturation changes, to use the Leverett fractional flow formula", obtained by eliminating the unknown pressure gradient from the generalized Darcy equations for the separate phases. The formula presents difficulties in the case of counterflow, since the "fractional" flow may be negative, greater than unity, or, in the case of a closed system, infinite. Recently, it has been shown by several authors that the corresponding equations (with capillary pressure and gravity terms) for actual flow of the phase may be used just as well. These equations are in agreement with Pirson's1 statement that, if the two mobilities differ considerably from each other in a closed system, the flow is largely governed by the lower value. The present study was undertaken because of an apparent lack of experimental data on gravity counter-/low with which to test the theory. A 4-ft sand-packed tube in a vertical position was employed. Electrodes for determining saturations by resistivity were spaced along the tube, one phase being always an aqueous salt solution. Air, heptane, naphtha, or Bradford crude oil was used for the other phase. A reasonably uniform initial saturation was set up by pumping the phases through the system, alter which the tube was shut in and saturation profiles obtained at definite intervals. Cumulative flows over certain horizontal levels were obtained by integration of the distributions; hence, differentiation of the cumulative flows with respect to time gave instantaneous flow rates. To compare experimental and theoretical flow values, capillary pressures were assumed given by the final saturation-distribution curve. The upper part corresponds to the "drainage" region and the lower part to the "imbibition" region, where trapping of the nonwetting phase occurred. While calculations indicated that the capillary pressure saturation function and, probably, the relative permeability saturation functions changed during the segregation, the relation of the measured rates to saturation distributions are in general accord with the frontal-advance equation. It appears that the Darcy equations, as modified for the separate phases, are generally valid for counterflow due to density differences. The usual method of predicting saturation changes, which involves a continuity equation and the elimination of the unknown pressure gradient from the flow equations, should therefore be applicable. However, the need for advance knowledge of drainage and and imbibition "capillary pressures" and relative permeabilities during various stages presents difficulties. INTRODUCTION The present study was undertaken because of a seeming lack of experimental data relating to vertical counterflow of fluids of different densities in porous media. In particular, it was desired to determine whether data obtained from these laboratory tests were in accordance with certain mathematical treatments of counterflow which have been proposed. The gravity "correction" has been incorporated into the flow equations (and, hence, into displacement theory) nearly as long as both have been used. field4 and laboratory5 data have generally borne out the validity of the theory as applied, for instance, to downward displacement by gas, with all fluids moving downward. However, the modifications for counterflow have only recently been pointed out. 2-3 It has been customary to use fractional flow rates instead of actual flow rates in displacement calcuIations. In the case of counterflow, this results in negative values, values greater than unity and, when rates are equal and opposite, in infinite values. As pointed out by Sheldon, et a1,3 and by Fayers and sheldon,2 actual flow rates may be used just as well. The fact that these may be of opposite signs for the two fluids does not present any difficulty.

By J. Brian Eby

The Gulf Coast of southern Louisiana during the year of 1940 was subjected to an extensive exploration and development campaign, as a result of which 16 oil fields and about 38 new producing sands were found. Although this record of discovery appears in keeping with the rate of 1939 actually in amount of new proven reserves, it may fall short of that of the previous year. Only five or six of the discoveries rated as first-class or important fields at the close of the year. The most prominent new fields opened during the year were Neale field in Beaure-gard Parish, the West Cote Blanche field in St. Mary Parish, the Stella field and the West Bay field in Plaquemines Parish, and the Lake Salvador field in St. Charles Parish. There were many important oil-sand discoveries in proven fields, such as in the Bayou Perot field, the Golden Meadows field, the Iowa field, West Lake Verrett field, and the Venice field. During the year, 1047 weUs were drilled in southern Louisiana, of which 768 were completed as oil-producing wells, 17 as gas wells and 262 as dry holes. The Neale field in northwest Beauregard Parish is considered one of the most important discoveries of the year. The f~eld centers around the north half of sec. 26, 'Y.3 S., R.I I W., just north of the town of Neale. It was discovered by the Atlantic Refining Co., using reflection seismograph to locate the structure. Production was found in the second well drilled in the Wilcox sand on the downthrown side of a fault. The structure is known as the "Tepetate" type, being similar to that of the well-known Tepetate field. There were 12 oil wells and 3 dry holes drilled during the year. The Wilcox sand in this field occurs between 8350 and 8400 ft. and averages 30 ft. in thickness. The West Cote Blanche Bay field, in West Cote Blanche Bay, St. Mary Parish, is a 1940 discovery by the Texas Company, credited to reflection seismograph exploration. The oil is from two sands occurring at 3110 to 3140 ft. and from 4950 to 5020 it. Four wells were drilled during the year, three oil wells and one dry hole. The deepest hole drilled reached 9491 ft. without encountering salt or dome material. In Plaquemines Parish, south of New Orleans, the California company has a new field known as the Stella field. The sand was found at a depth of 7485 ft., and 5 ft. of perforations made a well capable of producing 486 bbl. of oil in 24 hr. through a 9.is-in. choke. The oil is 42" gravity. The discovery well was drilled to a total depth of 10,258 ft. and other producing sands were indicated. A good field appears assured, although only one well was completed within the year. The Lake Salvador field, in the center of Lake Salvador, St. Charles Parish, gives promise of being one of the most important discoveries of the year. The discovery well was perforated at 9775 to 9800 ft. making 850 bbl. of 33.7° gravity oil daily through a 1/4-in. choke. Three wells were completed in 1940 but few details have as yet been made available.he Gulf Oil Corporation apparently has a good field in its wildcat discovery in West Bay, Plaquemines Parish. This well found

Jan 1, 1941

By M. Prats, D. G. Russell

The performance of a well in a bounded, layered reservoir with interlayer crossflow has been investigated mathematically. The system studied comprises a centrally located well in a bounded cylindrical reservoir composed of two layers of contrasting physical properties. The reservoir contains a single fluid of small and constant compressibility. In the case of a well producing at constant pressure, the production rate of the crossflow system declines exponentially after the early transient behavior dies out. For wells which produce with constant rate, the pressure-time relationship is linear following the transient. For very early production time, the production rate of the two-layer crossflow system behaves as that of the two-layer stratified system (the case in which the layers are in communication at the well only). Except for early time, in most practical cases the performance of a two-layer reservoir with cross-flow can be duplicated by that of a single-layer reservoir. The equivalent single-layer reservoir must have the same pore volume and the same drainage and wellbore radii as in the two-layer case. In addition, the equivalent reservoir must have a "kh" (permeability x thickness) product equal to the sum of the "kh" products of the respective layers in the crossflow system. If the porosity and permeability distributions are known, the production and pressure behavior of a well with and without crossflow can be predicted. From a comparison of the observed pressure or production performance of a well and the theoretical behavior, the occurrence of interlayer crossflow can be detected. INTRODUCTION When flow is possible across the bedding plane from a low-permeability layer into an adjacent layer of moderate or high permeability, the earlier depletion of the more permeable layer will cause such flow to occur. If this situation exists, the oil recovery from tight layers can be appreciable; thus, the economic ramifications of interlayer crossflow are apparent. The possible importance and extent of flow between adjacent and connected layers — whether resulting from capillary, gravitational, or viscous forces — have been the subject of considerable speculation for many years. Jacquard1 presented a rigorous analysis of the crossflow due to single-fluid expansion occurring between two adjacent and connected layers when the well produces at constant rate. His presentation was entirely mathematical, however, and no numerical results from evaluation of the mathematical solutions were presented. Our objectives in the preparation and presentation of the present paper are essentially twofold— (1) to analyze the behavior of a well which produces a single compressible fluid from a bounded, layered reservoir with interlayer crossflow, and (2) to present practical numerical results and simplified formulas to facilitate engineering analysis of reservoirs with crossflow. The constant-terminal-pressure case was analyzed rigorously, whereas the constant-terminal-rate case was treated only for semisteady-state conditions. DESCRIPTION OF THE IDEALIZED TWO-LAYER RESERVOIR The reservoir to be studied is assumed to be bounded and cylindrical in shape, with a completely penetrating well at its center. The reservoir is composed of two adjacent horizontal layers between which fluid is free to flow. Each layer is assumed to be homogeneous, isotropic and completely filled with a fluid of small and constant compressibility. The total thickness of the reservoir is small enough

By W. O. Philbrook, K. Natesan

A mathematical model was derived for the temperature change in a particle undergoing heterogeneous chemical reaction and heal exchange with a stream of fluid. The model has been applied specifically to the exothermic oxidation of spherical particles of zinc sulfide. Very good agreement was obtained between the theoretical prediclion and experimental observation. It was found that at no stage of the reaction was the particle subjected to a state of thermal instability. In studies of gas-solid reactions, it is generally assumed that the gaseous and the solid phases are at the same temperature throughout the reaction period. This is not strictly true since most of the reactions are either exothermic or endothermic in nature. This paper deals only with heterogeneous gas-solid reactions of noncatalytic type. In the case of exothermic reactions (e.g., roasting of sulfides), there may result an increase in temperature of the particle due to the release of the heat of reaction, and this increase in temperature may enhance the reaction rate and thus cause further release of heat. Such a "spiralling" effect may lead to a thermally unstable situation within the particle. On the other hand, in the case of endothermic reactions (e.g., calcination of limestone), there may occur a decrease in temperature of the particle as the reaction proceeds, leading to a virtual "quenching" of the reaction front. A general discussion of autothermic processes with emphasis on properties and reactor design is given by Van Heerden. 1 Levesque and cubicciotti 2 observed self heating of the sample in the oxidation of thorium. Anous et al. 3 observed self cooling of the sample in their dehydration studies on chrome alum. Cannon and Denbigh, 4 and Ong et al.5 reported self heating of the sample in their studies of the kinetics of oxidation of zinc sulfide. A typical plot of heat generation and heat loss rates with reaction temperature is shown in Fig. 1.'14 The Sigmoid curve represents the heat generation rate while the straight lines represent the heat loss rate. The main objectives of this analysis are to estimate the temperature increase of a single particle undergoing an exothermic reaction and to study the possibility of a thermally unstable situation within the particle. Also, a study of the dependence of the tempera- ture increase on different process variables has been attempted. A "she ll-by-shell" method has been proposed to analyze the problem. The shells may be made as small as necessary, and equations may be set up for heat transfer by various mechanisms. Such equations will have to be solved for each shell, with the boundary conditions for ith shell being obtained from the (i - 1)th shell, using a high speed digital computer. The oxidation of spherical particles of zinc sulfide is considered for this analysis, but the treatment is general enough to be applicable to other reactions and particle shapes. The oxidation reaction can be written as AH =« -115 kcal/mole ZnS [1] Such a reaction has been found to proceed in a topo-chemical manner; i.e., as the reaction proceeds, a progressively thicker outer shell of zinc oxide is formed, while the inner core of unreacted sulfide decreases. It has been found experimentally, both in the present work and in the previous investigations,4-6 that the particle retains its original dimensions. Therefore, at any given time, the particle may be

Jan 1, 1970

By B. H. Kear

Clustering of slip bands in different systems has been observed in both ordered and disordered Cu3Au crystals compressed in the <110> orientation. Certain features of the slip band patterns are explained in terms of reactions between dislocations with Burgers vectors at 120 deg; in a few rare cases, the slip band evidence suggests that the Products of such reactions form diffuse tilt boundaries between the differently slipped regions of the crystal, similar to the known behavior of ionic crystals, but not nearly so well defined. WHEN crystals with orientations favorable for multiple slip undergo plastic deformation, slip may occur in different systems in localized regions, so that clusters of slip bands are developed. This phenomenon has been observed in fee1-4 metals and also in ionic crystals having the sodium chloride structure.5-8 In the ionic crystals, the boundaries formed between the differently slipped regions of the crystal assume characteristic orientations and are associated with macroscopic tilts that are plainly visible on the sides of the crystal. Recently, this interesting feature was explained in terms of the formation of diffuse low-angle boundaries as a result of interactions between families of glide dislocations in the different systems meeting in the boundaries.9 This paper describes an attempt to obtain similar evidence for boundary formation in an fee crystal. The alloy Cu3Au was chosen for the present study simply because this material is currently being used in a general study of differences in deformation behavior of the ordered and disordered phases of this alloy, which will be described elsewhere. EXPERIMENTAL PROCEDURE The two specially oriented compression specimens used in the present study were prepared from a melt-grown single crystal by careful cutting, grinding and polishing. The finished specimens were about 6 mm by 2 mm in cross section by 6 mm tall, with their ends parallel to (101) and sides parallel to (111) and (121); the broad faces of the specimens were made parallel to (711). Both specimens were annealed in an evacuated quartz tube at 850oC for several hours, slowly cooled to 500°c, and then quenched into water in order to obtain the disordered state for the alloy. One of the specimens was partially ordered (with S- 0.8) by reannealing at 350oC for 100 hr. After these annealing treatments, both of the specimens were electropolished. 10 Finally, the specimens were compressed in the [loll orientation and their stress-strain curves were recorded. The deformation was carried out in increments of a few percent strain. At each stage in the deformation the specimens were unloaded, removed from the compression jig, and examined optically for slip bands. Before reloading, the specimens were repolished, so that the observed slip band patterns were characteristic of a particular stage in the deformation. EXPERIMENTAL RESULTS Fig. 1 show!; the stress-strain curves for the ordered and disordered specimens and also indicates the stages 1, 2, and 3 where the deformation was interrupted for examination of slip bands. The curves show marked differences in flow stress and in work hardening rate in the two specimens, as observed by previous workers.11,12 Also, it was found, in agreemement with the observations of Taoka and Sakata,&apos;3 that the plastically deformed disordered alloy showed the characteristic coarse slip bands of alloys, whereas the ordered alloy exhibited a fine slip band structure similar to that of pure metals. Slip Band Observations. In what follows, the description of the slip band patterns, with accom-

Jan 1, 1962

By H. Warlimont

Precipitation of cementite plates from carbon-rich austenite gives rise to localized formation of martensite in the matrix next to the precipitate upon quenching. The growth of this martensite is urmsually restricted. A distinct lattice relationship is found between this martensite and the cementite phase. It is concluded that the martensite is nacleated in the region of lowest carbon concentration at the austenite-cementite integace, with low-energy matching to the cementite lattice. The restriction of the growth of the martensite phase to the vicinity of the cementite plates can be explained by misfit in the austenite -martensite glissile interface and the uphill carbon gradient in the austenite. The investigation was carried out by light- and electron-microscopy and by electron-diffraction of thin foils. THE precipitation of cementite from carbon-rich austenite gives rise to a localized formation of martensite in the matrix next to the precipitate upon quenching. This behavior has been described previously by A. B. Greninger and A. R. Troiano1 for a 1.78 pct C steel ("pseudomorphic martensite"), and by A. Hultgren2 for a Fe-0.99 pct C—5.20 pct Mn steel. By measuring the axial ratio of the martensite phase,&apos; it was found that the carbon content of this martensite was lower than that of the martensite which formed without prior partial transformation to cementite. Therefore, it was concluded that lowering of the carbon concentration in the matrix next to the precipitate raised the M, temperature locally and thus led to nucleation of martensite at the ce-mentite-austenite interface. However, the restriction of the growth of the martensite phase to the vicinity of the cementite plates cannot be explained by localized carbon impoverishment alone. Under ordinary conditions a martensite plate which has been nucleated in a favorable site can continue to grow until it encounters a physical barrier, or until it encounters a compositional barrier in the matrix, where the total free-energy change for the reaction is not negative, since it has been shown by numerous experiments that the activation energy for growth of ordinary martensite is virtually zero.&apos; An investigation was conducted by transmission electron microscopy and electron diffraction to study this extraordinary martensite. It was expected that crystallographic in addition to compo- sitional conditions caused this abnormal mode of martensite formation. MATERIAL AND PROCEDURE An Fe-C-Mn alloy containing 1.15 pct C and 5.1 pct Mn was used for most of the experiments. For metallographic work, specimens 15 by 15 by 3 mm were used. For preparation of thin films, the initial specimen size was 15 by 15 by 0.7 mm. The heat treatment of each specimen consisted of austenitizing for 1/2hr at 1100&apos;~ in an argon atmosphere, subsequent isothermal holding in a lead bath at one of a series of different temperatures, and, finally, quenching into brine at room temperature. For metallographic examination, the specimens were mounted in bakelite (slight tempering effects resulted from the heat in the mounting press) ground, polished, and etched in nital. Thin films for transmission electron microscopy and electron diffraction were obtained by grinding the specimens to approximately 0.2 mm thickness and subsequent electrolytical thinning. The orientation relationships were evaluated from sets of electron micrographs and selected-area electron diffraction patterns of single units of the transformation products and the adjacent matrix. RESULTS In the alloy which was used for the experiments, proeutectoid carbide precipitates over a wide tem-

Jan 1, 1962

By R. E. Carter, C. Wagner, F. D. Richardson

By means of inert markers of radio-platinum, it has been shown that cobalt metal oxidizes by out-ward diffusion of cobalt atoms through the oxide. Oxidation rates have been measured at various temperatures and oxygen pressures and have been found to agree with the rates calculated from the Wagner equation and the authors&apos; values for the diffusion coefficient of cobalt in the oxide. The distribution of radio-cobalt in growing oxide loyers has been accurately measured and found to be different from that predicted from the Wagner oxidation theory. Attempts have been made to measure the change of lattice parameter of the oxide with composition. SEVERAL investigators have shown that cobalt metal oxidizes according to the parabolic law,1-3 but no detailed study has been made of the oxidation mechanism. Cobaltous oxide has a metal-deficient lattice, but the defect concentration which is dependent on the oxygen pressure is only approximately known.&apos; From the similarities in the structures of "CoO" and "FeO" and the rate laws governing the oxidation of cobalt and iron, Gulbransen- as suggested that cobalt, like iron," oxidizes by diffusion of cobaltous ions through the oxide layer. To substantiate this hypothesis, he has attempted to measure the oxidation rate of cobalt as a function of the oxygen pressure but has been able to report only that the rate depends on a "small" power of the pressure. On the other hand, Preece," Valensi,&apos; and Arkharov&apos; all have suggested from indirect evidence that oxygen diffuses through the COO to the metal-oxide interface. The present authors, in a previous paper,&apos; have shown that the rate of diffusion of cobalt in cobaltous oxide is dependent on the oxygen pressure. In that investigation, they also found that cobaltous oxide disks made by complete oxidation of cobalt metal were porous at their centers (Fig. 5L, ref. 4). Both these facts strongly suggest that oxidation of the metal proceeds via outward diffusion of cations. In order to establish the mechanism unequivocally, oxidation experiments were made with inert radioactive platinum markers, and the dependence of oxidation rate on oxygen pressure was measured. In addition, an attempt was made to determine the form of the cation vacancy gradient, which the marker experiment showed must exist across a growing oxide layer. This was done by depositing radioactive Co on the surface of a cobalt disk and then measuring the tracer distribution across the oxide layer produced by partial oxidation of the metal. Finally, an X-ray examination was made in an attempt to find the expected change of lattice parameter of COO with oxygen pressure. Experimental The apparatus and materials used were substantially the same as those previously described by the authors.4 Marker Studies: The use of inert markers to follow oxidation reactions was first attempted by Pfeil" in 1929, and radioactive markers have recently been used by Davies et al.&apos; In the investigation reported here, the markers were applied as an (NH4)2PtCI6 slurry in several thin streaks across both faces of four disks of cobalt metal 1 mm thick and 14 mm in diameter. The disks were then oxidized almost to completion at 1200°C in pure oxygen. After oxidation, they were mounted and sectioned and auto-radiographs were taken to locate the markers. Oxidation Rate: The oxidation rate of cobalt was measured at 1148°C at oxygen pressures ranging from 0.0055 to 1.0 atm and at 1000°, 1148", and 1350°C under 1 atm of oxygen. The rate was deter-

Jan 1, 1956

By C. S. Matthews, M. J. Fischer

Distortions caused by dip on five-spot sweep pattern were determined by visual experiments on a model composed of parallel plates of glass with holes drilled at the well positions. This model war designed to simulate a reservoir depleted of its primary oil and containing a gas phase. Prior to interference, it was found that the injected fluid took a nearly circular shape about the injection well for the cases studied. However, these circles moved down-dip considerably under the influence of gravity. It was concluded that pattern flooding should be practical for many dipping reservoirs. A quantitative measure is given of how much the well position should be altered to allow for dip. Experimental deternzinarions of injectivity showed this to be about the same in a dipping reservoir as in a horizontal one. INTRODUCTION This investigation was undertaken at the suggestion of the Pacific Coast area, Shell Oil Co., where a pilot water flood in a dipping reservoir was being carried out at the time this paper was in preparation. Prior to the undertaking of this flood there had been considerable speculation as to how gravity would distort a flood pattern in a dipping reservoir. The thought was expressed in some quarters that a five-spot flood would not be applicable to a dipping reservoir because the flood pattern would elongate in the direction of dip and would never form a "seal" around each five-spot. If the flood pattern elongated sufficiently, both the oil and the water might flow largely downdip rather than into the pattern producers. In view of the importance of the California water floods, it was deemed important to determine the effects of gravity on a five-spot pattern in a dipping reservoir. Previous work had also been carried out in this laboratory,1 but only for the single-fluid case. The present investigation extends these results to multifluid cases. Several sets of pictures of flood fronts are presented so that the process can be visualized. From these pictures, curves are obtained which show the correct drilling position for achieving equal times of oil-bank breakthrough. Several injectivity curves are also presented which may aid in prediction of injection rate. ASSUMPTIONS The present results were obtained with a model composed of two parallel plates of glass spaced about 1 mm apart. When the inertial forces are small, as in these experiments, the flow between the plates follows Darcy&apos;s law and is analogous to flow through porous media. In using these plates, it is not possible to scale effects of capillarity correctly as regards a transition zone between injected and displaced fluid. Calculations show, however, that effects of such capillarity should not be important in determining the gross flooding pattern in the field. In fact, in this model the capillary forces tend to circularize the pattern to a greater degree than in the field. To preserve a large ratio between the viscous forces and the circularizing capillary forces in the laboratory model, viswus glycerine was used as the flooding liquid and the rate of flooding was very high. The circularizing force is believed negligible in these experiments. In addition to the effect of the surface tension y, which tends to circularize the pattern, another capillary force must be considered. This is the adhesion tension y cos, which acts at right angles to the circularizing term y. If the plates in the model are "wetted" the same all around the periphery, then the adhesion tension,

Jan 1, 1957

By Danforth R. Hale, R. E. Blair

Minerals for electronic and optical uses divide easily into two sections: (1) quartz and (2) minerals other than quartz. Quartz Quartz, having a great usefulness discovered by the radio communication enthusiasts about 1918, has become a subject of amazingly expanded interest in the US over the past decade as a man-made mineral and a multimillion dollar crystal-growing business. An economic summary of the commercial growing of quartz crystals has a place in a handbook directed to the mineral engineering industry when it is remembered that quartz crystals have long been an important commercial mineral, and that the raw material for "cultured quartz"-that is to say, quartz crystals grown through the ingenuity of man-is still natural quartz. Nearly all the natural crystals come from Brazil. The larger pieces which meet rigorous standards of quality are used for electronic and, to a lesser extent, optical components. Smaller pieces and fragments are used for vitreous silica. The need for high quality material in quantity led to US government-sponsored research programs in the 1940s that have resulted in the factory growing of beautiful crystals of prescribed shape, size, and quality. The development of the cultured quartz crystal is typical of man&apos;s success in adapting the product of the mine to increasingly sophisticated uses. A remarkable achievement perhaps, but foreshadowed by experiments in 1908 by Giorgio Spezia (1908), an Italian geologist studying the relative effects of temperature and alkaline environment on the solubility of quartz. Modern radio equipment is most often controlled as to frequency by the presence in the circuit of a separately added "crystal"-the 1918 discovery responsible for the existence and growth of the quartz industry. The "crystal" is quartz, but this component is a carefully oriented and prepared slice from a crystal, but not a crystal as recognized by a rock hound or seen in a museum. How quartz operates to control frequencies is not a proper subject for a handbook on industrial minerals, and references should be consulted (Cady, 1964; Mason, 1964). Quartz belongs to that class of materials called dielectrics: those that do not conduct an electric current but permit electric fields to exist and act across them. Quartz shows the "piezoelectric effect," which means that when a quartz plate is mechanically deformed against its natural stiffness, one of its surfaces becomes negatively charged, the other, positively charged. When the plate is released from the stress quickly, the charges disappear as the plate regains its original shape, but because of mechanical momentum the plate deforms in the opposite direction (to a lesser amount) and the surfaces correspondingly become charged in the opposite direction. By coating the two surfaces thinly with metal and attaching flexible wires, these charges may be brought into an electronic circuit. If the surfaces are suddenly electrically charged by movement of current through the wires, the "converse piezoelectric effect" occurs -the plate deforms. Carry the thought further and it is realized that an alternating current flowing through the wires responds to the mechanical oscillation of the plate and is keyed to this oscillation. By controlling the thickness of the plate its mechanical vibration frequency can be varied through a wide range. One type of quartz plate, called the AT-cut, having a precisely defined orientation with respect to the crystallographic axes of the crystal, vibrates on a microscopic scale much as a book would deform when placed flat on a table and the top cover moved parallel back and forth with the hand. There are at least 17 other orientations which have been studied, some of

Jan 1, 1983

By Danforth R. Hale

Minerals for electronic and optical uses divide easily into two sections: (1) quartz and (2) minerals other than quartz. Quartz Quartz, having a great usefulness discovered by the radio communication enthusiasts about 1918, has become a subject of amazingly expanded interest in the U.S. over the past decade as a man-made mineral and a $3 million crystal-growing business. An economic summary of the commercial growing of quartz crystals has a place in a handbook directed to the mineral engineering industry when it is remembered that quartz crystals have long been an important commercial mineral, and that the raw material for “cultured quartz”- that is to say, quartz crystals grown through the ingenuity of man-is still natural quartz. Nearly all the natural crystals come from Brazil. The larger pieces which meet rigorous standards of quality are used for electronic and, to a lesser extent, optical components. Smaller pieces and fragments are used for vitreous silica. The need for high quality material in quantity led to U.S. government-sponsored research programs in the 1940s that have resulted in the factory growing of beautiful crystals of prescribed shape, size, and quality. The development of the cultured quartz crystal is typical of man&apos;s success in adapting the product of the mine to increasingly sophisticated uses. A remarkable achievement perhaps, but foreshadowed by experiments in 1908 by Giorgio Spezia (1908), an Italian geologist studying the relative effects of temperature and alkaline environment on the solubility of quartz. Modern radio equipment is most often controlled as to frequency by the presence in the circuit of a separately added "crystal"-the 1918 discovery responsible for the existence and growth of the quartz industry. The "crystal" is quartz, but this component is a carefully oriented and prepared slice from a crystal, but not a crystal as recognized by a rock hound or seen in a museum. How quartz operates to control frequencies is not a proper subject for a handbook on industrial minerals, and references should be consulted (Cady, 1964; Mason, 1964). Quartz belongs to that class of materials called dielectrics: those that do not conduct an electric current but permit electric fields to exist and act across them. Quartz shows the "piezo-electric effect," which means that when a quartz plate is mechanically deformed against its natural stiffness, one of its surfaces becomes negatively charged, the other, positively charged. When the plate is released from the stress quickly, the charges disappear as the plate regains its original shape, but because of mechanical momentum the plate deforms in the opposite direction (to a lesser amount) and the surfaces correspondingly become charged in the opposite direction. By coating the two surfaces thinly with metal and attaching flexible wires, these charges may be brought into an electronic circuit. If the surfaces are suddenly electrically charged by movement of current through the wires, the "converse piezoelectric effect" occurs -the plate deforms. Carry the thought further and it is realized that an alternating current flowing through the wires responds to the mechanical oscillation of the plate and is keyed to this oscillation. By controlling the thickness of the plate its mechanical vibration frequency can bevaried through a wide range. One type of quartz plate, called the AT-cut, having a precisely defined orientation with respect to the crystallographic axes of the crystal, vibrates on a microscopic scale much as a book would deform when placed flat on a table and the top cover moved parallel back and forth with the hand. There are at least 17 other orientations which have been studied, some of

Jan 1, 1975

By M. King Hubbert, David G. Willis

A theoretical examination of the fracturing of rocks by means of pressure applied in boreholes leads to the conclusion that, regardless of whether the fracturing fluid be of the penetrating or non-penetrating type, the fractures produced should be approximately perpendicular to the axis of least stress. The general state of stress underground is that in which the three principal stresses are unequal. For tectonically relaxed areas characterized by normal faulting, the least stress should be horizontal; the fractures produced should be vertical with the injection pressure less than that of the overburden. In areas of active tectonic compression, the least stress should be vertical and equal to the pressure of the overburden; the fractures should be horizontal with injection pressures equal to or greater than the pressure of the overburden. Horizontal fractures cannot be produced by hydraulic pressures less than the total pressure of the overburden. These conclusions are compatible with field experience in fracturing and with the results of laboratory experimentation. INTRODUCTION The hydraulic-fracturing technique of well stimulation is one of the major developments in petroleum engineering of the last decade. The technique was introduced to the petroleum industry in a paper by J. B. Clark,&apos; of the Stanolind Oil and Gas Co. in 1948, and since then its use has progressively expanded so that by the end of 1955 more than 100,000 individual treatments had been performed. The technique itself is mechanically related to three other phenomena concerning which ah extensive literature had previously developed. These are: (1) pressure parting in water injection wells in secondary-recovery operations, (2) lost circulation during drilling, and (3) the breakdown of formations during squeeze-cementing operations, all of which appear to involve the formation of open fractures by pressure applied in a wellbore. The most popular interpretation of this mechanism has been that the pressure had parted the formation along a bedding plane and lifted the overburden, notwithstanding the fact that in the great majority of cases where pressures were known they were significantly less than those due to the total weight of the overburden as determined from its density. Prior to 1948, this prevalent opinion had already been queried by Dickey and Andresen,2 in a study of pressure parting; and by Walker,"&apos; who, in studies of squeeze cementing, pointed out that the pressures required were mostly less than those of the overburden, and inferred that the fractures should be vertical. J. B. Clark,&apos; in his paper introducing hydraulic fracturing, and later Howard and Fast," and Scott, Bearden, and Howard," also of Stanolind, postulated that the entire weight of the overburden need not be lifted in producing horizontal fractures, but that it was only necessary to- lift an "effective overburden," requiring a correspondingly lower pressure. Hubbert,7 in discussing the paper by Scott and associates, pointed out that the normal state of stress underground is one of unequal principal stresses; and in tectonically relaxed areas, characterized by normal faults, the least stress should be horizontal. Therefore, in most cases, fracturing should be possible with pressure less than that of the overburden and, moreover, such fractures should be vertical. Harrison, Kieschnick, and McGuire,8 also on the expectation that the least principal stress should be horizontal, argued strongly in favor of vertical fracturing. Scott, Bearden, and Howard6 observed that, when

Jan 1, 1958

By M. J. Pool, with Appendix by Larry Kaufman, R. W. Krenzer

Thermodynmic properties of the Cu-Mn system have been deterrrzined in the temperature range 973" to 1273°K by measuring the vapor pressure of manganese in equilibrium with alloys of compositions varying from 0.13 to 0.91 rnole fraction manganese using the Knudsen effusion technique. Activities of manganese calculated from the measured vapor pressures show large positive deviations. Calculated heats and entropies of mixing are positive with a maximum occurring at approximately 0. 7 mole fraction manganese. ThE investigation of thermodynamic properties of binary systems involving transition metals is of considerable interest at the present time. The incomplete subvalency electron levels of transition metals lead to unusual behavior in some alloys, and considerable information can be obtained by determining the thermodynamic characteristics of these systems and relating the thermodynamic behavior to observed physical properties. The Cu-Mn system, shown in Fig. 1,&apos; provides an example of an alloy system in which the determination of the equilibrium phase diagram and various physical properties has received considerable attention, but very little work has been done on measurement of the thermodynamic properties. Elemental copper and manganese have comparable electronegatives, atomic sizes, and cohesive energies, but differ in crystal structure. They form a continuous series of solid solutions only at high temperatures and the structure varies in a continuous manner from fcc at the copper-rich end to fct at the manganese-rich end.&apos; The purpose of this investigation was to measure the vapor pressure of manganese over a series of Cu-Mn alloys and from these values determine the thermodynamic properties of the binary system. Vapor pressure measurements were made in the temperature range 973" to 1273"K, remaining within the solid-solution region for each alloy studied. EXPERIMENTAL PROCEDURE The relative thermodynamic properties of solid Cu-Mn alloys were determined from vapor pressure measurements by means of the Knudsen effusion tech- nique. Several discussions of the theory can be found in the literature. In the case of copper and manganese, it is assumed that manganese is the only component subliming, so the vapor pressure of manganese over the various alloys can be determined directly by measuring the weight loss of the effusion cell. This is a valid assumption since the vapor pressure of manganese is about four orders of magnitude higher than the vapor pressure of copper in the temperature region of interest. The vapor pressure of manganese over the alloys at any given temperature is then related to the weight loss of the effusion cell per unit area per unit time. An upper limit of 1.5 x 10"s has been measured for the ratio of polyatomic to monoatomic molecules for manganese vapor in equilibrium with solid manganese at 1180°K, so it was assumed that manganese vapor is monoatomic. The effusion cells, fabricated from high-purity alumina, are 26 mm high, 18 mm OD, and have a wall thickness of 1 mm. Three different sized holes of 2.03, 2.54, and 3.18 mm diam were drilled in the lids from the inside face to minimize chipping, and the lids were then slip-cast onto the cells to provide a gas-tight seal. Alumina was selected for this particular application both because of its resistance to thermal shock and reaction with manganese vapor. In the ideal case, the orifice of the effusion cell should have a knife edge so that effusion through the orifice

Jan 1, 1970

By R. I. Jaffee, F. C. Holden, H. R. Ogden

Ti-Mn alloys were studied in order to determine the factors affecting the mechanical properties of &stabilized titanium alloys. The principal compositional factors have been found to be solid-solution strengthening, the martensitic transformation, and instability of the P phase. Structural factors, such as grain size and shape, were found to have more influence on ductility and toughness than on strength. THE alloys of titanium with the &stabilizing elements offer the chief hope for developing useful heat treatments. Conversely, the heat-treatment response possible with the p-stabilizing elements causes difficulties such as weld embrittlement and thermal instability during service at elevated temperature. Therefore, it is of considerable technical importance to understand the factors that govern the heat-treatment responses in these alloys, so as to be able to soften the alloys if they are embrittled by an adventitious heat treatment, to render them stable in service, or to harden them while maintaining adequate ductility and toughness. The Ti-Mn system is a good example with which to demonstrate the factors that govern strength and heat-treatment response in. a P-stabilized system. The region of the a-j3 transformation, after the work of Maykuth, Ogden, and Jaffee,&apos; is shown in Fig. 1. The a solubilities are low. This means that, in the two-phase a-p field, partition of manganese between the two phases occurs practically only to the P phase. The solid-solution effects are therefore chiefly the result of solution in the ,8 phase. The eutectoid occurs at 20 pct Mn and 550°C, and proceeds very sluggishly. It can be ignored in heat treatments in hypo-eutectoid alloys, except for long-time storage at low temperatures below the eutectoid temperature. Even here, there is some question that diffusion proceeds far enough to involve eutectoid decomposition. Three compositional factors bear on the mechanical properties and structure of titanium a-P alloys. These are: 1—solid-solution strengthening, 2—mar-tensite transformation, and 3—P instability. Combined with the purely structural factors of grain size and shape, these govern the properties of the alloys. Perhaps the most important factor is solid-solution strengthening. The facts that manganese dissolves in a titanium to a maximum of only 0.5 pct and most of the manganese partitions to the p phase dominate the structure and properties of the a-/3 alloys. Because of the overwhelming preference of manganese for the ,3 phase, the P phase is harder and the a phase is softer. The relative amounts of both phases may be modified by heat treatment in the a-P field as application of the lever rule in the two-phase field clearly shows. A critical temperature in the Ti-Mn diagram is 800°C. This is the P transus temperature of the 6.4 pct Mn alloy, which has the lowest manganese content which will form all retained-P phase on quenching to room temperature. Any quench performed from below 800°C will produce a structure consisting of only a, a plus retained P, or retained p, for alloys of the compositions used in this work. For alloys containing less than 6.4 pct Mn, any quench from above 800°C will always result in structures

Jan 1, 1955

By Frederick H. Williams

The object of this paper is to bring to the attention of those members of the Institute who are interested in the subject, a method for the estimation of manganese, which has been frequently used in the labratory of the Vulcan Steel Works during he last eight months, and which is deemed worthy of more general use. It is simply an adaptation of well-known processes, for the purpose of determining this element in pig iron and steel. In general, the method consists in precipitating the manganese as binoxide dissolving in dilute sulphuric acid in the presence of an excess of a standardized solution of oxalic acid, and titrating the remainder of the oxalic acid left unoxidized with permanganate of potash. For this method, therefore, two standardized solutions are needed, viz., a permanganate solution and an oxalic acid solution. The permanganate solution is made so that 1 C.C. is equivalent to 1 mgr. of iron. By using so weak a solution and keeping tile bulk of the solution to be titrated down to 75 C.C. or a little leas, the accuracy of the process is greatly increased, since the final reaction is almost if not quite as sharp as if a stronger solution were used. The oxalic acid may be of almost any strength, but if made so that 1 c.c. requires 3 O.C. of the permanganate to oxidize it, it will auswer well. The process is then, as follows: from 1 to 2 grams of. pig iron or steel ate dissolved in 40 to 50 C.C. of concentrated nitric acid with the aid of heat. As soon as solution is erected, in the awe of steel, add gradually and cautiously, the solution being kept boiling, sufficient pulverized chlorate of potash to precipitate the manganese as binoxide. Two grams will be a great abundance. In the case of pig iron, first remove the carbon and silica by filtering the solution through asbestos and washing with concentrated nitric acid. Filter the strong acid solution in which the binoxide has been precipitated, through asbestos with the aid of the filter pump. When it has entirely passed through wash well with water. Blow the contents of the funnel into the beaker in which the precipitation was made and rinse the funnel with a little water.

Jan 1, 1882

By O. B. Hopkins

There was no noteworthy development in the oil industry in Peru during 1933 and all activities were restricted to the producing fields. The output of the country increased above that of previous years but there still remained a substantial shut-in production at the close of the year. The total production during 1933 is estimated at 13,259,891 bbl., of which the International Petroleum Co., Ltd. contributed 11,205,-362 bbl. A relatively small amount of new drilling was undertaken during the year. The International completed only one new well although a number of the old producers were reworked and deepened. Comments on Tables There are four oil districts in Peru, as shown in Table 1, although only three of these are now being operated. The exhausted Pirin field was abandoned eight years ago. La Brea-Parinus.—The La Brett-Parinas fields are on the property of the International Petruleum Co., Ltd. in the westernmost part of Peru. These fields include a number of producing districts that are defined by complex fault blocks associated with anticlinal folds. Data covering all the items listed in the table are not available on these fields but can perhaps be supplied in part in the future. Lobitos and Restin.—These two fields belong to the Lobitos Oilfields Limited and are near the coast, 10 to 20 miles north of the La Brea-Parinas fields. According to the Department of Mines and Petroleum of Peru, 311 wells at Lobitos and 197 at Restin had been drilled to the end of 1927. Since that date there has been enough drilling to increase moderately these figures. The depth of wells is not available but it is believed that their average depth is slightly greater than in the La Brea-Parinas area. The productive horizons are of Eocene age. zorritos.—The Zorritos field is the northernmost in Peru and is operated by the Establecimiento Industrial de Petroleo de Zorritos. The field is on the coast about 70 miles north of Lobitos. The number of wells drilled in this field to the end of 1927 was 343, according to the Department of Mines and Petroleum of Peru. The depths of these wells are reported to range from 300 to 700 ft. The largest wells do not produce

Jan 1, 1934

By H. W. Reid

One of the outstanding features of the year was a further marked decline in the footage drilled. This is estimated at 169,000 ft., as against 218,000 ft. for the previous year, and 372,500 ft. in 1930. Owing to repair work and improved production methods, there was an increase of about 4.25 per cent in the amount of oil won, the production being estimated at 10,160,000 bbl., or an increase of 400,000 bbl. over 1931 and nearly 750,000 bbl. more than in 1930. (See Table 1.) At the end of November there were 28 rigs in operation. During the first 11 months of the year 54 new wells were started; the average depth of those completed was 2476 feet. Owing to the continued restriction of drilling programs there has been little of outstanding interest in the way of new plant or technique. The use of the acid bottle, for testing the verticality of wells while drilling, has increased considerably, and this is now in use in practically every well except the very shallowest. During the last six months of the year fairly extensive use has been made of electrical coring. The number of wells started in the Colony up to the end of November, 1932, was 1894. The average number of producing wells during the year was 789, or 41.7 per cent of the total. Of these, 214 were flowing wells, 473 pumping, 80 bailing or swabbing, and 22 were produced by air or gas-lift. Although the last category represents less than 3 per cent of the total, there has been a marked increase in the use of air or gas-lift as compared with 1931. During the year there were 16 companies engaged in producing oil, as compared with 14 in the two previous years. In addition to one small refinery which started to operate at the beginning of the year, the five existing refineries worked continuously. At the latter very little has taken place in the way of extensions, except at one in the Parry Lands—Pitch Lake—Point Fortin area, where extensive alterations and additions are in progress, including the building of a deep-water pipe-line pier. When this is completed there will be five loading terminals, all situated in the sheltered Gulf of Paria, or west, coast, capable of accommodating ocean-going tank steamers. There

Jan 1, 1933

By Eugene Jablonski

Statistical data on the Polish producing business are available only for the first half of 1939. Because of the invasion of the country during September by Germany and Russia all sources of information have stopped, and it is impossible to get even an approximate picture of the status of the industry after that date. The long declining trend of Polish production, which was finally checked during 1938, kept a further upward tendency during the first half of 1939, and there is good reason to believe that the upward trend would have been maintained. It is true, there was little hope of reviving the slowly dying Boryslaw field, although there still remained a slight possibility for an extension in its southwestern direction. Repressuring plans were still discussed, but. could not be put into effect because of extremely complicated and split-up lease ownership. The Gorlice-Lipinki ficld continued to be the main factor in the increase of the country&apos;s production. During the first half of 1939 this field received a further important extension in a southern direction. The Schodnica field continued to use repressuring with success. At the end of June, 21 exploratory wells were drilling, 14 of which were within thc Carpathians and 7 in the Miocene geosyncline of the Carpathian Foreland. All of the wildcat wells drilled within the Carpathians were on the struct,ural cxtcnsion of old established fields, but part of the wildcats of the Foreland were on new geological and geophysical prospects. The Opary gas field of the Foreland discovered last year has been further developed. The Government-owned Polmin completed its third gasser. This well penetrated two sands; the upper one, 118 ft. thick, was found at 1312 ft., with an initial pressure of 570 lb. and capable of produeiring 10 million cu. ft. per day. The second sand, 91 ft. thick, was found at 1690 ft., yielding 20 million cu. ft., with a pressure of 760 lb. The well Mieczyslaw, drilled about 3 miles further north on the flank of the structurc, found the first sand watered. The Pioneer No. 5, at Chodonice near Przemysl, which reported somc gas last year, was 5696 ft. deep at the end of June, still drilling in Miocene. Anothe well in the same vicinity drilled by the Gasolina was 1708ft. deep.

Jan 1, 1940

By William P. Mason

FoR reasons unnecessary to enter into here, I was called upon to contradict the statement that " closed metallic vessels, partly filled with water and heated, do not become shattered by violent explosion, but simply rupture by over-pressure;" and the following experimental results were obtained in support of my position : A piece of drawn brass tubing (telescope-tubing) 1 1/2 inches in diameter and 15 inches long was closed at both ends by screwing on heavy caps of bronze. Before closing the second end the vessel was half filled with river water, the cap was then screwed on, and the closed vessel was supported upon two iron anvils, and heated in the interval between the supports by a large Bunsen lamp. The resulting explosion (which was doe to over-pressure only and not to any more occult cause) was exceedingly violent. No small damage was done to the room in which the experiment was undertaken; and the noise was like that of a cannon. Those of the pieces which could be recovered are shown in Fig. 1. Upon examining the wreck, it was noticed that one of the heavy bronze end-caps had preserved its circular section and still contained that portion of the barrel of the tube which had been screwed into it, while the other end-cap contained no portion of the tube, and was moreover sprung into a shape more or less elliptical, as if from excessive lateral strain. It was also observed that the large pieces of the shattered boiler predominated towards the end which had been closed by the un-sprung end-cap. The reasonable explanation, in view of the facts, was, that over-pressure had caused the boiler to yield through the screw-threads at A B, Fig. 2, and the righthand end-cap had blown off, thus leaving the boiler half filled with water, greatly super-heated for the new (atmospheric) pressure to which it was suddenly reduced; that this water had consequently sprung instantly into steam with dynamite effect, shattering the tube and springing the remaining end-cap. The large pieces would be expected at the open end of the boiler, as at that point the "tamping "would have been that of the atmosphere only. This explanation assumes a rupture to have been caused by gradually increased pres-

Jan 1, 1893

By Eugene Jablonski

Statistical data on the Polish producing business are available only for the first half of 1939. Because of the invasion of the country during September by Germany and Russia all sources of information have stopped, and it is impossible to get even an approximate picture of the status of the industry after that date. The long declining trend of Polish production, which was finally checked during 1938, kept a further upward tendency during the first half of 1939, and there is good reason to believe that the upward trend would have been maintained. It is true, there was little hope of reviving the slowly dying Boryslaw field, although there still remained a slight possibility for an extension in its southwestern direction. Repressuring plans were still discussed, but. could not be put into effect because of extremely complicated and split-up lease ownership. The Gorlice-Lipinki ficld continued to be the main factor in the increase of the country&apos;s production. During the first half of 1939 this field received a further important extension in a southern direction. The Schodnica field continued to use repressuring with success. At the end of June, 21 exploratory wells were drilling, 14 of which were within thc Carpathians and 7 in the Miocene geosyncline of the Carpathian Foreland. All of the wildcat wells drilled within the Carpathians were on the struct,ural cxtcnsion of old established fields, but part of the wildcats of the Foreland were on new geological and geophysical prospects. The Opary gas field of the Foreland discovered last year has been further developed. The Government-owned Polmin completed its third gasser. This well penetrated two sands; the upper one, 118 ft. thick, was found at 1312 ft., with an initial pressure of 570 lb. and capable of produeiring 10 million cu. ft. per day. The second sand, 91 ft. thick, was found at 1690 ft., yielding 20 million cu. ft., with a pressure of 760 lb. The well Mieczyslaw, drilled about 3 miles further north on the flank of the structurc, found the first sand watered. The Pioneer No. 5, at Chodonice near Przemysl, which reported somc gas last year, was 5696 ft. deep at the end of June, still drilling in Miocene. Anothe well in the same vicinity drilled by the Gasolina was 1708ft. deep.

Jan 1, 1940

By Ernest Gayford

This is a nontechnical paper on flotation, subdivided under three general headings: (I) Definition of flotation; (2) what flotation is now doing in Utah; and (3) what is the future of flotation? Definition T. A. Rickard defines flotation&apos; as "the act or state of floating," from the French flottaison, water-line and flotter, to float. The dictionary defines flotation as "the science of floating bodies." The flotation process is a method of concentrating ores by frothing. Weinig and Palmer,2 define flotation as follows: What is the flotation process? Briefly, it consists in the agitation of finely divided ore in water containing bubbles of air or gas, a small amount of oil and, usually, other reagents, soluble and insoluble; under these conditions the small particles of native metals, sulfides, arsenides, antimonides, selenides and tellurides show a tendency to attach themselves to the films of the bubbles, and are thus carried to the surface of the water. The oxidized gangue minerals, such as quartz, feldspar, limestone, hematite, etc., show much less affinity for the bubbles, are easily wetted by the water, and either remain in suspension in the water, or sink to the bottom of the vessel. If the bubbles are sufficiently stable they can be removed, carrying their load of sulfide-mineral particles with them. Thus there can be effected a separation of the two classes of minerals from each other, assuming that the grinding has been sufficient to unlock all of the particles of different composition. The separation does not depend upon differences in specific gravity of the various minerals; in fact, the sulfides are usually heavier than the oxides, and some of the heaviest sulfide minerals are the easiest to float. A particle of mineral may be so large, however, that its weight will counteract its affinity for the film of the bubble. In most cases the ore must be fine enough to pass a screen having at least 48 meshes to the linear inch. Taggart3 defines flotation as follows: Flotation is a method of wet concentration of ores in which separation of mineral from gangue is effected by causing the mineral to float at or above the surface of a body of liquid pulp while the gangue becomes or remains submerged. The method

Jan 1, 1928