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By M. Muskat, F. Morgan, R. G. Russell

Core experiments with radioactive tracers are reported in which an artificial radioactive material, radiovanadium, was used in aqueous solution in a study of the mobility of connate water. Sandstone cores saturated with active water were first oil-flooded to simulate virgin sand conditions in which the pores are filled with oil and connate water. They were then subjected to flooding with inactive water. Measurements were made of the activity of various portions of the effluent as well as the activity of the core after the flooding process was completed. In additional experiments the distribution of activity along the core was measured during the flooding process. In still other experiments direct flooding tests were made on cores fully saturated with active water. In all cases it was found that after injecting into the core a volume of inactive water equal to a pore volume, the effluent contained more than 80 per cent of the active content originally in the core. It is felt that these results imply a high degree of mobility of the connate water when subjected to flooding, although at least a partial contribution of the effect of tracer transfer within the core cannot be definitely excluded. The implications of this result with respect to water-flooding, core analysis and electric logging are discussed. A better approach to determining the connate water saturation of oil-producing rocks, by measuring the fluid content of core samples at the surface, is by the use of crude oil or oil-base muds as the coring fluid. Although water flooding is of considerable importance in the recovery of ail, comparatively little is known with certainty about the role played by the connate water during the operations. Two possibilities exist. Either the connate water is retained in the formation while the flood water sweeps past, or it is pushed along to a greater or lesser degree by the flood. Thus far no explicit recognition in terms of quantitative studies appears to have been given to the displacement of connate waters by the intruding extraneous waters, although such a possibility might be important in determining the efficiency of the oil -displacement process in water-flooding operations, especially in argillaceous rocks. On the other hand, it is a common observation that the first water produced with the oil as a result of water-flooding is definitely saline.*.' Similar questions regarding the mobility of the interstitial water arise in the quantitative description of the advance of edge-water drives. In the interpretation of the water saturations determined from core analyses, when coring with water-base muds, it is generally assumed that the drilling fluid merely adds to the connate water without displacing the

Jan 1, 1947

By G. R. Purdy, J. A. Malcolm

The isothermal dendritic precipitation of y in p CuZnSn is compared with the isothermal formation of Widmanstatten a plates in p CuZn. Although both precipitates are evidently bounded by semicoherent interfaces, the dendritic shape of y evolves through smooth "sinuoidal" shape perturbations, while a-p interfaces tend to be strictly planar, or rnicroscopically faceted. An estimate of the average inter-facial free energy of cube-oriented y in p through the Mullins-Sekerka analysis indicates that it is low (of the order of 50 ergs per sq cm). Interface mication is apparently controlled by volunle dij'usion, and the observed anisotropy in growth probably results from anisotropy of inter facial free energy. Studies of the grain boundary precipitation of y in p indicate that the precipitate can grow in both $ grains, but becomes unstable with respect to the grain with which it shares a mobile semicoherent interface. Facets observed at the tips of Kurdjumov-Sacks-oriented Wid-manstatten a plates correspond to variants of an irrational hahit, near (231)0. Comparison with Hu and Smith's determination of relative interfacial free energies of a-(3 boundaries suggests that this system possesses an extremely deep o cup, which results in an ej'ective low-o zone. The possible effects of such a cup on the stability of a-p interfaces are discussed, a needles, grown during rapid continuous cooling, possess microscopically smooth interfaces, and are characterized by a high degree of' damage in the region of the boundaries. These boundaries, induced to move on tempering at 200"C, become faceted as equilibrium is approached, which seems to indicate that boundary structure and mobility in this system are dependent on the local degvee of departure from equilibrium MULLINS and sekerkal have elucidated the phase boundary stabilizing effect of surface tension. a factor not taken into account in previous treatments of morphological development. Their analysis applies to the isothermal growth of a pure spherical precipitate (planar in the limit of infinite radius) in a slightly supersaturated solution, under conditions of inter-facial local equilibrium and isotropy of interfacial free energy. More recently, several other factors which might tend to stabilize planar interfaces have received attention. These are: i) interface diffusion;4"8 and ii) slow interfacial reaction. cahn7 included a slight anisotropy in interfacial free energy, and showed that it has no stabilizing effect, but forces shape perturbations to reflect the anisotropy. shewmon4 noted that dendritic morphologies are rarely observed in solid-solid systems, and, in particular, postulated that slow interfacial reaction occurs at all boundaries between proeutectoid ferrite and austenite, except those which propagate parallel to {11 l)y planes (for Kurdjumov-Sachs [K-S] related phases). Previously, Aaronson~ had proposed interfacial reaction at the broad faces of Widmanstatten plates, and expected that the lateral motion of high-mobility incoherent ledge edges would produce planar precipitates bounded by law-mobility semi-coherent interfaces. The problem of interfacial reaction during the dif-fusional formation of precipitates has often been ignored, although it is apparent that a small component of chemical reaction must exist at any moving interface." Further, all solutions of the diffusion equations for boundary conditions corresponding to isothermal growth predict infinite growth rate at time zero, so that elements of interfacial reaction would be most easily detected at early times. However, reported deviations from diffusion control are comparatively rare," and the local-equilibrium diffusion-control model appears adequate for the description of many isothermal growth systems.'2"9 Cahn14 has treated the problem of migration of an interface which is able to reach positional energy minima, and concluded that such an interface, if subjected to a high local ther-modynamic "driving force", may migrate normal to itself without the benefit of ledges. As local equi-

Jan 1, 1968

By L. S. Darken

It has been known for sometime that in an ionic lattice, such as that of Ag,S or FeO, the migration velocity of the anion may differ markedly from that of the cation, the cation being usually the more mobile. It has been shown, for example, that during the formation of silver sulphide tarnish on silver, the tarnish layer grows principally by the motion of silver cations through an essentially stationary silver sulphide lattice. Similarly, the growth of wüstite scale on iron proceeds principally by motion of iron ions, this being accomplished with the aid of vacant iron lattice sites into which the iron may readily move. Likewise investigations of solid solutions of various salts show that there is usually considerable difference in the mobility of the different cations. Measurements of the mobility of various metals in liquid mercury indicate that the various metals move at different rates relative to the mercury. In view of the foregoing it seems reasonable to suppose that when any single phase solution is acted upon by a field, the atoms of different elements respond in different ways; in particular, that the force arising from a particular concentration gradient in a binary alloy would cause the atoms of one component to move with a drift velocity which is in general different from that of the atoms of the other component. The recent experiments of Smigelskas and Kirkendall' support this viewpoint, since they found, in essence, that during diffusion in alpha brass zinc moves appreciably faster than copper. This was evidenced by the relative motion of inert molybdenum wires. Such a phenomenon is incompatible with the place interchange theory of diffdsion proposed by several authors, most recently by Bir-chenall and Mehl.2 This theory has, however, also been questioned3v4 for other reasons, principally because of the high energy required for direct atomic interchange. The rather large difference between self-diffusivity, as determined by tracer technique, and mutual diffusivity, as determined with the aid of another element at low concentration, might also be interpreted as favoring the above idea; however. Birchenall and Mehl have pointed out that there is another possible interpretation of this difference; this is discussed later. A rather interesting and pertinent observation was made by Schwartz, who noticed that tungsten lamp filaments, heated by direct current, commonly fail by necking down in the region at the temperature gradient near the positive end, with a concomitant swelling at the corresponding position near the negative end. He introduces considerable auxiliary evidence to show that this phenomenon is occasioned by the motion of tungsten cations which migrate in the high temperature region from the positive end toward the negative end. The mechanism of this migration is not clearly understood. If, however, this experimental evidence be accepted, we are forced to conclude that alloying elements in the tungsten may migrate by the same or a Similar mechanism, whatever it may be, at a greater Or lesser rate, thus giving rise

Jan 1, 1949

By L. S. Darken

It has been known for sometime that in an ionic lattice, such as that of Ag,S or FeO, the migration velocity of the anion may differ markedly from that of the cation, the cation being usually the more mobile. It has been shown, for example, that during the formation of silver sulphide tarnish on silver, the tarnish layer grows principally by the motion of silver cations through an essentially stationary silver sulphide lattice. Similarly, the growth of wüstite scale on iron proceeds principally by motion of iron ions, this being accomplished with the aid of vacant iron lattice sites into which the iron may readily move. Likewise investigations of solid solutions of various salts show that there is usually considerable difference in the mobility of the different cations. Measurements of the mobility of various metals in liquid mercury indicate that the various metals move at different rates relative to the mercury. In view of the foregoing it seems reasonable to suppose that when any single phase solution is acted upon by a field, the atoms of different elements respond in different ways; in particular, that the force arising from a particular concentration gradient in a binary alloy would cause the atoms of one component to move with a drift velocity which is in general different from that of the atoms of the other component. The recent experiments of Smigelskas and Kirkendall' support this viewpoint, since they found, in essence, that during diffusion in alpha brass zinc moves appreciably faster than copper. This was evidenced by the relative motion of inert molybdenum wires. Such a phenomenon is incompatible with the place interchange theory of diffdsion proposed by several authors, most recently by Bir-chenall and Mehl.2 This theory has, however, also been questioned3v4 for other reasons, principally because of the high energy required for direct atomic interchange. The rather large difference between self-diffusivity, as determined by tracer technique, and mutual diffusivity, as determined with the aid of another element at low concentration, might also be interpreted as favoring the above idea; however. Birchenall and Mehl have pointed out that there is another possible interpretation of this difference; this is discussed later. A rather interesting and pertinent observation was made by Schwartz, who noticed that tungsten lamp filaments, heated by direct current, commonly fail by necking down in the region at the temperature gradient near the positive end, with a concomitant swelling at the corresponding position near the negative end. He introduces considerable auxiliary evidence to show that this phenomenon is occasioned by the motion of tungsten cations which migrate in the high temperature region from the positive end toward the negative end. The mechanism of this migration is not clearly understood. If, however, this experimental evidence be accepted, we are forced to conclude that alloying elements in the tungsten may migrate by the same or a Similar mechanism, whatever it may be, at a greater Or lesser rate, thus giving rise

Jan 1, 1949

By R. W. Olson, A. L. Benham

Viscous fingering was studied as it occurred in an open Hele-Shaw model (1 ft x 4 ft x 1/16 in.); it was also studied in the same model packed with 80-mesh glass beads during miscible displacements under unfavorable viscosity ratio conditions. It was determined that the lengths of 20 elements of the front were distributed normally around the average position of the combined elements under all conditions. Represented by the normal distribution, the length of the viscous fingers grew linearly with the distance traveled from the point of finger formation, increased with displacement velocity, and increased with increasing mobility ratio. Results obtained during the first few inches of displacement were of little or no use in predicting finger growth and/or finger length throughout the 4-ft model since the point of finger initiation cannot be predicted and would often occur several inches from the point of injection with either positive or apparent negative coordinates. The fingering occurring during a miscible slug displacement was much greater than would be predicted based upon the actual mobility ratios between in-place fluid and slug and between slug and following fluid, using the results described above for miscible displacement in the absence of a slug. Many of the experiments in the packed model showed that the rate of growth of the viscous fingers was diminishing toward the end of the displacement in the 4-ft long model, indicating that microscopic mixing, such as diffusion or dispersion, was decreasing the viscous fingering effect. INTRODUCTION Viscous fingering is a manifestation of a finger-shaped interface between displaced and displacing fluids occurring during typical miscible displacement projects for oil recovery. Its cause may be traced to the instability of a viscous fluid being displaced by a more mobile fluid. Viscous fingering takes on important significance in the miscible slug process 1.2 where it may be a dominant factor in determining minimum slug size. Experimental1-3 and theoretical4-7 studies of viscous fingering have been made by other investi- gators. However, an exhaustive study of the variables affecting viscous fingering had not been made. The present study was undertaken in an effort to determine the effects of some of the more obvious variables—such as mobility ratio, displacement velocity, distance displaced, and packing—upon viscous finger length and growth in a small laboratory model. It does not necessarily follow that conclusions reached by studying the results of this model study may be applied to the field. Future studies would have to evaluate the effect of model size on extension of these results. EQUIPMENT AND EXPERIMENTAL PROCEDURES A flow diagram for the equipment used in this study is shown in Fig. 1. Basically, it consisted of (1) a constant-rate pump for the injection of displacing fluid into (2) a model made up of two flat transparent plates spaced a small distance apart and (3) provisions for the production of fluid into a calibrated graduate. The displacing fluid contained a dye which allowed visual observation of finger spacing and length. The pump performed at rates from 2.5 cc/hr to 480 cc/hr, while pumping a light mineral oil into a bladder in a closed glass container holding the displacing fluid. The model was made up of two plates of 1-in. Plexiglass with dimensions 1-ft wide by 4-ft long. These were spaced 1/16 in. apart so that the internal model dimensions were 1-ft wide x 4-ft long x 1/16

By P. R. Sperry, P. A. Beck, Hsun Hu

As described by means of quantitative pole figures, the inside texture of highly rolled aluminum and copper strips may be approximately described by four equivalent ideal orientations near (123) [121]. If rolled in reversed passes, the surface texture of copper is also near (123) [121], that of aluminum is (100) [011]. The inside texture of highly rolled brass is (110) [112]. The surface texture is the same, if rolled in reversed passes. The surface texture of all three metals is related to the inside texture, but asymmetrical, if rolled without reversal between passes. MANY previous investigations dealing with the subject of the present work were reviewed by Wassermann.1 Barrett,2 Brick,3 and Richards.' The recent introduction of quantitative methods for pole figure determination by Decker, Asp, and Harker,5 Schulz5 and others made it possible to reinvestigate some of the finer points which the earlier more qualitative photographic methods left undecided. The rolling textures of silver and of 70-30 cartridge brass have been quite consistently characterized by the ideal orientation of (110) parallel to the plane of rolling and [112] parallel to the rolling direction. On the other hand, it has been recognized by several investigators that certain other face-centered cubic metals, such as copper and aluminum, developed rolling textures rather different from that of brass. These textures have been variously described by the following ideal orientations, singly or in combinations with each other: (110 [112]: (112) [111]; (135) [335]; (135) [211], etc. The discrepancies usually have been attributed to the lack of sharpness in the textures and to the attendant difficulty of associating "ideal orientations" with pole figures showing great scatter of orientations. It seemed desirable to investigate by the new quantitative methods to what extent the apparent lack of sharpness may have been brought about by the qualitative methods used previously, rather than by the textures themselves, and to decide, if possible. between the various ideal orientations which have been proposed. Another problem, not satisfactorily settled by earlier investigations. concerns surface textures in rolled metals. For instance, in rolled aluminum the surface texture in some cases appeared to be similar to the texture inside the sheet, whereas in other cases it was reported to be entirely different.' The conditions under which such differences may have arisen, and the possibility of the occurrence of different surface textures in other face-centered cubic metals do not appear to have been examined in detail. The present work was undertaken to investigate the above questions. Some of the results obtained have been described- riefly. Experimental Procedure Specimen Preparation: In the present investigation 2s aluminum, electrolytic tough-pitch copper, and commercial 70-30 brass were used. These materials were available in the form of cold-drawn rods. 1 in. diam for tough-pitch copper and commercial 70-30 brass and 11/2 in. diam for 2s aluminum. The cold-drawn bars were alternately annealed and rolled 30 pct lengthwise in several cycles until a penultimate thickness of 0.500 in. was reached. The intermediate and the penultimate anneals were carried out for 30 min at 380°C with 2s aluminum, and for 30 min at 550°C with 70-30 brass. For tough-pitch copper, the intermediate anneals were 30 min

Jan 1, 1953

By F. B. WEEKS

I HAVE chosen for my subject a mining district which in an article published four years ago I referred to in the following words: "One of the un- usual anomalies of mining development and history is that a district having added thirty or more millions of wealth to a principal mining state, situated within four to six miles of two transcontinental railways and two auto highways, and within 150 miles of the most widely advertised part of the United States, should have been so completely lost sight of that probably not one mining man in ten can tell offhand where it is situated." But this district never was a dead one: it was only slumbering. During the past four months, day by day, it has been emerging from that state of slumber.

Jan 1, 1929

By W. A. Wall, R. L. Kidd

IN present-day flotation practice, grinding of the flotation feed is carried to extremely fine sizes, 70 to 80 per cent minus 200 mesh being customary. The greatest flotation losses occur in the coarsest and finest sizes, but the losses in the very fine sizes are, of course, much the more important because of the large proportion of fines in the feed. These losses are particularly high in zinc ores so a study of the effect of size on the flotation of sphalerite has been made. The mineral used in these experi¬ments was a pure sphalerite, especially free from copper, from the Joplin district in Missouri. The sizes coarser than 200 mesh were separated by screening, the sized mineral then being deslimed on a Wilfley table. The sizes finer than 200 mesh were obtained by water elutriation as described by H. R. Bradford (M. S. Thesis, University of Utah, 1932) ; particles finer than 6.5 microns could not be obtained with the apparatus used.

Jan 1, 1933

By C. W. Mueller, P. H. Robinson

A technique was developed for depositing single -crystal films of silicon on single-crystal sapphire substrates via the pyrolytic decomposition of SiH4/H2 mixtures. Electron diffraction and X-ray Laue reflection examinations of these films revealed single-crystal patterns. These films were characterized by measuring conductivity type, thickness, resistivity, and Hall mobility. Chemical etching, dislocation staining, and electron-microscopy examination have indicated the presence of low-angle grain boundaries and microtwinning in the silicon films. The role of the sapphire substrate with respect to its quality, orientation, surface finish, and thermal and chemical treatment was investigated. Hall mobility as a function of sapphire orientation was measured. A mobility equal to 88 pct of bulk silicon mobility was attained. Insulated-gate field-effect transistors which have a transconductance of 4000 pmho at 6 ma were fabricated using these films. THE technology of the fabrication of microelectronic circuits with active and passive components directly on a single wafer of semiconductor material has attained a high degree of perfection during the last few years. One inherent difficulty with the single-wafer approach has been undesirable coupling between components arising from the common base material. Several techniques have been developed for minimizing this coupling and obtaining good electrical isolation between components; however, these result in extra capacitance being added to the circuit. The extraneous capacitance of the connecting leads, resistors, and capacitors degrade circuit performance and limit the high-frequency operation of these circuits. Recently there has been considerable interestl-3 in the deposition of silicon films upon insulating substrates. The use of silicon as the semiconductor allows the subsequent utilization of the large amount of technology which has been developed for silicon for the fabrication of good active components. A sapphire substrate supplies an excellent insulating material which at the same time gives a thermal-conductivity improvement of an order of magnitude over glass-type substrates. This paper will describe the results obtained for the deposition of single-crystal silicon layers upon single-crystal sapphire substrates as well as the characterization of these films. I) APPARATUS The 'system used for the growth of silicon films on sapphire substrates by means of the pyrolysis of SiH4/H2 mixtures is shown in Fig. 1. The all-quartz reaction chamber is water-cooled and includes a quartz optical-flat window for use in conjunction with a 5 kw, 2.5 Mc per sec constant-temperature controlled rf generator. The temperature sensor for the rf generator is a thermopile which is focused through the quartz optical flat onto the susceptor surface. With this system the rf generator will hold the temperature of the susceptor to about +0.3°C at 1200°C. The susceptor is supported on a quartz sled inclined to the gas flow to increase the uniformity of the deposition. The water jacket surrounding the reaction chamber is used to keep the quartz wall temperature low enough to limit the decomposition of the silane to the rf-heated susceptor which contains the sapphire substrates. This eliminates the reaction of silicon with the hot quartz to form SiO which deposits out on the apparatus walls, thus obscuring vision, and interferes with the optical measurements of the temperature as well as with the growth process itself. Provision is also made for "n"- and 'p"-type doping by using mixtures of either phosphine or diborane in hydrogen which are added to the silane during the growth process. The hydrogen used is the purest commercially available tank hydrogen further purified by use of a palladium diffuser. The susceptors which were used include 1) spectro-scopically pure graphite, 2) high-purity molybdenum, 3) high-resistivity silicon using a low-resistivity insert to facilitate coupling to the rf generator, 4) silicon carbide-coated graphite. The latter two susceptor materials produced silicon films on sapphire substrates with more reproducible resistivities. Prior to silicon deposition all connecting lines as well as the reaction chamber are thoroughly flushed with argon and then hydrogen. After the hydrogen flow is set, the growth temperature is adjusted to 11009 to 1150°C, and when thermal equilibrium is reached the silane flow is started. The flow rate of the hydrogen must be fast enough so that turbulent flow occurs in the size of reaction tube used, otherwise a streaked nonuniform silicon deposit occurs. After the deposition

Jan 1, 1967

By Harold B. Janzen, M. A. Nobles

Campbell and Martin1 described a new exploratory logging tool which was developed as the result of a new concept of the phenomenon that takes place when a porous formation containing mobile hydrocarbons and irreducible interstitial water is invaded by mud filtrate. They postulate that invasion will create a bank of interstitial water between the flushed zone and the undisturbed formation. This postulate was confirmed by Wyllie.' Thus, if R,, is greater than R, and mobile hydrocarbons are present, the resistivity profile with increasing radii from the borehole is high:low:high, as shown in Fig. 1. If mobile hydrocarbons are absent, the bank of interstitial water is indistinguishable from the undisturbed formation and the resistivity profile, when R is greater than R,, is high:low, as shown in Fig. 2. The zone containing the bank of interstitial water and residual oil was named the "low zone". Campbell and Martin conducted extensive electrolytic wedge and resistivity analog model studies to select a logging system that would reflect the presence or absence of the low zone. The system they selected was that of a family of lateral curves. The model studies indicated that the presence of a low zone could be detected in approximately 60 to 70 per cent of the producing sand reservoirs with a family of lateral curves provided that the sonde effectively occupies 90 per cent of the diameter of the hole. These studies were conducted with D, = 5d. The presence or absence of the low zone is best determined by a plot of the apparent resistivity vs spacing as shown in Figs. 3 and 4. A dip or inflection in the profile that repeats at successive depth intervals is considered diagnostic. To reduce the shunting effect of the hole and mud, a sonde of insulating material that is surrounded by a series of flexible rubber bumpers was designed. The bumper efficiency is considered to be the ratio of the bumper diameter to the hole diameter. Field tests conducted by Campbell and Martin on 10 wells with a tool that provided for station readings indicated that dips or inflections could be detected in 19 out of 25 known producing zones. INSTRUMENT DEVELOPMENT Halliburton developed a logging system to simultaneously and continuously record eight lateral curves. The instrumentation is described in the literature.' The original logs made

By A. R. Calawa, T. C. Harman, M. Finn, P. Youtz

A study has been made of the growing, annealing, and diffusion parameters in PbSe, Pb1-ySnySe, and Pb1-xSnxTe. Single crystals of these materials have been grown using the Bridgman technique. For all of the above materials the as-grown crystals are p type with high carrier densities. To reduce the carrier concentration and increase the carrier mobility, the samples are annealed either isothermally or by a two-zone method. From isothermal anneals, the liquidus-solidus boundary on the metal-rich side of the stoichiometric composition has been obtained for some alloys of Pb1-xSnxTe and on both the metal- and seleniunz-rich sides for PbSe and alloys of Pbl-ySnySe. In Pbo.935 Sno.065 Se carrier concentrations as low as 5 x1016 Cm-3 and mobilities as high as 44,000 sq cm v-1 sec-1 at 77°K have been obtained. Inter diffusion parameters mere also studied. The ddiffusion experiments mere identical to the isothermal or two-zone annealing experiments except that the samples were removed prior to complete equilibration. The resulting p-n junction depths were determined by sectioning and thermal probing. Inter diffusion coefficients for various temperatures were calculated for both PbSe and Pb0.93Sn0.0,Se. RECENTLY, there has been considerable interest in the PbTe-SnTe and PbSe-SnSe alloys with the rock salt crystal structure. The unusual feature of these systems is the variation of energy gap EG with composition. Several investigations1-3 have shown that EG for the lead chalcogenides decreases as the tin content increases, goes through zero, and then increases again with further increase in tin content. The possibility of obtaining an arbitrary energy gap by selecting the composition is an especially attractive feature of these alloys for applications involving long-wavelength infrared detectors and lasers. In addition, some unusual magneto-optical, galvanomagnetic, and thermomag-netic effects should occur for alloys with low band gaps. If uncompensated low carrier density crystals can be obtained, then a small carrier effective mass, a large dielectric constant, and the resultant high carrier mobility should yield enormous effects at low temperature in a magnetic field. The relative variation of the energy gap with pressure should also be very large for these low gap materials. The primary purpose of this paper is to provide some information concerning the preparation of low carrier concentra- tion, high carrier mobility, and homogeneous single crystals with a predetermined alloy composition. I) DETERMINATION OF ALLOY COMPOSITIONS In all of the work described in this paper, the composition of lead and tin chalcogenides in the alloys was determined by electron microprobe analysis. Separate X-ray spectrometers are used to make simultaneous intensity measurements of the Pb La1 and Sn La1 lines emitted by the sample under excitation by a beam of 25 kev electrons focused to a spot about 2 µm in diam. These intensities are compared to the intensities of the same lines emitted by standards under the same conditions. The standards used are the terminal compounds of each pseudobinary system, i.e., PbTe and SnTe for Pbl-xSnxTe alloys, PbSe and SnSe for Pbl-ySnySe alloys. The composition of the sample is then obtained from theoretical calibration curves which relate the weight fractions of lead and tin in the alloy to the measured ratios of X-ray intensities for the sample and the standards. The lead and tin calibration curves for each alloy system were calculated by using corrections for backscattered electrons,4 ionization,5 and absorption,6 and assuming that the atom fraction of tellurium or selenium in the sample and standards is exactly +. Results obtained by using the microprobe are in good agreement with those obtained by wet chemical analysis. II) CRYSTAL GROWTH FROM THE VAPOR Early work on the vapor growth of PbSe was carried out by Prior.7 He used small chips of Bridgman-grown single crystals as the source material and frequently converted the whole charge of a few grams into one crystal. In the present work, vapor growth occurred using a metal-rich or chalcogenide-rich two-phased alloy powder as the source material. Small, nearly stoichiometric crystals are formed on the walls of the quartz tube. The procedure will now be described in detail. Initially, a 100-g charge containing (metal)o.51(chalco-genide)o 49 proportions or (metal)o.49(chalcogenide)o. 51 proportions of the as-received elements in chunk form are placed in a fused silica ampoule. After the ampoule is loaded, it is evacuated with a diffusion pump and sealed. The sealed ampoule is placed in the center of a vertical resistance furnace. The region containing the ampoule is heated to about 50°C above the liquidus temper-ature for the particular composition used. After about one-half hour at temperature, the elements are reacted and the molten material homogenized. The ampoule is quenched in water. The quenched ingot is crushed to a coarse powder for vapor growth experiments and to a fine powder for the isothermal annealing experiments which are discussed in a later section. Vapor growth experiments were carried out using the powdered, metal-rich or chalcogenide-rich alloys

Jan 1, 1969

By C. M. White

CITIZENSHIP is a rather abstract subject on which a great deal could be said-a subject on which a great deal is said -and still one which too many of us seldom think about and seldom work at. Too many of us engineers and business men have but a vague idea of citizenship. We think that if we go to the polls on election day and obey the laws scrupulously, with the exception of an occasional traffic violation, we are pretty good citizens and are doing our duty by our city, state, and nation. But when you think it over, that's a very passive observance of the important right of counting oneself a citizen of a country. There is nothing very positive in that attitude. There is nothing that indicates that we have sufficient interest to really go out and do a job for the -welfare of our country, forgetting any personal advantages or inconveniences that might arise. In other words, this type of voting-on-election- day, law-abiding citizenship does not keep us awake a single minute; it does not take any particular thought or require the expenditure of any time or energy.

Jan 1, 1939

By J. A. Ede

THE object of the writer is to call attention to a rather unique aggregation of economic products distributed over a line of succeeding formations about 3 mi. long, to be seen within a few miles of La Salle, Ill. Fig. 1 is an ideal section of the stratification exposed and exploited along a distance of 3 1/5 mi. in a southwesterly direction from the quarry of the Utica Hydraulic Cement Co. located near the historic site of Kaskaskia village to the Oglesby, shaft at Oglesby. No attempt has been made to cover the whole field, special mention only being made (with the exception of two places) of the operations found along the course or parallel to the direction assumed in the ideal section. I have used Fig. 2, after J. H. Bent and De Witt Kelly, to locate the relation of the La Salle anticline to the coal mines of this district and to show the operation of No. 1 and 3 mines of the Illinois Zinc Co.

Jan 9, 1919

By AIME AIME

THE quarters provided for the session on Milling Methods, Monday afternoon, Feb. 17, were filled to capacity. Galen H. Clevenger presided and notables, such as A. W. Fahrenwald, A. O. Gates, F. A. Thomson, W. L. Zeigler and others who had not graced a milling meeting in New York in recent years, or per- haps even never before, were actually present and spoke "in person." The first paper, by A. W. Fahrellwald (T. P. 275), entitled "Classifier Efficiency ; An experimental Study," was summarized by the author, who clearly showed the inconsistency of determining the efficiency of a classifier by means of sizing tests, especially where the material classified consists of a mixture of minerals of different specific gravities. In place of sieve analysis the procedure recommended involves the use of a glass settling-tube which is considered to give ideal classification and thus serve as a standard against which mill classification will be compared and relative efficiency calculated. This procedure sounds logical. Perhaps the greatest difficulty may lie in securing an ideal classifier acceptable to every one.

Jan 1, 1930

By Robert T. Gdagher, Allison Butts

EDUCATIONAL trends as reflected in curricular changes are of interest and importance in engineering educa¬tion both as matters of record and as considerations for the future. The data on which the evidence of this report is based were obtained by sending questionnaires to all schools in the United States granting the undergraduate degree in mining engineering, metallurgy, or metallurgical engineering. The questionnaire had two parts, one inquiring as to the general nature of revisions made or planned, and the other asking for information on specific courses added to or dropped from the curriculum, or given more or less time than formerly. The frequency with which curricular changes are made, even in normal times, is notable. Although it was expected that the period since 1939-40 would show numerous revisions, it was somewhat surprising to find that of 62 mining or metallurgical curricula in existence in 1939-40 and reported in the present survey, 58 had been revised or are shortly to be revised, 52 having already been changed during this period. Moreover, approximately half of the mining schools that have already revised their curricula, and probably a similar proportion of the metallurgical schools, are about to make further important changes.

Jan 1, 1948

By W. G. Sinclair

THE North Texas district presented in this paper includes the counties of Archer, Baylor, Clay, Cooke, Foard, Hardeman, Jack, Knox, Montague, Wichita, Wilbarger and Young. It corresponds with the Texas Railroad Commission's district No. 9. Table I conforms with the nomenclature of pools as designated by the Commission. Most of the oil and gas produced in this region, generally referred to as the Red River uplift, comes from the Pennsylvanian strata. In recent years, however, increasing amounts are being developed in both the Mississippian and Ordovician.

Jan 1, 1946

By W. G. Sinclair

The wartime momentum of exploration continued throughout the year 1945 despite the end of hostilities in mid-August. The table below illustrates drilling activity in the various categories: Completed wells. . . . . . . . . . . . . . . . . . . . . . . . 401 Wildcats.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .104 Wildcat discoveries, oil.. . . . . . . . . . . . . . . . . . . 2 Wildcat discoveries, gas-condensate.. . . . . . . 4 Development wells.. . . . . . . . . . . . . . . . . . . . . .297

Jan 1, 1946

By W. T. Weller

In Part I, a study of pressure build-up curves calculated for conditions under which both oil and gas flow led to the conclusion that the presence of a dispersed free gas phase in an oil reservoir must be taken into consideration to estimate accurately average reservoir pressure and permeability from build-up curves. Familiar methods based on the assumption of no free gas can be extended to the two-phase case by using total compressibility and mobility in place of single-fluid compressibility and mobility. These methods give correct values for average pressure and permeability when gas saturation is small. Errors become larger as the gas saturation increases. However, for the use to which the results will be put, the methods are satisfactory for reservoir engineering purposes. An improved method of calculating the performance of depletion-type reservoirs is presented in Part 2. Because the mathematical relationships describing simultaneous flow of oil and gas are quite involved. simplifying assumptions are made to provide means of obtaining approximate solutions of reasonable accuracy. One such approximate method now in use is the constant-GOR solution. It involves the assumption that at any instant, the ratio of total gas flow rate (both free and disolved) to oil flow rate is the same at all points in the reservoir. The approach is not applicable unless the free gar saturation in the reservoir is everywhere greater than the critical gas saturation. This paper presents a modification which, by avoiding the constant-GOR assumption, makes the method applicable to all reservoir conditions, and so far appears to be more accurate than the constant-GOR solution and to he comparable in required compuctation time. PART I— BUILD-UP CURVE ANALYSIS INTRODUCTION Pressure build-up characteristics of shut-in wells have been used for many years by engineers to evaluate average reservoir pressure, effective permeability thickness of the pay section, effectiveness of well completion (skin effect) and reservoir size. A number of methods of analysis have appeared from time to time."" Without exception, these methods are based on the assumption that the reservoir contains but one fluid of constant small compressibility and constant mobility. It has been suggesteda" hat these single-fluid methods may be applied to data from reservoirs containing both oil and gas by substitution of some effective total properties of the multiphase system in place of the corresponding single-phase properties. The present investigation was undertaken primarily to evaluate this approach. METHOD A number of theoretical build-up curves were calculated for conditions of two-phase flow, under the assumption of certain reservoir and fluid properties, and were analyzed by single-fluid methods with appropriate total compressibility and total mobility values for the corresponding single-fluid properties. Results of the analyses were compared with the assumed conditions. The theoretical build-up curves were completed by procedures similar to those of West, Garvin and Sheldon." Since these calculations require a considerable amount of computer time, an attempt was made to derive an approximate calculation method. The attempt was unsuccessful for calculating build-up curves, but the effort did result in a new approximate method of calculating the performance of solution gas drive reservoirs, which appears to be an improvement over the constant-GOR method" used previously (see Part 2). The West, Garvin and Sheldon calculations involved the following assumptions: (1) the reservoir is circular and completely bounded, with a completely penetrating well at its center; (2) the porous medium is uniform and iso-tropic, with a constant water saturation at all points; (3) gravity effects can be neglected; (4) compressibility of rock and water can be neglected; (5) the composition and equilibrium are constant for oil and gas; (6) the same pressure exists in both the oil phase and the gas phase; and (7) no afterproduction occurs, i.e., the well is shut in at the sand face for build-up. These assumptions make it possible to describe two-phase flow of oil and gas by the partial differential equations:

Jan 1, 1967

By S. A. Mersol, C. T. Lynch, F. W. Vahldiek

The microhardness of single crystals of tungsten disilicide has been investigated by the Knoop method. The average random room-temperature hardness of the WSi, matrix was 1350 kg per sq mm. Hardness crnisotropy was noted with respect to plane and indenter orientation as determined by single-crq.stal X-rny studies. Annealing at 1600" and 1800°C decreased the average hardness to 1310 and 1230 kg per sq tnm, respectively, and produced a second phase identified by X-ray diffraction and electron-microprobe analysis to be wSio.7. Ball-impact experiwzents produced rosettes at 850°C. Optical and electron microscopy showed evidence of slip and cross slip and twinning produced by microhardness indentations. Prismatic (100), [001] slip was found and cor~elated with hardness data. THE present study was undertaken to investigate the hardness anisotropy of as-grown and annealed single crystals of tungsten disilicide. The existence of the silicide WSiz in the W-Si system has been well-established and its structure thoroughly investigated zachariasen2 found WSi, to have a tetragonal C type of structure, similar to that of MoSi, with lattice parameters a = 3.212A, Kieffer et al. studied the W-Si system and measured the density and microhardness (at a 100-g load) of both polycrystalline WSi, and WSi,.,. The values found were 9.25 g per cu cm and 1090 kg per sq mm for WSi,, and 12.21 per cu cm and 770 kg per sq mm for WSi0.7, respectively. According to Samsonov et a1.5 the microhardness of polycrystalline WSi2 is 1430 kg per sq mm (at a 120-g load). EXPERIMENTAL The WSi, single-crystal boules investigated in this paper were grown by a Verneuil-type process using an electric arc by the Linde Division of the Union Carbide Corp.6 The largest specimens were 8 mm in diameter by 16 mm long. The crystals had an average density of 9.01 g per cu cm with a tungsten • silicon content of 99.9 wt pct. The major impurities were: 87 ppm O, 41 ppm N. 54 pprn C, 500 ppm Zr, 50 ppm Na, and 50 ppm Mn. The crystals were silicon-poor, the average silicon content being 22.20 pct (stoichiometric value is 23.40 pct), and tungsten-rich, the average tungsten content being 77.70 pct (stoichiometric value is 76.60 pct). As-received single crystals were ground and analyzed by powder X-ray diffraction technique using Cu Ka radiation. Laue and layer line rotation patterns were obtained on cleaved sections of WSi, single crystals. Electron-microprobe traverses of representative crystals were done using a Phillips-AMR electron microanalyzer. Carbon replicas were used to prepare electron micrographs. This work was done with a JEM-6A electron microscope. Prior to the metallographic examination, the specimens were mounted in Lucite and then polished for short times on polishing wheels using 9-, 3-, and 1-p diamond-grade pastes. Finally they were fine-polished with Linde A powder for 24 hr on a Syntron vibratory polisher. The samples were etched with 4H 2 O:1HF:2HNO3, which is a medium fast-acting etchant. The combination 1HF:2HNO3:5 lactic acid is also a satisfactory etchant. Annealing runs for selected specimens were made at 1600" and 1800°C for 3 hr at 1.0 to 3.0 x 10-5 mm Hg. A Brew tantalum resistance furnace with WSi2 powder for setters was used. The WSi2 powder was the same as that used for the crystal growth. Temperatures were measured with a calibrated W, W-26 pct Re thermocouple and a microoptical pyrometer. Powder X-ray diffraction, emission spectrographic, and electron-microprobe analyses were done after the annealing runs. For microhardness measurements a Tukon Microhardness Tester Type FB with a Knoop indenter was used. Although measurements were taken at loads ranging from 25 to 1000 g, the 100-g load was chosen as the standard load. All measurements were taken at room temperature. Only indentations of cracking classes 1 and 2 were considered.' DISCUSSION OF RESULTS Powder X-ray diffraction analysis showed the as-received crystals to be single-phase WSi2. Laue and layer line rotation patterns obtained on cleaved sections of WSi2 single crystals proved them to be tetragonal WS 2 2 The results also indicated that the c axis of the crystal was oriented parallel to the boule or growth axis. Electron-microprobe traverses across the matrix of the as-grown crystals showed them to be homogeneous WSi,. Optical and electron microscopy of etched crystals, however, revealed that they contained minute amounts of the "golden" and the "blue" second phases as opposed to the "white" or WSi2 phase. These two second phases were concentrated in inclusion and etch-pit

Jan 1, 1965

By F. F. Craig

Many full-scale waterflooding operations are preceded by pilot floods, one purpose of which is to provide an estimate of recoverable oil. A laboratory model study was made to determine the influence of the producing wells' effective productivity on the oil recovery efficiency of single five-spot pilots, as well as single injection well pilot floods. The effective productivity is indicated by the value of Condition Ratio, defined as the actual well productivity to that of on undamaged and non-stimulated, normal-sized well in the same formation. The effects of initial gas satrcration and mubility ratio on recovery eficiency were also investigated in this model study. Model test results skowed that at favorable mobiliry ratios, a five-spot pilot flood can provide a direct quantitative estimate of the recoverable oil in the pilot area. If the pilot producer's Candition Ratio is 2.2 or more, upwards of 90 per cent of the recoverable oil in the pilot area is recovered from the inside producer, regqrdless of the mobility ratio or initial gas saturation. This Condition Ratio can be achieved with preyent fracturing techniques. Model studies also showed that over the range of imposed injection pressure differences and regional pressure gradients normally encountered in field operations, there was no effect on the recovery efficiency of a five-spot pilot waterflood. Model studies of single injection well pilot waterfloods showed that with no initial gas saturation, the total oil recovery at the offset producing wells can indicate the oil recovery possible by full-scale waterflooding. It is essential that the Condition Ratios of the offset wells be above 1.4. If an initial gas saturation exists prior to water injection, the recoverable oil cannot be directly evaluated by a single injection well pilot flood. However, the production per formance of such a flood can be used to provide information on volumetric sweep efficiency. INTRODUCTION Oil reservoirs are conlplex structures and cannot always be fully studied in the laboratory. Therefore, many operators consider it prudent to evaluate a waterflood prospect by means of a pilot flood. Pilot waterfloods generally involve one of two well arrangements: a single five-spot pilot waterflood, involving four injectors and an internal pilot producing well; and a single injection well pilot flood (sometimes called an inverted five-spot pilot) having one injector and four sur- rounding pilot producers. Some pilot floods are composed of multiple five-spot pilot patterns. To yield information applicable to field-wide performance, the pilot must be located in a representative portion of the reservoir. Pilot floods generally are conducted for one or more of the following reasons: (1) to determine whether water could be injected at desirably high rates, (2) to determine whether an oil bank or zone of increased oil saturation is formed by water injection, and (3) to estimate the oil recovery by waterflooding. Many of the early pilot water-floods were conducted for only the first two reasons. As soon as a buzz in oil production was obtained in the pilot, water injection was initiated throughout the entire lease or field. A number ot laboratory studies have been directed toward determining conditions under which a pilot flood could yield a quantitative estimate of the oil recovery possible by full-scale pattern flooding. One of the early studies of single five-spot pilot flooding' showed that well damage to the inside pilot producer could reduce the total amount of oil recovered. In a study of the single injection well pilot flood pattern,' the results indicated that if the model boundaries were no closer than a half-well spacing beyond the pilot pattern, the pilot performance in the laboratory is unaffected by these boundaries. In another study,? he effect of initial gas saturation and mobility ratio on the ratio of production to injection rate for various groupings of five-spot patterns was defined by mathematical and analog methods. In a study4 involving both potentiometric and flow model experiments at a mobiliry ratio of unity, four different pilot patterns were studied. These included a single five-spot, a single injection well pilot, a cluster of four single injection well pilots and six inverted five-spots. In this study the ratio of well diameter to the distance between injection and producing wells was held constant at 1:1000. The effect of the 7 ratio-—the ratio of the pressure drawdown at the producing wells to the pressure build-up at the injection wells on the pilot performance-was studied. The values of 7 ratio ranged from 0 to 0.34. Results showed that both the total oil recovery and the total fluid production from the pilot relative to the cumulative injection increased with increasing values of the 7 ratio. The effect of both the ratio of injection to producing rates and mobility ratio on the oil recovery performance of a liquid-saturated single five-spot pilot flood was studied in a series of flow model tests.5 Rate ratios ranged from one to four, and mobility rates ranged from 0.1 to 10. Resulls of these tests showed that at low rate ratios, the pilot producers may recover up to four times the recover-

Jan 1, 1966