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By R. E. Collins, Paul B. Crawford

Potentiometric model studies have been made of ertically fractured reservoirs. All fractures originated at he well and extended into the reservoir for various distances. Studies were made to determine the areal sweep efficiencies for line-drive patterns. The areal sweep efficiency for the unfractured system studied war 70.6 per cent. It was found that if the vertical fracture war paralIel with the direction of flood, the areal sweep efficiency may be considerably reduced, approaching zero in some instances. If the fracture was at right angles to the direction of flood, the areal sweep efficiency may be greater than that for the unfractured system. The sweep efficiency depends on the length and orientation of the fracture and direction of the flood. It is concluded that considerable effort should be made to determine the nature and direction of fractures before initiating a flooding program. Such information is required if the maximum sweep efficiency is to be obtained and channeling is to be reduced to a minimum. INTRODUCTION The recent development and application of fracturing techniques to petroleum reservoirs has served to focus considerable attention on the effect such fractures may have on secondary oil recoveries. The opinion has been expressed that fracturing may not alter appreciably the water flooding possibilities. Others have thought that channeling may occur and that the creation of fractures may serve to substantially reduce the possibilities of conducting a successful water flood in the reservoir The purpose of this study was to obtain quantitative estimates of the effect of vertical fractures on the areal sweep efficiencies of line-drive flooding patterns. In presenting this work on vertical fractures, it is not to be inferred that the present fracturing techniques result in producing a vertical fracture. The types of fracture which are created are not known with certainty in every case. Some are believed to be horizontal, others inclined along bedding planes, and some data indicate vertical fracturing. Each fracture will probably exert a different influence on the sweep efficiency of the secondary recovery program; consequently each fractured well should perhaps be considered as a separate problem, requiring a careful analysis. Preliminary work on the effect of fractures on producing capacity of a well indicated that for practical purposes many fractures may be treated as having a nearly infinite permeability This assumption appears to be valid in some instances where the permeability of the fracture is only 10 or 100 times greater than the permeability of the matrix. It is known to depend on the type, orientation and length of the fracture. In realization that fractures of only 0.01 in. width have calculated permeabilities near 5,000 darcys, it is believed that many fractures may be considered as of near infinite permeability without incurring serious error. Primarily for this reason this study was made with fracture analogs of very great permeability compared to the matrix. FRACTURED SYSTEM ANALOG The pattern sweep efficiencies reported here were obtained with the aid of a potentiometric model. The application of this type model for solving reservoir problems has been described in the literature.1,2,3 The electrolyte reservoir was 20 in. wide by 30 in. long by approximately % in. deep. The liquid depth was constant, which corresponded to a constant permeability-feet product from the injection to the production well. The electrolyte reservoir was built to correspond to a unit in the line-drive pattern shown in Fig. 1. This figure shows part of an infinite array of wells having alternate rows of fractured and unfractured wells. The area within the dashed rectangle shows the area generally studied in the model. In using the model to represent a fractured system, a thin strip of copper was soldered to the well or wells and the length and orientation of the strip was made to conform to the vertical fracture under consideration.

Jan 1, 1955

By F. R. Cattoir, R. W. Kimball, C. T. Anderson

ONE of the principal impurities in all steels is sulphur. Sulphur-bearing, manganese-free steels exhibit hot shortness. Manganese is added to steel to improve the hot-working properties. If no sulphur were present in steel, it is probable that hot shortness would be nonexistent. This paper is the first of a series to be issued by this Laboratory reporting the measurements of hot forgeability tests and the physical properties of Fe-C alloys to which additions of various alloying elements have been made. The present paper describes the results- obtained by the addition of varying amounts of sulphur to Fe-C alloys. To obtain control over residual elements in the various charges melted in the arc furnace, it was considered advantageous to use sponge iron from one source as the melting stock rather than scrap metal having an unknown history. Small amounts of unwanted alloying elements might be introduced into the charge when scrap was used, thereby influencing the results of the various heats. A sponge iron having a high silica-lime ratio was used. Ore from Sunrise, Wyo., had been reduced to sponge iron and briquetted at the Bureau of Mines sponge-iron plant at Laramie, Wyo. The briquettes were 5 in. in diam and 2 to 3 in. in thickness, and weighed about 10 lb each. The chemical analysis of the sponge iron is as follows: C, 0.67 pct; Mn, 0.10; SiO2, 4.75; CaO, 1.4; P, 0.044; S, 0.72; MgO, 0.4; A12O3, 1.1; total Fe, 87.5; Fe metallic, 79.2; and reduction, 90.5 pct. Where a reducing agent was required, crushed graphite electrodes usually were used. The charcoal available contained 0.20 pct S. An analysis of the available coke showed it to contain 0.70 pct S. Where high sulphur heats were required, elemental sulphur additions were made to the ladle. Limestone of good quality was obtained locally and had the following analysis: CaO, 53.7 pct; MgO, 0.8; ignition loss, 42.4; R2O3, 0.2; SiO2, 3.0; and P2O5, 0.014. Melting Procedure Sponge iron was melted to produce metal stock for the experimental alloys in a silica-lined, three-phase, direct-arc, size ST, Moore Rapid Lectromelt furnace with a 500 kva rating. Fig. 1 shows this furnace installation. About 25 tons of sponge iron was melted in 75 heats, averaging 927 lb of sponge iron to the heat. An addition of carbon was required to complete the reduction of a portion of the iron oxide remaining in the sponge to prevent high losses of iron oxide in the slag and a low carbon content in the resulting metal. As reducing agents in preparing the melting stock, charcoal, coke, and a carbon product resulting from the thermal decomposition of natural gas were used. The quantity varied from 20 to 60 Ib per furnace charge, with an average of 38 lb. An average analysis of the metal obtained gave 0.52 pct C, about 0.01 pct Mn, 0.070 pct P, and 0.092 pct S. The average yield of metal was 647 lb with 241 1b of slag, the sponge-iron recovery being 70 pct. The metal obtained in melting the sponge iron was cast into pigs weighing about 20 lb each to facilitate recharging into the furnace for further refining. The pouring of the pigs is shown in Fig. 2. The average power consumption for the production of the 24 tons of metal obtained was 1704 kw-hr per ton.

Jan 1, 1954

By D. R. Walker, M. C. Shaw

Dimitri Kececioglu (Allis-Chalmers Manufacturing Co., Milwaukee)—The idea of applying metal cutting theory to comminution and vice versa is very impressive. Among others, the demarcation of wheel-grinding data into two regions, namely Kick's and Rittinger's, draws attention here. A study of Figs. 6 to 9 shows the following: In Fig. 6, 1 point out of 8; in Fig. 7, 4 points out of 26; in Fig. 8 only 1 point out of 13; and in Fig. 9 practically none out of 13 points fall out of curve No. 2. Also when grinding particles smaller than 5x10." in. it is difficult to measure very accurately the grinding forces, chip geometry, and particle size. In view of the above it would be difficult to make a positive and distinct demarcation of the Wheel-grinding data into two regions, namely, Kick's and Rittinger's. The idea of using machine grinding to determine the comminution properties of materials is indeed unique. The following cautions come to mind, however, regarding applicability of machine grinding data to comminution: 1—Grinding gives uniform particle size, whereas comminution gives a variety of particle sizes in the same process. The fact that grinding gives uniform particle size is not necessarily an advantage because in comminution the overall energy under actual comminution is desired and comminution invariably results in the production of a variety of particle sizes. 2—In grinding, a small particle is ground off a comparatively large surface. In comminution small bodies are broken down to smaller bodies. This makes it difficult to establish a concept of reduction ratio in machine grinding. 3—The mechanics of machine grinding involve direct shearing action under very high strain and comparatively high compression at the shear zone, whereas: comminution involves direct dynamic compression and surface friction with comparatively little strain and shear. Consequently the mechanics of machine grinding appear to be different from those involved in comminution. Hence one might arrive at erroneous con- clusions when comminution characteristics are eval-uated from machine grinding results. It is noticed also that functions other 'than Eq. 16 which do not involve the concept of direct proportionality of useful energy input to new surface area created (Eq. 2 and particularly Eq. 12) may be derived to fit the, data of curve No. 2. One such relationship may be u = ct-", where c is a positive constant and n is a positive constant less than unity. This, of course, is made possible because data of a very small range. of particle size are being fitted by the curves of No. 2 and the hereby suggested relationship. A sound comminution theory should be applicable to a relatively large range of particle size. George B. Clark (Department of Mining Engineering, University of Illinois)—While the experimental work of Walker and Shawin this article is of intrinsic value in revealing certain fundamental aspects of machine grinding, milling, and related processes and in adding to the store of information concerning the comminution of solid materials by this particular process, it appears doubtful that the results of their research can be employed to verify either Kick's or Rittinger's theories. Both these laws were originally developed and proposed on the basis of very simple, idealized hypotheses. The creation of parallel idealized physical laboratory conditions which would be required for either their proof or disproof appear to be well beyond the scope of human ingenuity, at least at present. One great weakness of the imputed verification is that the spread of the points plotted on the graphs is not sufficient to permit accurate 'curve fitting. The range of particle sizes included in the belt and wheel grinding is not extensive enough to show any general trends, particularly for the horizontal portion of the curves, said to represent Kick's laws. That the milling; grinding, and turning data obtained by Walker and Shaw for both metals and minerals happen to comply with. certain interpretations of these two theories under certain specialized conditions

Jan 1, 1955

By E. B. Burwell, R. H. Nesbitt

Designed by army engineers, the NX borehole camera provides the most economical method of subsurface exploration so far devised. Continuous cylindrical color photographs now reveal minor flaws in foundation bedrock not always disclosed by borehole samples. A unique projector transforms the photographs into true-to-scale images of three dimensions. ANEW milestone in the progress of photography and subsurface exploration was reached when the Chief of Army Engineers announced the development of the NX borehole camera. In obtaining continuous undistorted cylindrical color pictures of dry or water-filled borings the device surpasses all other cameras designed for photographing interior surfaces of pipes, wells, and conduits. The usefulness of the camera and the unique projector that comes with it are at once apparent. To the geological, mining, and civil engineer alike it signifies the end of guesswork with respect to underground conditions that have eluded identification by conventional core-drilling methods. To the medical profession it may well signal new progress in photo optics which could result in cylindrical color photographs supplementing the X-ray and existing photographic methods used in exploratory surgery. The pilot model of the camera has more than paid for itself as a result of its success in bringing to the surface at two dams information previously obtainable only by costly drilling of mansized boreholes for subsurface on-the-spot examination. Such bores cost as much as $200 per lineal foot as against $10 per ft for the conventional 3-in. or NX exploratory core borings from which the present invention derives its name. The NX camera can now photograph completely the interior surface of these borings. Research and development for the first camera and projection equipment were conducted by Engineering Research Associates, Division of Remington Rand, Inc., under the technical supervision of the Geology and Geophysics Branch, Office of the Chief of Army Engineers in Washington, in accordance with plans and specifications furnished by this branch. Subsequent modifications of the camera-lowering device, transporting equipment, and special field tools were made in the Corps of Engineers' Ohio River Division Laboratories in Cincinnati. The background of this development is interesting. Among the more difficult foundation problems involved in construction of concrete dams are those resulting from bedrock imperfections that escape disclosure by conventional exploration methods. Often these imperfections are of sufficient magnitude to introduce costly changes, especially when their presence is discovered only after foundation excavation is well in progress. Bedrock flaws most frequently camouflaged may be ruptures resulting from the enormous stresses to which rocks have been subjected, or they may be planes or zones of weakness related to chemical alteration and underground erosion. Obviously, detailed information on their location, dimensions, and structure is important, as these factors can affect the stability of a dam and the security of life and property downstream. Their discovery and appraisal entail extensive subsurface exploration. At present the most economical exploratory tool available to geologists and engineers is the small-diameter diamond core drill by means of which cores of the foundation bedrock are recovered for examination and testing. All too often, however, these samples fail to disclose minor foundation flaws that may be of major importance before a structure is completed. As a result, the small-diameter drillings are supplemented generally by more reliable but much more costly shafts, tunnels, or large-diameter calyx drill holes that permit the investigator to examine the foundation rocks in place. It was to reduce the number and cost of these expensive and time-consuming investigations, as well as to obtain more complete information on rock structure from the smaller borings, that the NX borehole camera was developed. That it has been eminently satisfactory in accomplishing that purpose is demonstrated by its success most recently at the Folsom dam, under construction on the American River, 23

Jan 1, 1955

By B. B. Wood, M. J. Rzasa, E. W. Hough

An apparatus for the determination of fluid-fluid interfacial tension by the pendant drop method has been constructed. The apparatus is refined beyond those previously described in that the samples are introduced into an evacuated windowed cell without contacting air or mercury. Interfacial tension data are reported for the water-methane system between 74 and 280°F and 15 and 15,000 psi. The variation of wettability of the stainless-steel dropper tip with pressure and temperature was observed incidentally to the measurements. INTRODUCTION The most refined previous apparatus --for the determination of fluid-fluid interfacial tension at reservoir conditions was built by Hauser and Michaels.' These authors used the pendant drop method, previously investigated by Andreas, Hauser, and Tucker.' Recently, Fordham3 has made the pendant drop method an absolute one by numerical integration of the differential equation of drop shape. It is necessary to know the difference in density of the two fluids and the acceleration due to gravity in order to evaluate the interfacial tension from measurements of drop dimensions. Contact angle is not involved in the measurements by this method. Some precise tests of the method have been made at atmospheric pressure and 77°F by Douglas," who found agreement with established values to within about 0.1 per cent for water and air, cyclohexane and air, benzene and air, and benzene and water. No values of interfacial tension from the recent pendant drop apparatusJ have been published by Hauser and Michaels. However, values for the water-benzene and water-decane systems are given in Michaels' thesis5 or Dressures from 15 .to 10,000 psi and temperatures from 73 to 268ºF. Some determinations on gas-oil and gas-water systems in the range of 15 to 4,000 psi and 78 to 178°F have been made by Hozott,' by the drop-volume method. The capillary rise method has been used to investigate the interfacial tension in gas-oil systems at 88°F to several thousand psi by Swartz.7 Other determinations in gas-oil systems at pressures under 1,000 psia have been made by Jones: and Beecher and Parkhurst.9 The scarcity of data for pressures above 5.000 psi is apparent. APPARATUS An assembly drawing of the working section of the interfacial tenqion apparatus is given in Fig. 2. 'The endanant drop (A) is housed in a pressure chamber having glass windows (B). An agitator (6) is provided. The metal parts of the apparatus coming into contact with the sample are made of AISI: Type 316 steel. Drain grooves are provided around the whdows so that the sample in contact with the O-rings is not returned to the working section when the pressure is reduced. A schematic arrangement of the apparatus is given in Fig. 3. The working section containing the pendant drop (A) is filled by samples from bombs (B) with the aid of the vacuum system (C). The O-ring sealed pistons (D) used to separate the sample from the hydraulic fluid are shown together with the pressure production and measurement system (E). A front view of the apparatus is shown in Fig. 1. Most of the hydraulic system is at the top of the panel. The pump and displacement piston are at the lower right. The Variacs for the air bath heaters. the camera. and the vacuum gauge are a1so visible on the panel. The working section together with a window closure and a drop-forming tip closure are shown in Fig. 9. The carbon arc light source with filter is visible in the upper part of the picture. Two sides of the air bath with the impeller and a part of the convection shield can also be seen. The assembled air bath is shown in Fig. 10.

Jan 1, 1951

By Bernhard Blumenthal

A melting process was developed by which high purity electrolytic uranium crystals can be converted into sound ingots without serious contamination. Careful preparation of the crystals, melting in a high vacuum, and directional solidification led to a metal of better than 99.993 wt pct purity. The metallographic examination showed a substantially clean metal with only residual amounts of a second phase which responded to heat treatment. The density of high purity uranium is 19.05 g per cu cm. FOR the study of the fundamental properties of uranium and its alloys, a base metal of high purity is needed, and an investigation was started at Argonne several years ago to examine various methods of preparing high purity uranium. Early success was achieved by the fused salt electrolysis process in preparing high purity metal in crystal form,' and the problem became that of melting the crystals into ingots without contamination. The electrolytic crystals contained a few ppm of heavy metals, less than 15 ppm C, and large quantities of potassium and lithium in the form of trapped fused salt electrolyte. On melting in vacuo in magnesia or urania crucibles, the metal picked up considerable quantities of carbon and some iron, copper, and silicon but lost most of the potassium and lithium. It was not metallographically clean, and much research work was necessary to determine the optimum melting conditions for minimum contamination. This work has resulted in the development of a melting procedure by which sound ingots can be prepared with only a limited contamination by carbon. In the section entitled "Melting of the Electrolytic Metal," the equipment and processes that have been developed for melting the electrolytic crystals are described in detail. The "Metallography" section is devoted to the metallography of high purity uranium, and the section "Density of High Purity Uranium" contains the first property measurement on high purity uranium—a density determination. Melting of the Electrolytic Metal Apparatus—Melting and Vacuum Equipment: Uranium may be melted in either resistance or induction-type electric furnaces. Resistance heating was found to be preferable to induction heating for melting down the electrolytic crystals, for several reasons: Although induction heating permits fast heating, this advantage cannot be utilized when crucibles with limited thermal shock resistance are used. Temperature control of induction-heated melts is poor, and the stirring effect increases the rate of contamination of the melt from the crucible, slag, or the furnace atmosphere; liquation and controlled solidification are difficult to carry out. Because of these objections, resistance heating was chosen. A 10 kw Globar resistance furnace of low heat capacity permitted uniform heating of a uranium charge to its melting point in 45 min. The furnace was insulated with a removable aluminum shield so that, after melting and removal of the shield, the furnace could be quickly cooled to room temperature. The furnace was equipped with an apparatus for directional solidification; see Fig. la. The crucible was suspended in the center of the furnace; and when the melting was complete, the crucible was slowly lowered into the cold end of the furnace tube. Solidification took place upward from the bottom; and when the rate of lowering was small, a sound ingot free from sink holes and shrinkage cavities was produced. To remove the large quantities of gas contained in the electrolytic crystals, melting in a high vacuum is mandatory. While, from the standpoint of contamination, melting in a highly purified argon atmosphere appeared feasible, lithium and potassium removal proved less efficient under such conditions. Also, a vacuum-melted ingot has a cleaner surface than one melted in an inert atmosphere. The vacuum system must be of very high pumping speed and leak tight so that a vacuum of less than 2x10-7 mm Hg is attainable when the system is pumped down cold. The system must have a high pumping speed, so that the pressure maximum which may rise to 1x10-4 mm during heating can be quickly reduced

Jan 1, 1956

By Mason K. Banks

A process has been developed which produces spodumene concentrates assaying 6.0 pct Li2O and 0.45 pct Fe2O3, with 70 to 75 pct recovery of spodumene. Two flotation separations are required: the simultaneous removal of mica, feldspar, and quartz as a froth product using a cationic collector, and the subsequent removal of iron-bearing minerals as a froth product while spodumene is depressed as a tailing. SINCE the close of World War II there have been numerous developments resulting in the increased use of lithium by industry. Notable among these has been the development of an industrial lubricant, based on lithium stearate, which is fluid at low temperatures, stable at high temperature, and insoluble in water. A new bleaching agent, lithium hypo-chlorite, has also been developed recently.' Other well-known uses are listed below: 1—Lithium oxide in ceramics reduces firing time, lowers melting temperatures, lowers thermal expansion, raises refractive index, and improves chemical resistivity. 2—Lithium carbonate and lithium strontium nitrate are used in pyrotechnics for their brilliant red color.' 3—Lithium chlorides and fluorides are used as fluxes for welding aluminum and magnesium.' 4—The affinity of lithium for nitrogen is the basis for a process used in purifying helium." 5— Lithium chlorides and bromides are used in air conditioning for their powers to absorb organic amines, ammonia, and smoke.6-—Lithium hydride has been used as a source of hydrogen to inflate life rafts and balloons used by the Air Forces and Navy.' 7— Lithium metal and lithium hydride are useful in the atomic energy program in connection with the production of the isotopes of hydrogen." During the 1942-45 period of World War 11, Solvay Process Co. operated a flotation plant with a daily capacity of 300 tons of ore for the production of spodumene concentrate near Kings Mountain, North Carolina. The operation was shut down upon reduction of wartime demand for lithium chemicals, and until recently there has been no production from the Carolinas. In April 1950 an investigation of the problem of spodumene flotation from North Carolina ores was begun at North Carolina State College Minerals Research Laboratory at Asheville, N. C. This laboratory, operating under the combined auspices of North Carolina State College, North Carolina Department of Conservation and Development, and the Tennessee Valley Authority, undertook the spodumene project at the request of Foote Mineral Co. of Philadelphia. The work, involving a period of 15 months of intensive batch and pilot plant investigation, was completed in June 1951 and resulted in development of a process for concentration of spodumene by flotation which has been hereto unrecorded in the literature. A similar approach has been used before on iron, ilmenite, and other minerals, but the literature shows no record of its having been applied to spodumene. Parts of the process are now being used on a commercial scale at the Foote Mineral Co. plant near Kings Mountain, N. C., which has been in production since July 1951. It is the purpose of this paper to describe some of the results of the investigation. The Orebodies Spodumene-bearing pegmatites occur in a narrow belt 24.5 miles long and 1.8 miles wide extending southwestward from Lincolnton to Grover, N. C. According to statements judged to be conservative, the tin-spodumene belt of the Carolinas contains an estimated 4,300,000 tons of pegmatite ore averaging 15 pct spodumene. This amounts to "a reserve of at least 650,000 tons of spodumene (more than 20,000 tons of metallic lithium) to a depth of 100 ft."' This figure includes only bodies having an average thickness of 35 ft and length of 550 ft. There are hundreds of pegmatites in the belt, many of which are less than 10 ft wide. The largest pegmatite in the area has a maximum thickness of 395 ft and maximum length of 3250 ft.' These larger pegmatites are composed principally

Jan 1, 1954

By J. R. Dawson, J. A. Glunt

VESTA No. 4 and 5 mines supply most of the high volatile coal required for Jones & Laughlin's byproduct coke plants. Until 1944 all coal produced in these mines was loaded by hand. Pressure to mechanize at Vesta was brought on by the manpower shortage in World War 11, and in 1943 a decision was made to change to mechanical loading. It was the opinion of those concerned that by use of selective mining the coal would be clean enough to be processed by the existing preparation plants. At that time coal cleaning at Jones & Laughlin consisted of hand picking the larger sizes at the mine tipples and wet washing at plants located at the Pittsburgh and Aliquippa Works. A typical section of the Pittsburgh seam as it occurs at Vesta is shown in Fig. 1. The 14 to 16 in. of drawslate immediately over the coal is too soft to be used for roof and must be taken down, leaving the rooster coal just above for roof. In selective mining an attempt is made to mine the coal under the drawslate first and then load out the drawslate separately as refuse. In full seam mining slate and coal are shot down at the same time and loaded out. Mechanical loading at Vesta created new problems. It was found that selective mining, even when carefully applied, increased the refuse in the raw coal to such an extent that the washers at the mills were unable to handle it. Large tonnages of refuse were being transported, a reject disposal problem was created, and good metallurgical coal was being loaded out and lost. In addition, the selective method handicapped operation of the loading machines. Fig. 2 shows how the ash content of the raw coal increased as mechanization proceeded at No. 5 mine. New Preparation Plant: After an exhaustive study of this situation by J & L management, is was decided that a preparation plant should be constructed at the mines, capable of handling full seam mined coal and large enough to process full production of both No. 4 and No. 5 mines. It was decided that from the standpoint of inside operation and haulage the new plant should be located as near as possible to the old No. 5 tipple on the Monongahela River near Vestaburg. Full seam mining at Vesta could be expected to produce a tremendous volume of refuse along with the coal, since 14 to 16 in. of slate would be mined with an average 78 in. of coal. Disposal of this refuse required serious consideration in selecting a plant site. The only area near Vestaburg large enough for disposal of the plant refuse was across the Monongahela River at LaBelle. Ample space was available here, and construction at this location would not interfere with operation at the No. 5 tipple. It had been noted over the years that the sulfur content of the coal produced at Vesta was gradually increasing, and there was every indication that this increase could be expected to continue as the mines developed further from the river. It was decided to construct a three-part separation plant with complete blending facilities to produce both metallurgical and steam coal. In this system an attempt is made to reduce the sulfur in the metallurgical coal in a secondary cleaning process. Construction of the new preparation plant got under way early in 1947 and continued until the spring of 1950. The plant was designed to handle 2400 tph of raw coal containing 30 to 35 pct refuse. Cost of outside buildings and equipment was about $14 million. Total cost of the plant, together with improvements and changes made at this time, was approximately $21 million.

Jan 1, 1957

By E. W. Hough, B. B. Wood, M. J. Rzasa

An apparatus for the determination of fluid-fluid interfacial tension by the pendant drop method has been constructed. The apparatus is refined beyond those previously described in that the samples are introduced into an evacuated windowed cell without contacting air or mercury. Interfacial tension data are reported for the water-methane system between 74 and 280°F and 15 and 15,000 psi. The variation of wettability of the stainless-steel dropper tip with pressure and temperature was observed incidentally to the measurements. INTRODUCTION The most refined previous apparatus --for the determination of fluid-fluid interfacial tension at reservoir conditions was built by Hauser and Michaels.' These authors used the pendant drop method, previously investigated by Andreas, Hauser, and Tucker.' Recently, Fordham3 has made the pendant drop method an absolute one by numerical integration of the differential equation of drop shape. It is necessary to know the difference in density of the two fluids and the acceleration due to gravity in order to evaluate the interfacial tension from measurements of drop dimensions. Contact angle is not involved in the measurements by this method. Some precise tests of the method have been made at atmospheric pressure and 77°F by Douglas," who found agreement with established values to within about 0.1 per cent for water and air, cyclohexane and air, benzene and air, and benzene and water. No values of interfacial tension from the recent pendant drop apparatusJ have been published by Hauser and Michaels. However, values for the water-benzene and water-decane systems are given in Michaels' thesis5 or Dressures from 15 .to 10,000 psi and temperatures from 73 to 268ºF. Some determinations on gas-oil and gas-water systems in the range of 15 to 4,000 psi and 78 to 178°F have been made by Hozott,' by the drop-volume method. The capillary rise method has been used to investigate the interfacial tension in gas-oil systems at 88°F to several thousand psi by Swartz.7 Other determinations in gas-oil systems at pressures under 1,000 psia have been made by Jones: and Beecher and Parkhurst.9 The scarcity of data for pressures above 5.000 psi is apparent. APPARATUS An assembly drawing of the working section of the interfacial tenqion apparatus is given in Fig. 2. 'The endanant drop (A) is housed in a pressure chamber having glass windows (B). An agitator (6) is provided. The metal parts of the apparatus coming into contact with the sample are made of AISI: Type 316 steel. Drain grooves are provided around the whdows so that the sample in contact with the O-rings is not returned to the working section when the pressure is reduced. A schematic arrangement of the apparatus is given in Fig. 3. The working section containing the pendant drop (A) is filled by samples from bombs (B) with the aid of the vacuum system (C). The O-ring sealed pistons (D) used to separate the sample from the hydraulic fluid are shown together with the pressure production and measurement system (E). A front view of the apparatus is shown in Fig. 1. Most of the hydraulic system is at the top of the panel. The pump and displacement piston are at the lower right. The Variacs for the air bath heaters. the camera. and the vacuum gauge are a1so visible on the panel. The working section together with a window closure and a drop-forming tip closure are shown in Fig. 9. The carbon arc light source with filter is visible in the upper part of the picture. Two sides of the air bath with the impeller and a part of the convection shield can also be seen. The assembled air bath is shown in Fig. 10.

Jan 1, 1951

By H. G. Doll

A new electrical logging method called Laterolog is described which provides for better recording of formation resistivity. In this method a current, preferably of constant intensity, is forced into the formation perpendicularly to the wall of the hole as a sheet of predetermined thickness by means of a special electrode arrangement and of an autonlatic control system. The essential advantages of the Laterolog over the regular resistivity logs are explained. With the Laterolog, the mud column has much less influence than with conventional methods. The Laterolog is, therefore. particularly useful in wells drilled with highly conductive mud. Moreover. when the electrode system is located opposite a bed of moderate or small thickness, the disturbing effect of the adjacent formations becomes practically eliminated, provided the bed is thicker than the sheet of current. which itself is usually a few inches to a few feet thick. The sequences of beds are. therefore, much more sharply differentiated, and, in many cases, it is possible to read directly from the logs values close to the true resistivities of the formations without further corrections. Field examples are shown to illustrate the results of the method in various types of formations. INTRODUCTION As soon as it was introduced into the petroleum industry, electrical logging roved to be a powerful instrument for the delineation of the strata traversed by bore holes and for correlation of such strata." Research and engineering efforts were mostly devoted at this early time to the design of the techniqurs which could provide the best data for these purpoes. Later, attention was directed toward the quantitative analy5i.s of electrical logs, in order to obtain information on. reservoir characteristics, and, in particular, on oil and water saturation.3,4 Efforts have been made, accordingly, with a view to improving the already existing methods, or to finding new methods which could satisfy these new requirements." Quantitative analysis implies a determination as accurate as possible of the true resistivity of the formations. In fact, however; the "apparent resistivity" recorded in front of a given bed by a conventional electrical logging method is frequently quite different from the true resistivity of this bed. This is due to the combined influence of the mud column, of the adjacent formations both above and below the bed, and of the invaded zone, in which the original fluid has been more or less replaced by mud filtrate. When the beds are thick enough, and, as is frequently the case in sand and shale formations, when their resistivity is not much greater than that of the mud, it is generally possible to obtain their true resistivity directly on the electric log, or at least to obtain an approximate value which can be corrected without undue difficulty by means of recently published charts known as "departure curves."" When the beds are thin, and particularly when, in addition. their resistivity is substantially greater than that of the mud column, the apparent resistivities recorded on conventional logs are seriously affected, and it is generally very difficult, if at all possible, to estimate their true resistivity with a good enough accuracy. In the most severe cases, such as are encountered in holes drilled through hard formations with muds of high salinity, the conventional logs are so distorted and rounded that they do not even show clearly the houndaries of the different beds. In order to overcome the effect of the mud column and of the adjacent formations, it is possible to make use of appro. priate systems whereby the measurements involve a comp3ratjvelv thin slice of space at the level of the measuring device. A mention is due, in this respect, to a measuring system. called the "guarded electrode;" invented by C. Schlumberger over 20 years ago. The system, schematically represented in

Jan 1, 1951

By C. Wachmann

The theory presented ill this paper makes possible examination of the phenomenological aspect of secondary oil recovery by alcohol flooding. Limitutions of the theory are contingent on three primary assumptions: (1) chemical equilibrium, (2) no fingering, and (5) no dispersion. The second assumption implies one-dimensional flow. In a geometric sense the theory extends the Buckley-Leverett construction to systems of two slightly miscible fluids and to systems of three components. This is made possible by considering single-phase fluids to be made up two phases, namely of an excess of one phase and a negative amount of the other phase. The procedure is discussed in the paper. The theory also permits direct determination of the relationship between the aqueous phase saturation and the concentration of water in the aqueous phase in a zone of variable composition. The velocity of planes of constant water concentration and of constant saturation can be computted likewise and the existence of saturation discontinuities inferred. Consequently the behavior of such a Zone, which may exist at some time between a displaced and a displacing fluid, May be determined. mathematical details are given in Appendices. Problems of experimental verification are pointed out on the basis of a supporting experiment. Implications of the theory and effects of violations of primary assumptions are discussed briefly. The major conclusion is that, if the primary assumptions are met, with pure alcohol and alcohol-rich .slugs piston-like displacement of oil and water is possible. INTRODUCTION The recovery of oil from porous media by alcohol displacement has been studied for several years. Extensive experimental investigations into alcohol flooding have been carried out in the laboratory although little has been done in the field. A large amount of practical information is available, the extent being indicated by the first three papers cited 1-3 and their respecrive bibliographies. This has permitted the Formulation of inferential theories. A more analytical approach in which theories are developed primarily by reasoning from known physical principles and relationships has, however, lagged behind. In fact, an analytically derived theory of alcohol displacement has not been available. The theory presented in this paper on oil and water displacement by alcohol from a porous medium is a result of the analytical approach. The theory is idealized, as certain assumptions had to be made to make the mathematics tractable and reduce complexity of argument. In particular, major assuptions concerning conditions of equilibrium, interfacial stability, longitudinal mixing, etc., led to the exclusion of fingering, for example, from all considerations. In many laboratory experiments reported in the literature fingering could not be avoided. There is, therefore, disagreement between theories based on experimental evidence available and the analytically derived theory presented here. This theory presented is based on known physical data and makes use of the Buckley-Leverett construction and its suggested extension. The mathematical derivation of the theory is given in Appendices. Three examples relevant to alcohol displacement are discussed to explain the use of this theory: (1) system of two immiscible fluids (the Buckley-Leverett case); (2) system of two slightly miscible fluids involving an extension of the Buckley-Leverett construction; and (3) system of three components, including injection of pure alcohol or alcohol-rich fluid as a special case, which involves a more general extension of the Buckley-Leverett construction. In these discussions strict assumptions were made to impose equilibrium conditions and exclude mixing and fingering. Effects of relaxing these assumptions and consequent extensions of the theory are indicated. The complexity of the alcohol displacement process makes experimental verification of the theory essential. Some relevant evidence is offered in this paper.

Jan 1, 1965

By Wallace W. Wilson

This DaoerAA calls to attention for the first time, to the writer's knowledge, a purported recovery of oil by substantially horizontal gas cycling that is considerably in excess of 50 per cent of the oil originally in place. The average angle of dip along the path of travel of the gas is less than one degree of arc. The best recovery by gas cycling previously brought to the writer's attention1 occurred in the case of the Mile Six Field in Peru, where about 68 per cent of the original oil in place has so far been recovered. In this case, however. the recovery was greatly aided 1)y the high dip angle of about 17.5". An approximate estimate of recovery was made by the method developed by the writer' for the case of the Cook Ranch Field, using an average relative permeability ratio function dictated by past experience with a number of good quality sandstones. A result of about 40 per cent recovery of the original oil in place wa* obtained after the 8.5 pore volumes of cumulative gas cycling undergone by the Cook Ranch Field. Tile writer desires to emphasize what appears to him as the sound engineering practiced at Cook Ranch, and also the care attending the taking of data and the high quality of the calculations made. It is impossible to take issue on factual grounds with any of the conclusions drawn in the paper. It is, however, desired to point out the difficulty of explaining the unexpectedly favorable oil recovery on ordinary theoretical grounds. It would be of interest to know whether relative permeability ratios have been measured on the Cook sand. The operator is inclined to attribute some of the excess benefit to settling of the oil across the bedding planes into the lower part of the sand. It is difficult for the writer to appreciate the importance of such an effect, inasmuch as the concomitant opening of excessive vacated pore space in the upper part of the sand would he expected to cause excessive bypassing of the gas. REFERENCE 1. Welge. H. J.: "A Simplified Method for Computing Oil Recovery by (Gas or Water Drive." Trans. AIME, (1952), 195, 91. AUTHOR'S REPLY TO MR. WELGE Welge has poined out clearly the difficulty of applying material-balance procedures in calculating the Performance of low-pressure, dispersed gas injection operations. There can be no argument that even with the most favorable assumptions of K,/K,, and with cumulative gas cycling in excess of normal expectations, the calculated oil recovery will be considerably less than the 72.5 per cent recovery realized from this project to Jan. 1, 1951. There probably are at least two reasons for the unusually high recovery from this reservoir, the effects of which would be difficult or impossible to calculate by known methods: 1. The operator did not use the same injection wells for the entire operation, and exercised considerable control over producing GOR by changing the locations of injection wells whenever well performance indicated excessive bypassing. Fifty-six wells were used for injection, not over 29 of which were in use simultaneously. This procedure resulted in frequent shifting of the fluid movement patterns in the reservoir and undoubtedly increased the ultimate recovery. The writer knows of no satisfactory procedure for calculating the effect of this practice. 2. Vertical movement of oil across the bedding planes of the reservoir rock hy gravity drainage tended to maintain a relatively high oil saturation, and hence a favorable K,/K, ratio, in the lower sections of the reservoir. As pointed out by Welge, this condition has aggravated the tendency for high producing GOR, but at the same time it has resulted in increased oil recovery. As may be seen from the performance charts for the various battery areas, operating (GOR'S have been quite high for the last several years of reported history.

Jan 1, 1952

By S. B. Casey

[ ] IN 1880, an electric arc was struck over metal for the first time to experiment with controllable melting. The glare of this arc has reflected on the stacks of the steel industry and continued to light the path of steelmakers in their never ending quest -for faster, more economical, and better ways of producing steel. William Siemens is credited with first employing the electric arc to melt metal in a closed hearth and produce basic metallurgical reactions. By the turn of the century, an Italian, named Stassano, was experimenting with ore reduction by the electric arc. In 1899, Dr. Paul Heroult, in France, used the direct arc principle for producing ferro-chromium. His experiments quickly led him to develop a dosed-top arc furnace for the production of steel, and his first commercial shipment was recorded in December, 1900. American steelmakers, quick to sense the possibilities of this method of melting, invited Heroult to our shores, where, in 1905, he was responsible for installing the first arc furnace on the North American continent. This furnace, at Sault Ste. Marie, was built for ore reduction. But Charles Holcomb, founder of Holcomb Steel. Co. of Syracuse, N. Y. contacted Heroult in 1905 and contracted for the first American direct-arc electric furnace for steelmaking. On April 5, 1906, the first heat was tapped from this 3-ton unit. The furnace was basic lined and powered by a single-phase, 500 kw generator, -producing high amperage at low voltage. It is interesting to note that, although the first few heats were made with cold charges, subsequent heats were duplexed. R. H. Bully, first superintendent of Holcomb Steel, persuaded the directors to purchase the unit to effect a more economical and efficient means of making tool steel by duplexing prime melting in a combustion fired furnace, and transfer of hot metal to the arc furnace for temperature adjusting, refining, and adding carbon and alloying elements. Today, duplexing is foreseen by some as the steelmaking process of the future. The promise shown by America's first arc furnace for ingot production quickly led to the purchase of a similar unit by The Firth Sterling Steel Co., in 1909, and to the purchase of the first arc furnace for production of steel castings, by the Treadwell Engineering Co., in 1911. From its humble start in 1906, production of arc furnace steel has never ceased to increase its yearly percentage of total steel production in the U. S., although certain other methods have declined or almost disappeared. By its ability to be used intermittently, the arc furnace gained favor and enhanced its reputation during depression days. When the attack on Pearl Harbor plunged us headlong into the long days of World War II, the arc furnace stood ready, flexible enough to be overburdened hearth wise 30 pct and power wise 25 pct, pouring its endless flood of alloy for the guns, tanks, ships, and planes which ultimately brought victory. During the post war boom, the now, proven virtues of low initial cost, faster installation, better yield, improved availability, and lower operating cost, enabled industry-particularly the small, new, independent producers-to locate strategically and profitably to meet the demand of an America that had been starved for new homes, appliances, cars, and highways. In the Korean police action, the arc furnace again proved itself by providing the latest alloys metallurgists could develop to meet the demands that the jet age and the innovations of guided missiles required. In today's peacetime prosperity, the arc furnace is continuing to provide the economic flexibility required to meet an ever increasing demand for better steel in the face of mounting costs, scrap shortages, and pressure toward decentralized location of industry.

Jan 1, 1961

By H. G. Doll

A new electrical logging method called Laterolog is described which provides for better recording of formation resistivity. In this method a current, preferably of constant intensity, is forced into the formation perpendicularly to the wall of the hole as a sheet of predetermined thickness by means of a special electrode arrangement and of an autonlatic control system. The essential advantages of the Laterolog over the regular resistivity logs are explained. With the Laterolog, the mud column has much less influence than with conventional methods. The Laterolog is, therefore. particularly useful in wells drilled with highly conductive mud. Moreover. when the electrode system is located opposite a bed of moderate or small thickness, the disturbing effect of the adjacent formations becomes practically eliminated, provided the bed is thicker than the sheet of current. which itself is usually a few inches to a few feet thick. The sequences of beds are. therefore, much more sharply differentiated, and, in many cases, it is possible to read directly from the logs values close to the true resistivities of the formations without further corrections. Field examples are shown to illustrate the results of the method in various types of formations. INTRODUCTION As soon as it was introduced into the petroleum industry, electrical logging roved to be a powerful instrument for the delineation of the strata traversed by bore holes and for correlation of such strata." Research and engineering efforts were mostly devoted at this early time to the design of the techniqurs which could provide the best data for these purpoes. Later, attention was directed toward the quantitative analy5i.s of electrical logs, in order to obtain information on. reservoir characteristics, and, in particular, on oil and water saturation.3,4 Efforts have been made, accordingly, with a view to improving the already existing methods, or to finding new methods which could satisfy these new requirements." Quantitative analysis implies a determination as accurate as possible of the true resistivity of the formations. In fact, however; the "apparent resistivity" recorded in front of a given bed by a conventional electrical logging method is frequently quite different from the true resistivity of this bed. This is due to the combined influence of the mud column, of the adjacent formations both above and below the bed, and of the invaded zone, in which the original fluid has been more or less replaced by mud filtrate. When the beds are thick enough, and, as is frequently the case in sand and shale formations, when their resistivity is not much greater than that of the mud, it is generally possible to obtain their true resistivity directly on the electric log, or at least to obtain an approximate value which can be corrected without undue difficulty by means of recently published charts known as "departure curves."" When the beds are thin, and particularly when, in addition. their resistivity is substantially greater than that of the mud column, the apparent resistivities recorded on conventional logs are seriously affected, and it is generally very difficult, if at all possible, to estimate their true resistivity with a good enough accuracy. In the most severe cases, such as are encountered in holes drilled through hard formations with muds of high salinity, the conventional logs are so distorted and rounded that they do not even show clearly the houndaries of the different beds. In order to overcome the effect of the mud column and of the adjacent formations, it is possible to make use of appro. priate systems whereby the measurements involve a comp3ratjvelv thin slice of space at the level of the measuring device. A mention is due, in this respect, to a measuring system. called the "guarded electrode;" invented by C. Schlumberger over 20 years ago. The system, schematically represented in

Jan 1, 1951

By Walter Crafts, D. C. Hilty

The liquidus diagram for the iron field of the Fe-S-O system has been derived experimentally. The solubility of oxygen in molten Fe-S alloys has been measured at several temperatures and found first to decrease slightly and then increase rapidly with increasing sulphur content. IT is well-known that the types, distribution, and amount of inclusions in any given steel are closely allied with the oxygen and sulphur contents of the metal, so that the term "deoxidation" as conventionally applied in steelmaking refers not only to the control of oxygen and oxide inclusions but to collateral modification of sulphide inclusions as well. Inclusions commonly occur in steel as mixtures of oxides and sulphides, sometimes closely associated and sometimes apparently completely divorced. Their effects on the properties of the metal may vary widely depending on their types and distribution as well as on their quantity. The mechanism by which inclusions form, however, and the means for controlling it are exceedingly complex and not well understood. Nevertheless, as described by Benedicts and Lofquist' and by Wentrup' all oxide and sulphide inclusions, excluding mechanically entrained matter, must result from specific modifications of the basic equilibria of the Fe-S-O system. In an investigation of the mechanism of deoxidation and inclusion formation being carried out at the Union Carbide and Carbon Research Laboratories, it became evident that quantitative data for the fundamental Fe-S-O system were essential to a better understanding of the problem. Consequently, the liquidus surface of the portion of the Fe-S-O diagram of interest in steelmaking has been determined, and the solubility of oxygen in liquid iron containing sulphur has been measured. Fe-S-O Diagram The portion of the Fe-S-O diagram of specific interest in steelmaking is the Fe-FeS-FeO corner. Of the contiguous binary diagrams for this partial system, only those for Fe-FeO and Fe-FeS are known with reasonable certainty.3 Several attempts to derive the FeO-FeS diagram have been made, chief among them being the work of Giani as reported by Oberhoffer,4 and, more recently, that of Vogel and Fulling." Although both Giani and Vogel and Fulling published diagrams for the FeO-FeS system, their observations indicated that the oxide component approximated Fe3O4 rather than FeO, so that there is doubt whether the system is truly binary. Benedicts and Lofquist and also Wentrup published qualitative sketches of the ternary diagram based on the assumption that it was of the type described by Marsh for a ternary system in which two of the contiguous binary systems are simple eutectic systems and the third exhibits a solubility gap in the liquid. Apparently, however, the only previous effort to establish the diagram experimentally was that of Vogel and Fülling whose results are reproduced in Fig. 1. Although defining approximately the limits of the miscibility gap and the location of the ternary eutectic, point E in Fig. I, Vogel and Fülling's diagram must be considered only semiquantitative. It was derived from a limited number of observations mainly along two quasi-binary sections, and the directions of the tie-lines and the location of the critical point, K in Fig. 1, were estimated by computation. Experimental Procedure The experimental technique employed for the present investigation involved melting mixtures of ferrous sulphide and ferric oxide in contact with iron. Since it was considered that in this part of the system the vapor pressures of sulphur and SO, are so low that they would not affect the results significantly, the melting was carried out in a current of argon to sweep out products of any initial re-

Jan 1, 1953

By K. Mukherjee

Instantaneous resistance change during martensitic transformation in Fe-30 at. pct Ni alloy has been studied using a low-noise electronic system. The smallest signals recorded in this investigation were of the order of 10 pv. These small signals did not show the initial increase reported by earlier investigators to support a double shear mechanism.&apos; A variety of pulse shapes and sizes was observed during "burst" transformations, and these signals were neither a linear function of the size of martensite plates nor of the volume fraction transformed. Even the smallest signals, presumably from single plates, showed complications resulting from elastic and/or plastic deformation, shock wave propagation, and so forth, which are inherent in the growth process of a martensite plate. The time of formation and interface velocity determined froni this experiment agree very well with the pioneering work of Bunshalz and Mehl.&apos; AN Fe-30 at. pct Ni (c0.005 pct C) alloy was used to study the time of formation of martensite plates. Martensitic transformations, unlike the nucleation and growth processes, are usually characterized by an extremely fast reaction rate. During the transformation, the crystal structure changes and this change is propagated through a finite volume of the parent crystal lattice within a very short time interval. The interface between the two phases probably consists of moving dislocations, and the time of formation of the plate depends on how fast this dislocation interface can move. Knapp and Dehlin~er or Cottrell and Bilby mechanisms, or similar dislocation models, can be used to calculate the time of formation of a martensite plate of a given size. In the past, conventional photographic technique475 as well as electrical resistivity techniques"~-" have been used to measure the time of formation of a martensite plate. The specific resistance of the martensitic phase in Fe-30 at. pct Ni alloy is lower than that of the austenite phase. Therefore if a current is passed through a small austenite sample in series with a large external resistance, then one would observe a voltage change across the sample as martensite is formed. Such dc measurements are shown in Fig. 1. The initial large voltage drop in Fig. 1, at the M, temperature, is due to a "burst" transformation where a large number of plates are formed in a cataclysmic manner within a very short interval of time. Even during the later stages of transformation as shown in Fig. 1, one can observe discontinuous voltage changes due to small bursts. In order to resolve the time scale of such discontinuous stages, the voltage signals are amplified and fed into a highspeed oscilloscope. In this investigation a low-noise amplifier was used for the first stage of amplification. The signal to noise ratio was further improved by the design of a pulse transformer. This transformer was capable of amplifying the signal by a factor of six. Voltage signals were studied over a wide time scale ranging from 2 sec to 0.1 psec. I) EXPERIMENTAL PROCEDURE A) Specimen Preparation. Specimens were cut from induction-melted Fe-30 at. pct Ni (<0.005C) alloy and cold-rolled to 0.2 by 1 mm cross section and an average length of 5 cm. During mechanical shaping, the specimens were strain-annealed at 950°C for 24 hr in vacuum. Finally the finished samples were vacuum-annealed at 1000°C for 6 hr and water-quenched to room temperature. The average grain diameter was 0.02 cm. B) Cooling System. The M, temperature of the alloy was -55°C. Fig. 2 shows the arrangement which was used to cool the specimen at a slow rate. The specimens were mounted inside a i -in.-diam hole in the 2-in.-long section of the copper specimen holder. This cavity was filled with silica gel. A dummy specimen was used under identical conditions for

Jan 1, 1969

By B. H. Caudle, B. M. Hickman, I. H. Silberberg

Secondary recovery projects often are not started in oil reservoirs until dictated by rising GOR&apos;s or declining oil production. Such circumstances require a well dispersed injection pattern to prevent the oil bank from bypassing the production wells. Many times this purpose is served by using the five-spot or line-drive patterns, in which half of the wells are made injection wells. A regular injection pattern is proposed that is based on the same well spacing as the five-spot but in which only a third of the wells need be converted to injection wells. Fluid flow model studies on this proposed pattern show that production histories will be as good as those for a five-spot pattern at mobility ratios of three and above. The model data are presented in a form that may be used to predict recoveries from both homogeneous and stratified formations. Introduction The injection of fluid into a petroleum reservoir usually is prompted by an actual, or predicted, loss in the productivity of the reservoir. Often, an oil reservoir is produced by pressure depletion until high GOR&apos;s dictate a change in policy. Fluid injection also causes increased ultimate recovery, but this usually is of less importance to the operator than is the maintenance of the production rate. It is a fact that the ultimate recovery in any particular fluid injection project is relatively independent of the number and spacing of the injection wells as long as the reservoir voidage through the production wells is balanced by the total injection rate. However, the response of a production well is directly affected by the distance it lies from an injection well. In places where the well productivities are declining, the injection wells should be spaced as evenly as possible among the producing wells ("dispersed" injection pattern). More particularly, if the production response depends upon the formation (and subsequent production) of an oil bank, each production well should be surrounded by injection wells. Otherwise, the oil productivity will increase very little as the oil bank moves past the well.&apos;.&apos; An evenly spaced injection pattern has the best chance of generating an oil kick in the production wells. If reservoir voidage and injection rates are to be equal, the ratio of injection wells to production wells must be equal to the ratio of the average injectivity to the average productivity (in reservoir volumes). This ratio is in strumental in choosing the injection pattern. Table 1 shows the production well to injection well ratio for the dispersed injection patterns that have been described in the literature.&apos;-&apos; All of these patterns will have comparable recoveries and response times (for the same basic distance between wells). The choice of pattern there fore depends upon the relative injectivity and productivity of the wells and upon the type of drilling pattern employed. Another important factor may be the ability of the proposed production wells to make up the lost productivity from those wells converted to injectors. These factors become more pronounced at the higher oil viscosities (low gravity oils). All other things being equal, the probable ratio of single well injectivity to single well productivity will be equal to the water-oil mobility ratio of the proposed flood. Thus, high mobility ratios (due to low gravity oil) should call for fewer injection wells — as long as these injection wells are "dispersed" to obtain more even pro duction response for the remaining wells. Secondary re covery projects in oil reservoirs seldom, if ever, will have mobility ratios requiring more injection wells than production wells. Thus, only the last five of the patterns listed in Table 1 will be of significant interest in oil recovery. Almost every development drilling program calls for the wells to be drilled along equally spaced rows and

Jan 1, 1969

By R. E. Ogilvie, J. I. Goldstein

The a and y solubility limits in the Fe-Ni phase diagram have been redetermined at temperatures above 500°C. Both a diffusion-couple and a quench and anneal technique were used. The solubility limits were measured with an electron-probe micro-analyzer. The nickel concentration at the phase boundary is increased below 700°C and the a solid-solubility range is much larger than had been previously measured. The solubility limits are also extrapolated to 300°C. It is suggested that the solubility of nickel in a FeNi reaches a maximum in the temperature interval 400o to 500°C. THE equilibrium diagram has been of great use in the field of meteoritics, where the phase relations between kamacite (a) and taenite (?) in metallic meteorites can be described by means of the Fe-Ni diagram. The study of metallic meteorites by electron-probe microanalysis has cast some doubt on the accuracy of the presently available Fe-Ni diagrams.1, 2 Recent thermodynamic studies of the Fe-Ni system also suggest that the diagram may be in error.3 For these reasons the high-temperature (800o to 500°C) part of the diagram was redetermined. INTRODUCTION The currently accepted Fe-Ni diagram is that of Owen and Liu.4 Above 910°C, there is a region of complete solid solubility, ? (fee). Below 910°C, the a (bee) phase is stable in pure iron. The effect of increasing amounts of nickel is to stabilize the y phase. The phases that form when Fe-Ni alloys are heated or cooled bear little relation to the equilibrium diagram. If an alloy is cooled from the y state and held at a temperature within the a + y field, no evidence has been found for the occurrence of the y - a transformation.5 If the alloy is cooled to low enough temperatures the y phase breaks down into a supersaturated bee phase called a2. In fact, in alloys over 27 pet Ni the y phase is retained at room temperature.6 The a, phase has the same composition as the original y. The temperature at which a2 forms, the M, temperature, has been determined experimentally.&apos; A state of equilibrium can be approached by cooling below M, to form a2 and then reheating the alloy into the two-phase region of the diagram. The y phase will then begin to precipitate out of the a2 phase and grow. The growth of the phase, however, is quite slow. Using the interdiffusion coefficients -Da of Goldstein et al.,8 it is estimated that it takes about 1 year to grow a 10-µ-wide region of ? at 700°C in a 5 pet Ni alloy. Owen and Liu4 used the technique just described to form the equilibrium phases. The phases present were determined by means of X-ray analysis. The accuracy of their diagram depends on the number of alloys available near the phase boundary at a given temperature. In this study two different techniques were used to determine the a/a + ? and ?/a + ? solubility limits. The inherent accuracy of both techniques was greatly improved over that used by previous investigators because the phase-boundary compositions were measured with an electron-probe microanalyzer. PROCEDURE The two methods used to determine the Fe-Ni diagram are the diffusion couple (D.C.) and the quench-and-anneal (Q.+A.) techniques. In the first method, diffusion couples whose diffusion path goes through a two-phase region of the phase diagram were used. A description of the technique used for making the diffusion couples has been described in a previous paper.&apos; After the diffusion treatment a discontinuity in the resultant concentration vs distance profile was measured. The nickel concentrations in the a and ? phases at the interface of the discontinuity are the solubility limits of the a and ? phases in the phase diagram at the diffusion temperature. If the interface com-

Jan 1, 1965

By E. M. Elkin, J. H. Schloen

All known methods of treating and recovering the various components of copper refinery slimes are discussed. The slimes treatment processes presently used by five copper refineries are described and flowsheets are given. A bibliography is appended. THE recent increase in anode copper production at the Noranda smelter placed an additional load on the Montreal East plant of Canadian Copper Refiners Limited. The consequent increase in the amount of anode slimes led to a careful consideration of the various methods of slimes treatment. A critical review of these methods is presented here in the belief that it would be of interest to copper refiners. No such review has yet been published, although a number of individual flowsheets have been described. To make the information of greater value, a questionnaire was sent to all copper refineries. While the overall response to the questionnaire was not entirely satisfactory, the foreign refiners gave much detail in their answers and expressed willingness to cooperate further if needed. Although the data below do not cover all refineries, it is thought that examples of all flowsheets currently in use are included. A comparison of these flowsheets should prove of interest. The paper is divided into two parts. One part deals with a discussion of all known methods of treating and recovering the various components of the slimes. The second describes the processes now in use at various copper refineries for the treatment of raw slimes up to the production of Doré bullion. A brief description of the two main electrolytic methods of parting Doré bullion is appended. Since the first commercial application of electrolytic refining of copper by J. B. Elkington in 1865, the treatment of anode mud or slimes has undergone many changes. The object of treating slimes has always been the recovery and separation of precious metals. With the passage of time, increasing attention has been paid to improvement in recovery and quality of byproducts, mainly selenium and tellurium. The original methods of treatment were crude, although relatively direct. For example," the slimes were fused on a dolomitic clay bed in a reverbera-tory furnace; the slag was removed and the resulting metal cupelled to silver and gold. In another process, the dried slimes were oxidized and scorified on the lead bath of a cupelling furnace. Later, these pyrometallurgical methods were modified by sulphuric acid leaching, followed by fusion with niter in a reverb eratory furnace. A preliminary oxidizing roast improved the leaching step. Straight hydro-metallurgy has not found practical application. No matter what method is employed, the result is Dorb metal—a silver-gold alloy, with or without the metals of the platinum group. Characteristics of the Slimes Anode slimes are made up of those components of the anodes which are not soluble in the electrolyte. They contain varying quantities of copper, silver, gold, sulphur, selenium, tellurium, lead, arsenic, antimony, nickel, iron, silica, etc. The color of raw slimes is grayish black and the particle size is —200 mesh. However, Baraboshkin and Gaev (Ref. 1, p. 37), describe light gray colored slimes from the electrolysis of secondary copper which are composed predominantly of sulphates and of basic salts. In anode furnace practice primary and secondary metals are not usually segregated and such slimes do not commonly occur. Copper in the slimes originates to a large extent in the cuprous oxide of the anodes and is therefore dependent on the oxygen content of the latter: Cu2O + H2SO4 + CuSO4 + H2O + Cu [I] Opinions have been expressed that some of the copper is formed by decomposition of cuprous to cupric sulphate Cu2SO4 ? CuSO4 + Cu PI The product of either reaction is very finely divided. Depending on the slimes composition, much of the copper is combined with sulphur, selenium, tellurium, etc. The balance of the copper is in the free metallic state.

Jan 1, 1951

By G. Krauss, J. M. Thompson, H. Y. Kumagai

Boron-doped p-type and arsenic-doped n-type source materials were used to deposit thin silicon films on amorphous fused quartz substrates by cathodic sputtering in argon atmospheres. All as-sputtered films were found to have high electrical resistivities of about 104 ohm-cm, despite controlled variation of the substrate temperature from 50O to 400°C. The high resistivity of the n-type films persisted even after postdeposition heat treatments as high as 1000°C, while p-type films showed a sharp decrease in re-sistivity to values on the order of 1 ohm-cm or lower after heat treatments above 650°C. X-ray and electron diffraction, together with transmission electron microscopy of the p-type films, revealed that the improved electrical properties resulted from two distinct processes. A primary crystallization or recovery within the pains, which were approximately 200Å diam in the as-sputtered films, accompanied the initial sharp drop in resistivity at 650°C. Following this process, a secondary recrystallization or discontinuous grain growth was nucleated in films heated at 1000°C. The resulting significantly increased size of certain grains and the corresponding decrease in grain boundary area accompanied an additional decrease in resistivity after heat treatment at 1000°C. The properties of thin silicon films are of interest because of their possible application in device technology. Although evaporated silicon films on amorphous substrates1-3 and both sputtered and evaporated germanium films4-&apos; have been studied in some detail, sputtered silicon films have not been widely investigated. It has been observed that evaporated silicon films deposited at substrate temperatures below approximately 600°C are amorphous.1,3,9,10 At substrate temperatures higher than this, the films are polycrys-talline, sometimes exhibiting a fiber texture with the fiber axis normal to the substrate surface.&apos; Similar results have been obtained with germanium films, although in this case the substrate temperature for the amorphous to crystalline transformation is reported to be as low as 150OC.5 The mechanism of film deposition by cathodic sputtering differs markedly from that of thermal evaporation. It might be expected, therefore, that the properties of sputtered and evaporated silicon films would also differ. The purpose of our study was to determine the effects of deposition conditions and heat treatments on the electrical resistivity, structure, and composition of thin silicon films sputtered on fused quartz substrates. EXPERIMENTAL DETAILS Apparatus. A schematic diagram of the sputtering apparatus is shown in Fig. 1. The vacuum chamber was enclosed by an 18-in.-diam by 12-in.-high Pyrex bell jar mounted on a stainless-steel base plate. Access holes in the base plate were used to supply argon gas to the chamber, to allow for various electrical feedthroughs, and to provide mechanical motion to the shutter between the source material and substrate. The chamber was evacuated by a pumping system consisting of a 720 liter per sec oil diffusion pump backed by a 13 cu ft per min mechanical pump. Ultimate pressures of less than 1 x 10-6 torr could be achieved. The substrates were securely mounted on the stainless-steel substrate holder by quartz tabs held in place by stainless-steel screws. Temperatures of the substrate holder were measured by a thermocouple inserted within the holder. A quartz lamp was used to heat the holder and temperatures as high as 420°C could be maintained. Deposition Conditions and Procedure. The substrates used were polished fused quartz slides 116 by 1-12 by 3 in. and were outgassed at 200°C for 1 hr at a pressure less than 1 x 10-5 torr before film deposition. This was followed by a presputtering period of 2 hr during which the movable stainless-steel shutter was so positioned that deposition on the substrate was prevented. At a sputtering voltage of 5000 v dc and an argon pressure of 0.03 torr, the cathode cur-

Jan 1, 1967