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By W. C. Ellis

IN an ingot of germanium solidified progressively from the bottom by a method' devised by J. H. Scaff and H. C. Theuerer, examination discloses ex- IH. C. Torrey and C. A. Whitmer, Crystal Rectifiers. p. 364. 1948. New York. McGraw-Hill Pub. Co. tensive twin relationships. A slice taken about midway in a cylindrical ingot approximately 3/4 in. in diameter and 1 1/2 in. in length, after etching and polishing to delineate different orientations, is shown in fig. la. The orientations of the regions designated with letters were determined by Laue X-ray back-reflection methods and plotted on stereograms. The orientation relationships of the designated components were determined by comparing the values for the nine angles between the three respective cube poles of each orientation with the values calculated in a formal treatment of octahedral multiple twinning in cubic crystals. Germanium, diamond cubic in structure, has the octahedral twinning habit. I am indebted to K. H. Storks for the calculation of the angular relationships of cube poles in octahedral twinning to four orders. The set of values for the nine angles is distinctive of the order of twinning. Confirmation for a multiple twin relationship is obtained from the determined indices of the mirror planes. These exist for all orders of twinning through the third and for some of the fourth." If the orientations are not those for twinning, then the nine angles for the cube poles do not correspond in value and distribution to those formally calculated. Since all nine angles must correspond in values and distribution of values to the calculated ones, the Laue method with a precision of one or two degrees is adequate to establish or deny with confidence the existence of multiple twins. Regions of the same orientation can also frequently be identified by the optical reflections. For example, the narrow twin bands in A at 2: 00 o'clock have orientation B1. The interesting twin relationships shown schematically in fig. lb were found for the section in fig. la. Most of this slice was made up of orientation, A, appearing in widely separated regions. Of the four possible first order twins of A, three were present in this slice and are designated by B with subscripts. Four second order twins of A are designated by C with subscripts. It is worth emphasizing that two of these, C, and C,, are second orders of A through the first order missing in this section. Two regions, designated by D with subscripts are third order twins of A. D2 is a sixth order twin of D,. All orientations found were ascribable to multiple twinning, as if the orientations in this section originated earlier in solidification from a single nucleus. The presence of extensive multiple twinning to- gether with the absence of other orientations appears to be a characteristic result in many instances of solidification of germanium. Fertile conditions for twinning probably exist in the array of atoms in the diamond cubic structure. The high order twins in the section shown, it is reasonable to presume, are the result of progressive octahedral twinning through several generations in the material freezing earlier. Some of these generations do not appear in this section, it is suggested, because their orientations with respect to the growth direction were unfavorable for survival. The extensive twinning is probably promoted during solidification by constraint imposed by volume increase, and to an irregular growth front. Twinning may also be due, in part, to the attempt of the solidifying region to attain the orientation most favorable to the growth direction (maximum thermal gradient). The nucleus for a twinned orientation could have its origin in a "stacking fault" on the close-packed octahedral plane. Further work is being done in which the course of twinning throughout an ingot is being studied. The results appear to be important in the general theory of solidification.

Jan 1, 1951

By B. B. Kunkle

The history of this refinery has been one of expansion. It now has the capacity to produce 240,000 tons of cathodes annually. A general flowsheet and descriptions of the plant layout, operations involved, and equipment used at one of the world's largest and most modern electrolytic copper refineries are presented. THE El Paso copper refinery of Phelps Dodge Refining Corp. was originally constructed by the Nichols Copper Co., in association with Phelps Dodge Corp. and the Calumet & Arizona Mining Co., in order to refine anode copper produced at the smelters of the two latter companies. Initial production was obtained from the plant in January 1930 and its annual refining capacity was 100,000 tons of anodes. In order to keep pace with Phelps Dodge Corp.'s increasing copper production in the Southwest, it became necessary in 1937 to increase the El Paso plant's refining capacity to 160,000 tons of cathodes annually. This was accomplished by adding two sections to the electrolytic tank house, increasing the number of anodes placed in each commercial electrolytic tank from 33 to 37, and making changes in the dc circuits which made it possible to put three generators on each of the two circuits instead of two, thus increasing the amperage on each circuit from 10,000 to 14,800 amp. The capacity of the two furnaces from which refined shapes were cast was increased by raising the sidedoor bays on the furnaces 6 in. An increase of 70 pct in the productive capacity of Phelps Dodge Corp.s Morenci Branch in 1942 again made it necessary to expand refining capacity. In order to accomplish this, Defense Plant Corp. set up a project to increase the capacity of the El Paso plant to 240,000 tons of cathodes annually. This project consisted of enlarging the tank house approximately 50 pct, the construction of another wire- bar furnace, and corresponding increases in other departments where necessary. The engineering work on this expansion was begun in March 1942. Actual construction was under way by August 1942, and the work was completed by March 1944. These additional facilities were purchased from Defense Plant Corp. by Phelps Dodge Refining Corp. in August 1949. The plant is in El Paso about eight miies east of the center of the city and near Highway 80 and the main lines of the Southern Pacific and Texas & New Orleans railroads. The plant site covers approximately 494 acres of company-owned land that is ideally adapted for its use, being well-drained sandy soil and having enough slope so that a minimum amount of excavation was required when the plant was constructed. There is still ample room on the plant site for any future plant expansion. The plant is constructed on four different ground levels and so arranged that the unrefined copper is unloaded on the highest level at the north side of the plant and the refined copper is shipped out from the lowest level on the south side of the plant. The receiving or unloading platform, weighing and sampling rooms, main floor of the tank house, acid and condensate storage tanks, and the slimes and copper sulphate plants are on the first or highest level. The tank house basement, yard scales, charging and furnace bays, balloon flue and stack, brick-storage building, substation and power house, boiler feedwater treating plant and pump house, water storage tanks, and change houses are on the second level. This second level also contains ample yard area for setting-up furnace charges, and for storage of custom scrap, cathodes, scrap anodes, blister, coke, and poles. The casting wheels, inspection conveyors, cathode shears, wire-bar scalping machine, slag

Jan 1, 1952

GENERAL GEOLOGICAL DESCRIPTION The uranium mineral appraisal herein described was made for an ore deposit in New Mexico. The uranium mineralization occurs as roughly tabular to lens-shaped deposits of varying thickness within the sandstone of the Jackpile formation of Jurassic age. The mineralization occurs at several horizons within the Jackpile formation, but is not always confined to specific beds. It often transgresses across stratigraphic layers, as demonstrated when attempting correlation of uranium gamma anomalies between adjacent drill holes. Preferred mineral trends have been established in some parts of the deposit, but are not always predictable when attempting to extrapolate beyond the zones defined by drill hole sampling. MANAGEMENT OF DRILL HOLE SAMPLE DATA All of the drill hole sample data used in the appraisal were obtained from interpretation of gamma-ray logs. A brief description of gamma-ray log sampling is given in Chapter 2. Two preliminary steps are involved in preparing gamma-ray logs into sample data normally acceptable for computer manipulation. 1) The gamma analog trace produced by the downhole probe must be digitized, i.e., counts-per-second (CPS) are recorded for each 0.15 m (1/2-ft) interval across the gamma-ray anomaly. The work is usually done on a "digitizer" while following the analog trace with an electronic stylus on a special tablet or table. The other alternative is to do the work manually. Some of the newest downhole logging equipment produces a magnetic tape output which can be read by a computer. 2) The gamma-ray CPS values must then be converted to equivalent U308 assay values, taking into consideration all appropriate correction factors. The US Atomic Energy Commission, now part of the Department of Energy, developed the theory and algorithm for this conversion in the 1960's, and though the work can be done manually, it is best done with the GAMRED (gamma-reduction) computer program. Fig. 14-1 illustrates a typical analog trace produced by the probe instrumentation, including gamma-ray trace (left), self-potential electric log (center), and resistivity log (right). Fig. 14-2 shows a form of the computer output after the analog data has been digitized to 0.15-m (1h-ft) intervals and converted to percentage U308 values for the same hole. The U308 grade bar graph on the right permits rapid visual inspection of anomalous values by depth and elevation. The converted U308 sample data were next processed by the SURVEY program that assigned to each assay interval [0. 15-m (1h-ft)] an X Y Z coordinate, taking into account all deviations indicated from downhole survey information. The output file of the SURVEY program was listed on the line printer for examination by project geologists, and also became the main input file for the URAN/ COMP compositing program, which is designed to group individual 0.15-m (/-ft) U308 sample values into larger intervals representing discrete anomalous zones according to a series of specified parameters entered into the program by the user. Composite U308 intervals were computed by the URAN/COMP computer program, the logic of which may be briefly described as follows: Step 1 The program searches for the highest U308 value in the hole and builds a composite by adding the highest grade interval on either side so long as the added value is greater than a minimum acceptable grade, and the total composite, after addition, meets minimum GT (grade times thickness) constraints. Step 2 The program loops back to find the next highest assay value in the hole not already included into a composite, until all anomalies above minimum cutoff grade are composited. Step 3 Individual composites are combined if they are closer than a specified minimum waste thickness, and the resultant composite grade still meets GT minimums.

Jan 1, 1980

By Milton F. Goodrich

The idea of using water-only cyclones to scalp clean coal from the feed to other devices has recently been gaining in popularity. 1,2,6 An indication of this popularity is that water-only cyclone scalping is already employed in a few commercial plants. Water-only cyclones scalp the feed to a heavy media vessel in the Warwick plant,3 to Deister tables in the Rowland plant,4 and to a heavy media cyclone circuit in the Amherst Coal Company's McGregor plant.5 Despite this trend, we found surprisingly little information in the literature on the performance of water-only cyclone scalping. Therefore, we undertook a study of its technical merits, limiting our investigation to a water-only cyclone scalper in conjunction with heavy-media cyclones. We felt this to be a reasonable combination of equipment, since both processes operate well on the same size coal. First, we developed simple mathematical relationships revealing general characteristics of the system. Next, we compared the clean coal yield and quality obtainable by the system on four different coals with that obtainable by heavymedia cyclone circuit alone and water-only cyclones middlings recirculation circuit alone. This was done by using computer program to simulate the operation of the three systems. Finally, we considered the effect that implementation of the system would have on a typical preparation plant circuit. The System The system chosen for study [(shown schematically in Fig. 1)] comprises two stages: a primary stage (PI) consisting of water-only cyclones, and a secondary stage (P2) consisting of heavy media cyclones. The water-only cyclones separate raw coal at a low specific gravity, producing a relatively small amount of high quality clean coal and a refuse containing much good coal. This refuse is then recleaned in the secondary stage, where the sharper separation of heavy media cyclones, operated at a higher specific gravity, reclaims additional clean coal. Finally, the clean coal from both stages is combined as the system's clean coal, while the refuse from the secondary stage becomes the system's refuse output. Theoretical Analysis Two assumptions lie behind the following theoretical analysis. The first assumption is that partition curves can represent not only the performance of each stage but also the performance of the system as a whole. These curves show partition number as a function of specific gravity, where partition number is either the percent or fraction of a raw coal with a given specific gravity reporting to clean coal. The second assumption is that these curves are independent of the raw coal characteristics. At any specific gravity the system's partition number is solely a function of the partition numbers of each stage. For convenience, we use the following variables in describing this relationship: g = specific gravity, PS(g) = the partition number of the system at specific gravity g, P1(g) = the partition number of the primary stage at specific gravity g, P2(g) = the partition number of the secondary stage at a specific gravity g. For this system, we can show algebraically that the relationship is: [Ps (g) = PI (g) + (1- P1(g)) P2 (9)(1)] With this equation the system's partition curve can be determined if the partition curves of each stage are known. By definition, the partition numbers P1(g) and P2(g) must each be less than, or equal to, one. Placing these constraints on Eq. (1), we arrive at the relations: [Ps(g) % P1(g) and Ps(g) % P2(g)(2)] Thus, at any specific gravity the system's partition number is always greater than that of both stages. [Figure 2] shows typical partition curves. Curve I represents the primary stage, which consists of water-only cyclones operating at a separating gravity of 1.3. (The separating gravity or the

Jan 1, 1979

By N. L. Carwile, G. W. Geil

A metallographic study was made of deformation twinning (Neumann lamellae) in ingot iron slowly deformed in tension at —196O and —150°C. The results showed that twinning is initiated mainly during the initial stages of plastic deformation. However, the breadth of the twins generally increases with increase in strain up to fracture of the specimen. HE results of an investigation of the effect of low I temperatures on the flow, fracture, strain hardening, and strain aging characteristics, and the true stress-strain relationship for specimens of ingot iron deformed in tension were reported recently.1,2 In that study specimens of ingot iron, in different initial conditions, were slowly deformed in tension at various temperatures between —196" and +100°C. A phenomenon observed, but only briefly reported, was the formation of deformation twins (Neumann lamellae) in the specimens deformed at the lower temperatures. Preliminary metallographic examination of these specimens indicated that there was apparently some correlation between the deformation twinning and the strain of the specimen and that this factor merited further investigation. Some recent investigations have indicated a direct association of Neumann lamellae and the fracture of the metal. Bruckner".' * postulated that the twinning immediately precedes the fracture and the latter is initiated by the stopping of the propagation of twins, either at subgrain boundaries or at other structural features. Tipper and Sullivan5 postulated that Neumann lamellae are initiated by the shock or a shock wave set up at fracture in the still highly stressed unbroken metal, and that a high rate of deformation is a necessary condition for their formation. An extensive metallographic examination, therefore, was made of many of the specimens used in the study of ingot iron at this Bureau and of additional specimens deformed to selected strains under various conditions. The present paper summarizes the effects of deformation under these conditions upon the breadth and scope of the deformation twins. Other features of twinning will be discussed in another paper. Material and Testing Procedure All of the specimens were prepared from one lot of ingot iron, as hot-rolled, of chemical composition other than iron as follows: C, 0.02 pct; Mn, 0.02; P, 0.005; S, 0.018; Si, 0.002; Cu, 0.10; 0, 0.058; and N, 0.002. Cylindrical tensile specimens with a 2 in. gage length were used. The reduced section was slightly tapered from each end; the diameter (0.438 in.) at the midsection of the gage length was about 0.003 in. less than at the ends. The specimens were finished to the final dimensions by grinding and polishing in the axial direction. The ends of the specimens were machined with 3/4 in. x 10 threads and the shoulder fillets were machined to a radius of 0.75 in. The specimens were extended slowly in tension (deformation rate less than 0.5 pct reduction in area per minute) while immersed in an appropriate cryogenic liquid maintained at the desired temperature. The minimum diameter of the specimen was measured during the test by means of a specially designed reduction of area gage accurate to 0.0001 in." A detailed description of the testing equipment and the method of maintaining the desired temperature is given in a previous paper.' Each specimen, after deformation to a specified strain at a selected temperature, was sectioned longitudinally and examined metallographically. The preparation of specimens for metallographic examination was carried out in the usual manner by mechanical polishing and etching. Results and Discussion Deformation twins in specimens of ingot iron extended slowly in tension at —196" and —150°C are shown by the representative micrographs of Figs. 1

Jan 1, 1954

By P. E. Arnold, G. S. Ansell

RELAXATION in metals has been studied in detail by many workers in recent years.1-5 These studies have shown that there is an energy-loss peak observed in a metal placed in mechanical resonance at low frequencies which may be correlated with various metallurgical processes. These experiments have been largely used to study single-phase materials. In order to study the effect of a finely dispersed second phase in a metal matrix upon this phenomenon, the relaxation behavior of an aluminum-aluminum oxide SAP-Type alloy in both the fine-grained as-extruded and coarse-grained recrystallized conditions was investigated by the use of internal-friction measurements. The alloys studied, designated MD 2100, consist of a matrix of commercial-purity aluminum containing a finely dispersed second phase of aluminum oxide. The aluminum oxide is present in this alloy in the form of fine platelets approximately 130A units thick and several microns on edge. The mean free path betwen dispersed platelets is approximately 0.5 p. The grain size of this alloy is extremely stable at temperatures as high as the melting temperature of the aluminum matrix. In the as-extruded condition the grain diameter is several microns, while in the recrystallized condition it is several millimeters in diameter. The damping characteristics of the alloy samples were determined using a torsional-pendulum device. The internal-friction constant was determined for this alloy in both the fine-grained as-extruded and coarse-grained recrystallized conditions over the temperature range from 343" to 923°K at frequencies of 0.9, 1.3, and 1.8 cycles per sec. An internal-friction peak was observed in testing the fine-grained alloys which was not observed for the coarse-grained alloys. This peak, which might be associated with a type of grain-boundary relaxation, was observed at each of the three different test frequencies for the fine-grained sample. The temperature at which the relaxation peak occurred for each of the three different frequencies is shown in Table I. From these data an activation energy of relaxation for each pair of frequencies was determined by comparing the temperature shift of the relaxation peak with frequency between each of the test frequencies, assuming that an Arrhenius-type rate equation is applicable. The activation energy of relaxation determined from these data is also shown in Table I. The mean value of the activation energy was about 6 kcal per mole. The activation energy for the relaxation process determined in this investigation indicates that the relaxation associated with the grain boundaries in this aluminum-aluminum oxide SAP-Type alloy is quite a different process than grain boundary relaxation in single-phase aluminum alloys. In these latter alloys, the activation energy for relaxation has been found to be the activation energy for self-diffusion, approximately 36 kcal per mole1,2 Where the activation energy is the same as the activation energy for self diffusion, it has been proposed that the relaxation phenomena is dependent upon vacancy formation and motion. It is apparent therefore, that, in this aluminum-aluminum oxide SAP-Type alloy, the relaxation must be due to another type of atom transport. It has been shown previously in studies of the high-temperature, low-stress, steady-state creep behavior of as-extruded aluminum SAP-Type alloys, that the activation energy for steady-state creep is one that may be characterized by the nucleation of dislocations from the grain boundaries. It is proposed that the relaxation behavior observed here is due to a similar effect. In this case, the internal-friction peak is a resonance behavior due to the time-dependent nucleation of dislocations from grain boundaries in the sample. A process of this type would have an activation energy which is undoubtedly stress-dependent and of the form Q = Q, + (dQ/du)u

Jan 1, 1962

By J. B. Agan, R. J. Fernandes

This paper utilizes the layered-system approach, modified to include areal sweep efficiency, to determine the miscible-slug size required and to predict the perfort7zance of a miscible-slug process in a highly stratified reservoir having a permeability variation of 0.76. The slug size in each layer was determined from theoretical calculations and laboratory data which showed that, to maintain miscibility in the reservoir, the slug size had to be 8.2 per cent of the floodable hydrocarbon pore volume. Economic considerations, however, such as the value of the miscible product injected, the cost of injection and the cost of reprocessing the miscible product, limited the amount of miscible product which could be injected into the lower-permeability layers. This resulted in subjecting only 60 per cent of the reservoir to a slug size sufficient to maintain miscibility. Utilizing the relationship of producing gas-oil ratio and areal sweep efficiency as a function of pore volume injected (as obtained from data published by Dyes, Caudle and Erickson2), the theoretical performance was determined. This prediction is compared with actual performance to date. Actual performance reflects an increasing percentage of tniscible product in the produced fluid to a particular level, which remains static for a short period and then increases again to a higher level. This performance suggests that the reservoir has performed as a layered system. It is concluded that the layered-system approach can be used to predict performance in a highly stratified reservoir and that economic consideration is a limiting factor in determining the amount of the reservoir which can be miscibly swept. INTRODUCTION The Paloma zone in the Paloma oil field, Kern County, Calif., is comprised of several sand members separated by siltstone, shale and/or cherty sections. Rapid facies changes within the zone indicate that the sediments were deposited in a "near shore" environment. As a result, the Paloma sands have a high permeability variation, and the Paloma zone is comprised of several sand reservoirs. Since one of the sand reservoirs containing crude oil was not receiving the benefits of gas injection, consideration was given to recompleting certain wells to isolate the sand in order to perform a miscible-phase injection project and, thereby, to increase its ultimate oil recovery. Before proceeding with the project, a review of the literature was made to determine the miscible-slug size that would be required to maintain miscibility throughout the displacement process. Although the review showed that considerable information was available for homogeneous systems, insufficient information was available to determine slug-size requirements and to predict performances for a highly stratified reservoir. This paper has been prepared to describe the method used to determine the miscible-slug-size requirement and to predict the performance of the miscible-phase injection project initiated in the Paloma oil field. Although the Paloma project has only been in operation since Aug., 1958, sufficient production history has been obtained so that a comparison can be made with the predicted performance. DESCRIPTION OF RESERVOIR The reservoir in which the miscible-phase project was initiated in the Paloma field is shown on Figs. 1 and 2. Reservoir properties are as follows: average sand thickness, 43 ft; porosity, 19.1 per cent; water saturation, 47.2 per cent: oil viscosity, 0.328 cp; reservoir temperature, 250°F; reservoir pressure, 3,500 psi: gas saturation, 21.2 per cent at time of miscible product injection; and total net hydrocarbon pore volume, 19,993,000 reservoir bbl. LIMITATIONS The method described herein utilizes a layer-system approach, where injection into and production from each layer is assumed to be proportional to the layer's fractional capacity. The effects of increased fluid mobility on injection and production rates, in layers which have had breakthrough, are not reflected in this method. There has been considerable controversy over the slug size necessary to maintain miscibility throughout the displacement process. In this method, the slug-size

By Robert E. Brand, Strathmore R. B. Cooke

For a study of the bonding that occurs in magnetite pellets during oxidation, cubes of magnetite, hematite, and quartz were prepared, each with one surface polished and nearly optically plane. These faces were fired together under pressure and at various temperatures to determine whether bonding would occur. Sections of surfaces that bonded were examined microscopically. An attempt was made to measure the strength effected by this treatment. EARLIER work1,2 has shown that the strength developed by fired magnetite pellets containing silica or silicates is due to three separate effects. Two of these are associated with the formation of slag in the interior of each pellet at temperatures above 1000°C, where the atmosphere is substantially though temporarily neutral. The third is independent of the silica content and is responsible for the development of a hard shell around the pellet during the initial stages of firing, a condition which permits the pellet to assume the increasing load of the overlying burden and prevents extrusion of the slagged and semi-liquid interior. Pellets made from hematite concentrates do not show these effects unless specific additives are incorporated, and it is these differences in behavior which in large part account for the difficulty in producing satisfactory pellets from such concentrates. Elsewhere it has been stated that "the most important factor responsible for the development of strength in fired magnetite pellets containing no additive is the oxidation of magnetite to hematite and the subsequent recrystallization and grain growth of this constituent."' The object of the investigation reported in the present paper was to study in detail the mechanism described above and to evaluate its contribution to the strength of the fired pellet compared with other possible mechanisms, excluding slag bonding. This was effected by placing together polished faces of two cubes prepared from specific minerals and then heating them under constant pressure at different temperatures both in air and in nitrogen. The materials used were magnetite, hematite, and quartz. The magnetite was coarsely crystalline material from western Montana, the hematite was Itabira ore from Brazil, and the quartz was of optical grade but of unknown origin. A high-grade Lebanon (Pennsylvania) magnetite concentrate was used to prepare briquets for the investigation of bonding strength. Analyses of the iron oxide materials are given in Table I. The specimens for furnace treatment were prepared with a carborundum cut-off wheel, which cut the minerals into cubes approximating % in. along each edge. Care was taken to make the sides as parallel as possible. The edges of the faces to be polished were beveled, and the cubes were mounted in brass rings with sealing wax, this being essential to prevent the specimens from rocking during polishing. To prevent excessive friction, the wax was recessed so that only the brass ring and the face of each specimen would be in contact with the polishing lap. Each specimen was then ground with No. 600 carborundum to produce a level surface before polishing. The Graton-Vanderwilt process was not used for polishing because of the long time required by this method, but several other methods were tried. Cloth laps using levigated alumina or chromium oxide did not produce the desired polish. Satisfactory results were obtained by means of a pitch lap: which was used for all the mineral cubes, with levigated alumina as the polishing medium. The lap was operated in a machine similar to those used in the preparation of single optical surfaces. It was run at low speeds and moderate pressures, and polishing was stopped occasionally to prevent overheating of the lap. A good polish with flat surfaces could be obtained in about 5 min. After polishing the sealing wax was removed either in hot water or in a solvent such as turpentine.

Jan 1, 1955

By R. S. Rickard, M. C. Fuerstenau

Anodic polarization curves for iron dissolution and cathodic polarization curves for copper deposition and ferric and hydrogen ion reduction were studied. These results were used to predict the relative rates of the reactions: The rates of the first two reactions were found to be first order with respect to the reacting ion, and the rale-controlling step was diffusion of the ions to the callzode surface. The rate of hydrogen ion reduction in an oxygen-free solution is dependent on the reciprocal of the square root of the hydrogen ion activity. In solutions containing oxygen, the rate of hydrogen reduction becomes dependent on the square root of the partial pressure of oxygen. At equal concentrations copper precipitation occurs about twice as fast as ferric ion reduction. In an air-saturated solution containing 0.01 M cupric ion at pH 2, the rate of hydrogen ion reduction zs about 10 times slower than that of copper precipitation. At pH values below 3, the rate of hydrogen reduction in oxygen-free solutions is very slozu. COPPER cementation has been utilized industrially for many years as a means of recovering copper from aqueous solutions. There are many different types of cementation plants, but all simply provide a means of contacting iron with relatively dilute copper solutions. In the past little or no attention has been paid to rates or mechanisms of the reactions involved. As a result, this and other studies'-3 have been undertaken recently to establish the important parameters in this system. The reactions involved in copper cementation by iron are: Since transfer of charge is involved in every case, these reactions should be considered from an electrochemical point of view. In any electrochemical system involving electrolytic conduction, passage of electrons necessitates ion transfer to the respective electrodes according to Faraday's law. The current in the system will be proportional to the rate of ion transfer, and, therefore, when the current in the galvanic cell is known, the rates of the reactions involved can be determined. Galvanostatic electrode measurements5" are applicable for these electrochemical studies, in that with this technique polarization curves (current density vs electrode potential) are established by impressing a constant current through an electrode and measuring the electrode potential. Once the current density, electrode potential, and reacting area are known for each reaction in this cementation system, the rates of the iron-consuming reactions can be determined. EXPERIMENTAL MATERIALS Several metal electrodes were used in this investigation; they are shown in Table I. Solutions were made with reagent-grade salts and conductivity water. Air, nitrogen, and oxygen were employed. All of these gases were saturated with water and degreased prior to use. EXPERIMENTAL PROCEDURE The experimental work was divided into two general areas. The first area involved galvanostatic measurements, which were used to determine the rates of reactions as a function of various parameters. The second area comprised actual cementation experiments to check the rates predicted from the electrode measurements. Galvanostatic Electrode Experiments. Polarization curves were obtained using a standard galvanostatic technique5'= with the apparatus shown in Fig. 1. The various electrode polarization experiments were run the same way except for changes in solution composition, polarity, and type of measured electrode. The general procedure involved the following steps: 1) a solution was made 0.5 M in sulfate ion and to the desired cation concentrations; this solution was placed in a constant-temperature bath and saturated with the desired gas; 2) the electrodes were cleaned and placed in the electrode holder; 3) the previously cleaned apparatus was assembled and immersed in a constant-temperature water bath (temperature controlled to ± 0.05"C); 4) the electrode was then positioned; the solutions were introduced, and the polarization meas-

Jan 1, 1969

By M. E. True, B. L. Stone

To cope with the problems encountered when drilling at greater depths and to reduce the amount of physical effort required on the part of drilling crews in making round trips, a new type of semiautomatic power-operated drilling machinery has been developed which permits round trips to be made without the drill pipe being touched by hand. This equipment consists of hy-draulically operated tongs which perform the stabbing, spinning, and tong-ing operations, and two power-operated racking units mounted in the derrick for carrying the pipe to and from the center of the hole and positioning it on the mat and in the rack. With this equipment all of the operations of the various units are controlled remotely by manipulation of hydraulic valve levers and electric switches. INTRODUCTION As horsepower rises to meet the demand for deeper drilling, it is necessary to increase the weight of surface drilling equipment. Also, the duration of repetitive operations in making round trips to change bits is greatly increased with depth. Harder formations encountered at greater depths reduce bit life rapidly, resulting in more frequent round trips and in some instances more time is consumed in changing bits than in drilling. Since the introduction of the first rotary employed to drill for oil in 18951, there has been relatively little change in the general procedure for making up, breaking out, stabbing, and racking drill pipe in making round trips to change bits. The conventional method of making round trips with the drill pipe requires that drilling crews lend strenuous physical assistance to manually operated tools. Although many new devices have been developed to improve efficiency, increase speed of making round trips, improve safety, and reduce the amount of physical effort required in handling drill pipe, it is considered a vital necessity to substitute automatic or semiautomatic power-operated machinery for many of our more or less manual operations if extremely deep drilling is to be carried out successfully on a production basis in the same manner as our shallower drilling of today. Field tests have been made of remotely controlled power-operated tongs, spinner, stabber, and racking equipment. The tongs, which include a built-in pipe spinner, are mounted on a column, are capable of gripping and supporting the weight of a 90-foot stand of drill pipe, and are provided with means for moving the pipe vertically as well as to and from the center of the hole. The racking equipment consists of two units, one at the level of the conventional monkey board and the other at the first girth on the ladder side of the derrick. Most of the physical effort of making round trips with drill pipe has been eliminated in that all of the operations of tonging, spinning, stabbing, and racking of pipe on the floor are controlled by an operator in a seated position by manipulation of hydraulic and electric valve levers and buttons. The driller is relieved of operating the cathead, leaving only the hoisting and slips to be controlled. Complete round trips are made without the drill pipe being touched by the drilling crews. Although the speed of pulling or running a single stand with the power-operated equipment is approximately the same as that with conventional equipment, it is possible to maintain this rate for long periods, whereas fatigue slows crews working conventionally during round trips, especially under adverse weather. After completing round trips with this equipment, drilling crews are not exhausted, consequently, are able to perform effectively their duties while drilling, which is essential for maximum over-all efficiency. Safety is substantially improved as the derrickman performs his duties from a platform enclosed by rails and the tong lines and spinning chain are eliminated from the derrick floor. The hazards encountered in racking drill pipe on the floor and in stabbing are also eliminated. Figure 1 shows a drawing of a derrick equipped with the power-operated drill'pipe handling equipment.

Jan 1, 1949

By M. E. True, B. L. Stone

To cope with the problems encountered when drilling at greater depths and to reduce the amount of physical effort required on the part of drilling crews in making round trips, a new type of semiautomatic power-operated drilling machinery has been developed which permits round trips to be made without the drill pipe being touched by hand. This equipment consists of hy-draulically operated tongs which perform the stabbing, spinning, and tong-ing operations, and two power-operated racking units mounted in the derrick for carrying the pipe to and from the center of the hole and positioning it on the mat and in the rack. With this equipment all of the operations of the various units are controlled remotely by manipulation of hydraulic valve levers and electric switches. INTRODUCTION As horsepower rises to meet the demand for deeper drilling, it is necessary to increase the weight of surface drilling equipment. Also, the duration of repetitive operations in making round trips to change bits is greatly increased with depth. Harder formations encountered at greater depths reduce bit life rapidly, resulting in more frequent round trips and in some instances more time is consumed in changing bits than in drilling. Since the introduction of the first rotary employed to drill for oil in 18951, there has been relatively little change in the general procedure for making up, breaking out, stabbing, and racking drill pipe in making round trips to change bits. The conventional method of making round trips with the drill pipe requires that drilling crews lend strenuous physical assistance to manually operated tools. Although many new devices have been developed to improve efficiency, increase speed of making round trips, improve safety, and reduce the amount of physical effort required in handling drill pipe, it is considered a vital necessity to substitute automatic or semiautomatic power-operated machinery for many of our more or less manual operations if extremely deep drilling is to be carried out successfully on a production basis in the same manner as our shallower drilling of today. Field tests have been made of remotely controlled power-operated tongs, spinner, stabber, and racking equipment. The tongs, which include a built-in pipe spinner, are mounted on a column, are capable of gripping and supporting the weight of a 90-foot stand of drill pipe, and are provided with means for moving the pipe vertically as well as to and from the center of the hole. The racking equipment consists of two units, one at the level of the conventional monkey board and the other at the first girth on the ladder side of the derrick. Most of the physical effort of making round trips with drill pipe has been eliminated in that all of the operations of tonging, spinning, stabbing, and racking of pipe on the floor are controlled by an operator in a seated position by manipulation of hydraulic and electric valve levers and buttons. The driller is relieved of operating the cathead, leaving only the hoisting and slips to be controlled. Complete round trips are made without the drill pipe being touched by the drilling crews. Although the speed of pulling or running a single stand with the power-operated equipment is approximately the same as that with conventional equipment, it is possible to maintain this rate for long periods, whereas fatigue slows crews working conventionally during round trips, especially under adverse weather. After completing round trips with this equipment, drilling crews are not exhausted, consequently, are able to perform effectively their duties while drilling, which is essential for maximum over-all efficiency. Safety is substantially improved as the derrickman performs his duties from a platform enclosed by rails and the tong lines and spinning chain are eliminated from the derrick floor. The hazards encountered in racking drill pipe on the floor and in stabbing are also eliminated. Figure 1 shows a drawing of a derrick equipped with the power-operated drill'pipe handling equipment.

Jan 1, 1949

By R. J. Brown

Design of a submarine pipeline system is governed by many factors, one of which is the effect of transverse horizontal currents on the pipeline structure itself Although this feature alone can be of utmost importance to the life span and stability of the underwater pipeline, it is usually the least recognized, with these hydro-dynamic forces being either completely overlooked or grossly underestimated. In an attempt to supply the methods and means for stabilization of sub-marine pipelines, much capital has been spent by pipeline companies. Design criteria incorporated by these organizations extend over a broad spectrum of engineering with bases varying from pure theory to cut and dry methods. A history of numerous failures has substantiated the postulate that many of these submarine pipelines have been underdesigned from the stability standpoint. By the same token, equally as many have been excessively overdesigned with resultant excess expenditures. An attempt has been made in this paper to establish the magnitudes of these hydrodynamic forces by measuring the lateral current-induced differential pressure distribution around the periphery of the submarine pipeline. INTRODUCTION The expenditure of money for research by corporations obviously requires beneficial results to justify the investment. One of the functions of the engineer is first to make the problem known and then to provide a means of solution at the least possible cost. The initial procedure is to investigate all pertinent published technical articles on the subject to determine if this problem has been previously solved. If resolution of this problem is not obtainable, the next course of action is to evaluate through experiments these forces and their magnitudes. On the specific subject of drag and lift, the accumulation of data is provided from three separate and distinct sources: from experience, from theoreticians and through experimental observations. The experience source has proved costly with money wasted either because of underdesign and failure or excessive expenditures for overdesign, and has not been sufficient to form a definite conclusion on these hydrodynamic forces. The pure theoretician is often not completely cognizant of the situation and his works bear little adaptation to the real problem. The experimentalist has his own problems with regard to obtaining results from small-scaled models and successfully adapting them to the larger prototypes. Each method has its own advocates who diligently adhere to their own separate routes as being the only means of resolving this problem. However, a review of the various methods of analysis leads one to the conclusion that if the advantages of all three are combined, a reasonable solution to this problem can be reached. Briefly then, the problem is to obtain the magnitudes of the forces on the submarine pipeline subjected to a lateral current by investigations of previous design considerations, by a study of existing theoretica1 data and by appropriate experimentation. This paper deals mainly with obtaining experimental data and the interweaving of theoretical and experience factors for resolution of these forces. APPARATUS AND PROCEDURE These tests were performed in 1961 at Collins Construction Co.'s main office near Port Lavaca, Tex. Test equipment consisted of a steel tank 3 ft high by 4 ft wide by 40 ft long, with several pumps circulating the water through the tank via suction lines from the downstream portion of the tank and discharging from the pumps directly into the upstream end of the tank. For reduction of turbulence, a wire section was constmcted in the upstream portion and straightening vanes in the form of pipes, screens, etc., were used to reduce the vortex and eddy action in the tank (Fig. 1). A venturi was built at the test specimen for obtaining velocity sufficient to simulate actual conditions. This full-scale test was initiated to eliminate the error introduced in modeling and obtain a truer picture of forces actually encountered. Six- and 10-in. specimens were prepared by

Jan 1, 1967

By J. M. W. Mackenzie, M. H. Buckenam

Flotation experiments using stearic, oleic, linoleic, linolenic, and ricinoleic acids and naturally occuring products rich in these acids as collectors for calcite are described. The results confirm the validity of the rule of Hukki and Vartiainen relating the collecting power and unsaturation of the C18 acids. Reasons for this relationship are discussed and a close relationship between mineral depression and critical micelle concentration is reported. It has long been recognized that the unsaturated fatty acids are in general superior flotation collectors to their saturated homologues. Whereas earlier workers concentrated on saturated and monoethe-noid acids, recent investigations have centered on oleic, linoleic, linolenic, and the substituted mono-ethenoid acid: ricinoleic. From studies of the collecting properties of palmitic, oleic, linoleic, and linolenic acids on ilmenite, rutile, hematite, and magnetite, Hukki and Vartiai-nenl concluded that the collecting power of fatty acids increased with unsaturation of the hydrocarbon chain. Sun, Snow, and Purcel12 investigated the collecting properties of unsaturated fatty acids as collectors for phosphate ores and concluded that the collecting power increased with increasing unsaturation of the hydrocarbon chain up to two double bonds and that further unsaturation decreased the collecting power. More recently Sun3 studied the collecting power of the C18 fatty acids stearic, oleic, linoleic, and linolenic on 37 minerals. The results of these experiments with a few exceptions showed that the collecting power of the acids increased in the order stearic, oleic, linoleic, and linolenic. The relative collecting powers of linoleic and linolenic acids were in many cases altered by the cleanliness of the mineral surface prior to flotation. Sun concluded that linolenic acid may become oxidized by atmospheric oxygen during flotation, a reaction which would reduce its effectiveness as a collector. This deduction is supported by Gaudin and Cole4 who concluded that oleic and linoleic acids do not undergo appreciable oxidation of the double bonds during flotation but that the linolenic acid double bonds are measurably affected. The most complete investigation on the influence of hydrocarbon chain unsaturation on the collecting properties of fatty acids is that of Kivalo and Lehm~svaara.~ These workers using linolenic acid of a higher purity than Hukki and Vartiainen showed that this acid was superior to oleic and linoleic acids as a collector for magnetite. They also found that ricinoleic acid was a more effective collector for this mineral than the other acids investigated, an observation particularly apparent at high collector concentrations. Seeking to explain the superiority of the unsaturated acids these authors considered the effects of critical micelle concentration, surface activity, hydrolysis, and cross sectional area of the hydrocarbon chain in relation to unsaturation. Using what, according to the results of Caviere are erroneous surface tensions of the soap solutions of these acids, they concluded that the surface activity decreases and the critical micelle concentration increases with increasing unsaturation. In view of the data of Cavier, whose results show that surface activity of these soaps increases with unsaturation, the deductions of Kivalo and Lehmusvaara are open to criticism. The degree of hydrolysis of the soap solutions as measured by Kivalo and Lehmusvaara decreases as the unsaturation of the fatty acid increases, a result which helps to explain the superiority of unsaturated acids as collectors. In view of the superiority of unsaturated acids as collectors for many minerals, attention has been directed towards the utilization of fatty acid raw materials such as tall oils and linseed oils which contain considerable quantities of these acids. This paper describes test work to determine the effect of unsaturation of the hydrocarbon chain on the collecting properties of fatty acids on calcite, and includes comparable test work using natural products rich in unsaturated acids. TEST WORK Reagents: The pure fatty acids used were oleic, linoleic, and linolenic. Of these, oleic was supplied by British Drug Houses Ltd. and the others were produced by the Hormel Inst. When not in use these

Jan 1, 1961

By J. H. Schulman, M. H. Buckenham

Although much interest has been taken in the use of mixed collectors in flotation, this investigation is probably the first in which oppositely charged collectors have been considered. The results obtained and the techniques used could well be applied in the behavior of other mixe the behavior of other mixed collector systems and could possibly explain the effective flotation results which have been reported when various collector combinations have been used. Collectors conventionally employed in flotation systems are soluble in water, but many of their homologs of longer hydrocarbon chain length are insoluble. The properties and behavior of these insoluble compounds may be conveniently studied when they are spread as monolayers at the air/water interface on the Langmuir-Adam trough. Although some extrapolation is involved in applying effects observed at this interface to the solid/liquid interface where the action of collectors is most important in flotation, the technique nevertheless is most useful for the study and interpretation of flotation phenomena. Of particular interest in this field are investigations on the insoluble monolayers of the fatty acids, alkyl sulfates and alkyl amines; the penetration of these insoluble monolayers by soluble surface active components and their interaction with metal ions from the underlying solution.'-' Unfortunately, the insoluble xanthates and related compounds do not exhibit stable monolayer properties due to rapid oxidation at the air/water interface and, therefore, cannot be studied directly in this way. These approaches have enabled Leja and Schulman8 to suggest mechanisms explaining dynamic attachment of mineral particles to air bubbles involving collector-frother interaction and the adsorption of collectors onto mineral surfaces. In this and other papers 9-12 considerable evidence is presented to support the concept of collector-frother and metal ion-monolayer interaction and to emphasize the value of monolayer techniques in elucidating the flotation system. Molecular interactions resulting from monolayer penetration are determined by the nature of and the association between both the polar and nonpolar groups of the two molecules concerned. Stable complexes are formed on penetration when interaction takes place between both the polar and nonpolar groups, and although the resultant complexes are not necessarily true chemical compounds, the properties of the molecularly associated complexes are very different from those of the individual components. Shortening of, or changes from, a straight hydrocarbon chain in one of the reacting molecules reduces considerably the stability of the associated complex as do changes in temperature, pH and substrate composition. The effect of hydrocarbon chain length becomes most important when observed effects are to be applied in flotation studies where soluble homo-logs and, therefore, much shorter hydrocarbon chain lengths are used. The present investigation is based on Langmuir trough work carried out by Bowcott,l3 who studied the penetration of insoluble amine monolayers by potassium lauryl xanthate. Bowcott observed that cetyl amine monolayers were readily penetrated by xanthate, but found that with time the high film pressures resulting from penetration and association fell off, indicating decomposition and ejection of xanthate from the film. This decomposition was pH dependent. Of particular interest in this work were studies on an equimolecular mixed monolayer of the fully N-substituted ammonium compound, for example, cetyl trimethyl ammonium iodide (CTAI) and potassium cetyl xanthate. Despite the fact that the CTAI is water soluble and the xanthate on its own is incapable of forming a monolayer, the mixed film was stable up to a surface pressure of 67 dynes per cm. In this condensed state the xanthate was stabilized against atmospheric oxidation, although iodine injected beneath the film caused an immediate collapse. The stabilizing of xanthate against oxidation by association with an alkyl trimethyl ammonium bromide (TAB) could be important in flotation, and a study of the performance and behavior of mixed collectors therefore was undertaken. A modified Hallimond tube operated under controlled conditions was used to evaluate flotation. Surface tension measurements were made to investigate the properties of the soluble

Jan 1, 1963

By Franklin J. Hill, Theodore D. Tiemann

Sized fractions of Wisconsin Gogebic taconite were reduced with hydrogen over the temperature range from 600° to 1000°C. In general, the degree and rate of reduction increase with temperature. Particle size has no observable effect except in the smaller fractions at 900°C and above, where reduction is impeded, possibly due to the siliceous nature of the ore. Gaseous diffusion appears to be significant as a rate controlling factor at certain stages. THE depletion of high grade iron ore reserves in the United States has established the need to utilize all available iron ore deposits, both in long range planning and from the viewpoint of national emergency. This has led to extensive research and development in this field. The beneficiation of Wisconsin Gogebic taconite ore has been previously studied by investigators at the University of Wiscconsin, 1 the United States Bureau of Mines,, Battelle Memorial Institute, 3 and others. Methods investigated have included concentration by flotation processes, magnetic and gravity separation, magnetic roasting and various combinations of them. The foregoing studies have been concerned with the production of an enriched ore suitable for blast furnace use. If the ore could first be reduced to metallic iron and then beneficiated, the product could be used directly in the open hearth or electric steel-making furnace. The by-passing of the blast furnace should enhance the economic feasibility of the beneficiating process. The work reported here,4 was undertaken to establish data on the hydrogen reduction of Wisconsin taconite that would eventually lead to the development of an economic direct reduction process for this and perhaps other low grade siliceous ores. The volume of work on direct reduction can be judged by the fact that 240 direct reduction processes were patented in the United States alone up to 1951, 5 and numerous additional processes have since been developed. Some of the factors contributing to direct reduction development are: 1) The increasing capital cost of the blast furnace and its accessory equipment. 2) The decreasing availability of high grade domestic ore. 3) The high cost of steel scrap for use in the open hearth and electric furnaces. In general, direct reduction processes can be divided into two types; those using a solid reductant (coal, peat, lignite) usually carried out in a kiln, and those using a gaseous reductant (H2, CO) in a shaft furnace or a fluidized bed retort. As there is no low cost coal readily available in northern Wisconsin but natural gas could be quite easily obtained, it is believed a gaseous reductant process would offer the greater feasibility for use on Wisconsin taconite. It is hoped that this preliminary work will beof interest to other investigators in this increasingly important field. TACONITE ORE The ore used in the investigation was obtained originally from the U. S. Bureau of Mines, and consisted of a representative composite made up from trench samples of the Norrie, Pabst, Plymouth, Pence, and Yale members of the Wisconsin Gogebic range iron formation. Chemically, the ore contains approximately 52 pct SiO, and 30 pct Fe. X-ray diffraction and other studies indicate the principal minerals to be quartz (SiO2), hematite (Fe2O3), and goethite (Fe2O3. H2O). Minor amounts of iron containing silicates, siderite (FecO3), and magnetite (FeO-Fe2O3) are present. The iron minerals and quartz are so finely disseminated that the ore requires grinding to less than 200 mesh (74 µ) for essential liberation.l,2 The iron content of each of the several size fractions studied is shown in Table I. EXPERIMENTAL METHOD The method used throughout the investigation was based on that developed by the U. S. Bureau of Mines in Minneaopolis6,7 in which the course of reduction is followed by the loss in weight of the ore sample. More specifically, a 100-g sample of the size frac-

Jan 1, 1962

By L. A. Weitzenkamp, N. M. Bashara

A study of the electrical conductivity of gold films less than 200 in thickness indicates a negative temperature coefficient of resistance and a thermal actiuatlon energy of less than 0.25 ev. The films consist of discrete metal islands of linear dimensions from a few angstroms to 1000A. Films were able to withstand applied fields up to 60,000 v per cm before breakdown occurred. A model for the conduction mechanism is proposed which involtes a Potential barrier due to work junction, irriage forces , and an electrostatic potential arising from separating an electron from a neutral island leaving behind a positively charged metal island. Activation energies of less than 0.25 ev ave consistent with this model, which includes a tunneling andor Thermal mechanism for conduction between the separate metal islands. An apparent satuvation effect in conductivity at high fields is observed experimentally. The saturation effect may be explained by the influence of the electrostatic contribution to the potential barriers for the transition through several islands adjacent to the original island which was activated to give up an electron. The proposed model gives Poor quantitative agyeement for the intermal electrical field between islands. ThIS paper will relate the structure of discontinuous metal films to the electrical properties and will emphasize the following topics: 1) the relation of the conduction mechanism to particle size and a comparison of particle size from electrical measurements with electron-microscope studies; 2) the saturation of the conductivity at high electric fields; and finally, 3) a comparison between the external field applied and the apparent field between particles. che- latter comparison points to a need for a modification in the model for the conduction mechanism first proposed by orter' and expanded by Neugebauer and webb2 which will be dealt with in the discussion. The paper is based on results on gold films on glass microscope slides. The clms were vacuum-evaporated and were about lOOA thick, thickness being measured by interferometry. It has been observed that metal films of this thickness do not exhibit bulk metallic conduction. Films thinner than some critical thiclmess, depending upon substrate temperature and other factors, have conductivities which increase with increasing temperature with thermal activation energies of less than 0.25 ev. Electron-microscope studies3 have shown that these films consist of discrete metal islands having linear dimnsions from a few angstroms to approximately 1000A. When the metal is being vacuum-deposited on the substrate, islands on the order of a few angstroms appear first. As the deposition continues the islands may tend to agglomerate into larger particles and may eventually grow together into a continuous film,3''' In our tests the conductivity of the gold films was found to be about ten orders of magnitude less than the bulk conductivity of gold. When oxygen was introduced into the test chamber the conductivity decreased by a factor of about one-third. This can be related to an increase in work function for gold caused by adsorption of oxygen, as reported by Oullet and Rideal.s Exposure to an atmosphere of water vapor caused an increase in conductivity by a factor of 2 or 3 when a low field was applied. When the films were exposed to water vapor under a high field the conductivity increased by as much as two orders of magnitude. The activation energies measured were much less than the work function for gold, 0.25 ev or less, with the smaller activation energies observed for thicker films. It will be shown that the activation energy is a function of particle size and spacing. In general the model for the potential between metal islands would include the effective work function, the image force, the applied field, and an electrostatic term. The electrostatic contribution arises from the potential required to separate an electron from a conducting sphere. According to Neugebauer and webb2 the maximum potential due to the field and the electrostatic term only is

Jan 1, 1967

By H. A. Lesser, H. L. Stone, G. H. Bruce

ESSO PRODUCTION RESEARCH CO., HOUSTON, TEX. A mathematical model that represents the conduction heating of a rock formation of limited permeability is formulated. Heat is introduced by the injection of a hot condensing gas into horizontal fractures through the formation. The fractures are assumed to be equally spaced; the flow of fluid is linear. The model consists of three coupled partial differential equations and two functional relationships. Temperature histories for both fractures and formation are obtained by numerical procedures. Application of the model in predicting in situ heating of oil shale is illustrated with four sample cases. Influences of shale thermal diffusivity, fluid pressure in the fracture and fracture spacing upon heating rate are demonstrated. In all cases considered, several years were required to heat all the formation to 700F with 1,000F steam. Less than 32 per cent of the injected heat was utilized for heating the shale. To facilitate extensive calculations of this type, a set of seven dimension-less quantities are derived. With this dimensionless system, the effect of controllable parameters on economics can be explored. INTRODUCTION Vast deposits of hydrocarbons are contained in oil shale formations in the western United States and in other countries. These hydrocarbons, known as kerogen, are difficult to recover because they are immobile solids and because the rock formations in which they are found have very limited permeability. The kerogen can be converted through pyrolysis to recoverable liquids and gases if the formation temperature is elevated to the range 600 to 800F. To accomplish this heating, the formation might be artificially fractured and a hot fluid injected into the fractures. If the injection and production wells are vertical and the fractures horizontal, interwell communication will be established and the hot fluid will flow from an injection well to a production well. In this process, some of the heat in the fluid will be given up and conducted into the formation. Products of pyrolysis will flow from the heated rock matrix into the fractures and be produced, commingled with the injected fluid. The practicality of such a process is strongly influenced by the rate at which heat can be transferred from the hot fluids to the formation. An analysis of this heat conduction problem is the subject of this paper. Linear flow of a condensing gas through a set of horizontal, equally spaced fractures is considered. Temperature histories for both fractures and formation are obtained from numerical procedures. The analysis also applies to formations containing streaks of natural permeability instead of fractures. Heat flow problems similar to the one treated here have been studied by other workers. Thomas1 has solved a radial problem in which he considers the injection of a noncondensing gas into a single, horizontal fracture and approximates the temperature profile in the fracture by a step function. The solutions to other problems, which are less similar to the present problem than the one treated by Thomas, have been reviewed by Spillette.2 In addition to these mathematical studies, a field test of an in situ shale oil recovery process using hot natural gas as the injected fluid has been reported.3 The first part of this paper is concerned with the mathematical development of the problem. The differential equations, boundary conditions and functional relationships which describe the physical model are formulated and the equations are cast into finite difference form. The method of solution of the difference equations is discussed (Appendix B). The second part of this paper presents results computed for a typical oil shale formation for which steam at 1,000F is the injected fluid. Fracture spacing, horizontal and vertical thermal diffusivities

Jan 1, 1967

By M. H. Caron

BASIC U. S. Patent 1,487,145 on ammonia leaching of nickel ores was issued to the author on March 18, 1924. Equivalent patents in other countries were obtained later. The Dutch Syndicate Brikcarbo became interested in the process in 1935; and a couple of years later the late Dr. H. Foster Bain sent samples of Surigao laterite iron ore to Delft and witnessed tests made there on this material for the Philippines Commonwealth. As a result, the author was asked in April 1940 by Dr. Bain to go to the Philippines to erect and take charge of a pilot plant for the process. The World War prevented carrying out this proposal. The Dorr Co. also became interested in the process at about the same period. The investigations by the Freeport Sulphur Co. on the process as applied to the Cuban nickeliferous laterites, which resulted in the Nicaro enterprise, and the results of this operation have been well described elsewhere.1,²,³,4,5 This Nicaro plant was, in operation for almost two years, and during this period produced about 10 pct of the world nickel production from laterites containing 1.35 pct nickel. This plant and its operation were war measures and, in view of this, activities were suspended in April 1947. The results obtained fully demonstrated the technical feasibility of the process and its economical aspects on a commercial scale. In this respect, it should be understood that it is probable that improvements may be made by further development, and that there are possibilities for advantageous application of the process to garnierite and similar ores with higher values in nickel than the laterite iron ores at Nicaro. While the articles cited above have given a certain amount of information, no general article containing all the important process data has been pub- lished. Since the process is of more than local interest, a fuller knowledge of the fundamental and practical factors of the method may be welcome to those interested in this new field of metals technology. The author, accordingly, takes pleasure in submitting this article to the AIME as it represents in a condensed form the results of many years of research. The brief outlines of the fundamental and other factors and the explanation of observed phenomena are presented with as little discussion of details as possible, consistent with clarity. It is a special satisfaction to the author to make some contribution of his own in return for the benefits of the many valuable publications issued by the Institute during his thirty years of membership. Ores Adapted for Ammonia Leaching: All nickel and cobalt ores which originate from weathering of peridotites or similar basic rocks having sufficient values are suitable for treatment by the ammonia leaching process after a preliminary reduction under proper conditions. The formation of these deposits was probably as follows: In the course of time the basic rocks were attacked by atmospheric agencies; MgO and SiO2 were gradually leached out, and secondary nickel minerals formed, such as garnierite, a hydrated silicate of nickel and magnesia. These secondary products are, however, not stable. They decompose in a further stage of weathering and ultimately only a relatively small residue of insoluble oxides remains, known as laterite iron ore with a small nickel content and very little cobalt. Under these mantles of laterite, richer nickel values may be found, usually indicated by the occurrence of garnierite. The more the ore is disintegrated by nature, the higher the iron content and the better the nickel extractions that may be expected therefrom. Table I shows extractions that may be expected from different types of ores, assuming treatment of -200 mesh products and that all precautions have been taken for obtaining maximum extractions. As for the distribution of the various nickel minerals and compounds that may be present, great variations may occur from locality to locality as well as vertically in a deposit. From such "run of

Jan 1, 1951

By Rollin A. Slater

This paper presents a composite of ideas on materials handling systems by describing the design of an over-all system for a hypothetical steel pellet plant located on the Great Lakes. The bulk materials handling industry has served for years as the skeleton and the central system of nerves and nourishment for the body of basic industries. During the past two decades, this body has undergone substantial growth and mutation to meet the surging demands of our national economy for more and better products. The steel industry has kept pace with spiralling demand by innovation which has resulted in new processes and improved designs which generally yield greater production from fewer units. Materials handling technology has likewise improved its techniques and currently has a new, stronger generation of equipment to perform its necessary supporting function. Drawing upon excerpts from several recent plant designs, this paper describes a basic approach to the selection and application of modern bulk materials handling systems to an entirely new steel plant. Specific details are not available for publication, and therefore the plant described herein is a composite of ideas. This imaginary plant will be located on the United States side of the Great Lakes and its owner will be called the Hypothetical Steel Corp. for purposes of discussion. TYPES OF EQUIPMENT The basic bulk materials handling systems and components required in a plant so situated are: lake boat unloaders; railroad train unloading systems; storage pile stackers and reclaimers; large bins and regulating feeders; and the conveyor systems — with their attendant controls— which connect the foregoing. PROGRAM OF DEVELOPMENT The initial work on the plant must be that of the process engineers who develop and refine the basic data, i.e., the logistics of all raw materials, waste materials and products within the plant. During this phase of study, the materials handling engineer may advance his planning only in basic areas such as movements at the dock and movements at the railroad. This initial planning work is concerned only with defining logical plant locations in the light of channels, currents, existing traffic, governmental regulations, locations of existing railroads and available rights-of-way. These systems alone have their own individual criteria which must be respected and accommodated in the final layout. All other elements, such as the arrangement of the blast furnaces, power house, coke plant, by-product plant, scrap preparation plant, BOF shop, and facilities for continuous casting, degassing, calcining, etc., are dictated by their own specific needs and their relation to each other. In the arrangement of these latter facilities, the materials handling system is secondary and must be designed to accommodate. BASIC LOGISTICS The result of the process engineer's work can be expressed in terms similar to those shown in Table I. Plants are customarily rated in terms of annual tons of ingots. Therefore, the basic size of this plant can be determined by referring to the BOF Shop wherein it is sized at 5 million tpy. From the base, the required hot metal can be traced to the blast furnace, which in turn indicates the amount of required flux, iron bearing materials and coke —which in turn establishes the demand for coal. Likewise, the total demand for flux can be determined by the combined demand of the lime plant and blast furnace. The generation of fines and waste products, which have significant value but are not usable as such, create the need for a sintering plant. From projections such as the foregoing, the complete flow of materials can be established and accommodated. The basic premise upon which this typical materials balance is predicted is that the plant will be a producer of high tonnages of non-SpecialtV- products. All basic raw materials (flux bearing, iron bearing, coal) will be prime quality. For example, the basic iron charge will be pellets, and the iron ore fraction will be sized lump, all of which

Jan 1, 1970

By Orson Cutler, Shepard

THE OBJECT of this paper is twofold: (1) To analyze the forces that cause air bubbles to spread on mineral surfaces in the flotation process; and (2) To develop a rational expression that will serve as a criterion of the floatability of minerals, to the end that the efficiencies of various flotation reagents can be accurately compared. Heretofore, the subject of the spreading of air bubbles has been dismissed with the statement that the surfaces of minerals on which bubbles spread are water-repellent. Imperfect understanding of the forces involved has led to the use, hitherto, of various erroneous formulas for the calculation of the comparative effectiveness of flotation reagents.

Jan 1, 1932