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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

By R. B. Gordon, D. A. Koss

Ultrasonic-atlenuation changes due to the formation of free dislocations have been observed during tensile tests of magnesium and LiF single crystals and samples of polycrystalline Results on the LiF and samples are similar: A preyield attenzration increase is observed which, however, be-corlzes smaller as the magnitude of the drop in load al yielding increases. This indicates that the yield point observed in these materials is due to dislovation rather than dislocation unpinning and that the initial density ' free dislocations must be low if the yield point is to be sharp,. Tests on the magnesium ere conducted at both 27" and 200C. Magnesium has the unusual property that the yield drop is larger at the higher test temperature and is accomplished by a decrease in attenuation. The latter is due principally to the temprovary pinning of detained dislocations by highly solute atoms. After strain aging., a stress as low as 0.3 bur suffices to unpin dislocations; microstrain measuements of sufficient sensitivity should. reveal plastic flow at stress levels this low IN another paper,' we describe the technique of simultaneously observing ultrasonic-attenuation changes and plastic microstrain during deformation of spher-oidized carbon steels. Changes of ultrasonic attenuation indicate damping effects caused by the oscillation of long, freely moving dislocation segments. Simultaneous microstrain measurements are used to indicate total dislocation motion. The dislocation-damping observations are most useful in the study of the early stages of deformation where the dislocation density is low and the plastic strain is small and relatively difficult to measure. Particularly interesting results are found in materials which display sharp yield points. Observations of these phenomena are reported here for three materials: single-crystal LiF and magnesium, and poly crystalline molybdenum. EXPERIMENTS Dislocation-damping effects were observed by measuring changes in acoustic attenuation with the ultrasonic-pulse method. The end faces of each of the specimens were ground flat and parallel and a quartz 10 Mc per sec, x-cut transducer was attached to one face. The bonding agents used were: a) "Nonaq" stopcock grease with magnesium, b) beeswax with LiF, and c) salol with molybdenum. With the LiF, the best acoustic signals were obtained at 45 and 50 Mc per sec; all other measurements reported are at 10 MC per sec. The Sperry Ultrasonic Attenuation Comparator2 was used to measure attenuation changes. In the

Jan 1, 1967

By E. E. Thurlow

The Geology Div. of Northern Pacific Railway Co. has adapted to its exploration efforts field procedures for geochemical sampling and semi-quantitative analysis which have been developed through research by the U. S. Geological Survey. The sampling is done in conjunction with reconnaissance geologic mapping on aerial photographs or during field checking of maps which have been prepared largely by photo-geologic interpretation. Stream sediment or soil samples are taken and readily soluble combined heavy metals are extracted with ammonium citrate followed by colorimetric titration with dithizone at the sample site. The effectiveness of this approach has been demonstrated both in positive and negative results, thereby assisting in the elimination of large areas of land from further immediate attention and in providing targets for followup exploration. An occa sional sample is submitted for spectrographic analysis as a check on the possible presence of other elements of economic significance. Field laboratory procedures are also being implemented for determining molybdenum, mercury, and other metals which may be valuable in themselves or useful as pathfinder elements in outlining mineralized areas. A lead-zinc occurrence in Oregon and a copper deposit in Montana were readily detected and outlined by stream sediment and soil sampling and a heavy metal anomaly that lacks obvious interpretation has been found in northwestern Montana. Detailed mapping and additional sampling are followed by other exploration techniques if warranted. Northern Pacific's program of reconnaissance mineral evaluation of company-owned lands and adjoining areas was outlined in a paper presented at the American Mining Congress meeting in Las Vegas four years ago. That report included policies and procedures with respect to mineral development on Railway Co. lands and may be referred to for information on these matters.1 In a sense this paper is a progress report on the use of geochemical prospecting in Northern Pacific's continuing mineral evaluation program. At this time there are positive results but as yet there is no real success story in the form of a minable ore body. GEOCHEMICAL PROSPECTING PROCEDURES The decision to use geochemistry as a reconnaissance exploration tool must be followed by research into sampling and analytical methods and into the interpretation of results. Various analytical methods were tried and evaluated by the Geology Div., including hot and cold acid extraction with and without fusion of the sample, panning and magnetic separation followed by dithizone testing of the magnetite, and cold aqueous extraction of metallic ions followed by indicator tests. Samples were first sent to the laboratory for analysis; later field laboratories were established and now virtually all testing is done at the sample site. It was concluded that, where applicable, the quickest dependable methods for reconnaissance use are the dithizone field tests for readily extractable heavy metals. This involves the simultaneous treatment of a sample, usually of soil or stream sediment, with two immiscible liquids; one a cold aqueous extractant (ammonium citrate) and the other a solution of dithizone in toluene or xylene.2 Dithizone is a colorimetric indicator that reacts quantitatively with copper, lead, zinc, and several other metals to form colored complexes in organic solvents. Results may be expressed in ml of 0.001 pct dithizone that are required to reach the blue end point, or calibration of the test results can be carried out with standard solutions of zinc; conversion factors would then be expressed in ppm, zinc equivalent. Calibration of dithizone solution with zinc standards indicates that 1 ml of 0.001 pct dithizone is equivalent to approximately 0.25 ppm of zinc. An authoritative report on dithizone field tests authored by H. E. Hawkes in the June-July 1963 issue of Economic Geology* states "The appeal of these techniques has been the simplicity and speed of the determinations as compared with more tedious laboratory determinations of trace metals in weathered rocks, soils, or plant materials. This obvious appeal, however, has often been more than matched by misuse of the method in such a manner that the results are

Jan 1, 1964

By Brown, R. W., G. H. Neill, R. G. Loper

All facets of ball sealer behavior must be known and understood to design for their optimum use in well treatments. The down-hole factors including the inertial forces, drag forces and holding forces have been discussed. Equations have been developed and presented for these forces. The use of these equations in this process will contribute to the most efficient use of an economical and proven ball sealer process. The urocedure presented has been used to successfully analyze field results indicating problems involving the use of ball sealers. These problems have been isolated and corrected in future treatments by using the procedure presented to revise the perforating program, the injection rate, the design of ball sealer stages and/or the type and size of ball sealers. The procedure presented also indicates that dislodgement of ball sealers occurs primarily in ultra slim-hole completions. INTRODUCTION The perforation sealing process has been proven highly successful and economical since it was introduced to the oil and gas industry in early 1956.' Since it has proved so successful in multistage fracture treatments at a much lower cost than conventional packers, the ball sealer process has become a byword in well completions.' Not only has it changed the design of fracture treatments, it has changed the concepts of selectively perforating and has greatly aided the success of the single-point and limited-entry techniques." Yet with all the advantages, there are still facets of ball sealer behavior that are not widely recognized. These must be known and understood to better design and execute the optimum ball sealer treatment. The down-hole behavior of ball sealers is influenced by a number of factors including an "inertial force", a "drag force" and a "holding force". These are considered in two phases—the initial seating of the ball and the forces tending to unseat the ball after contact has been made (see Fig. 1). This paper presents a theoretical study of these factors and formulas for predicting their influence. The authors acknowledge the fact that the flow equations presented herein describe the behavior of Newtonian fluids and do not cover the so-called power-law fluids. The assumptions made, however, are reasonable and well within practical limitations of the conditions encountered during field application. For example, it is assumed that the perforations are round with a discharge coefficient of 0.82. While this may not be exactly true, it has been verified within practical field limitations.' The discharge coefficient would not vary significantly even if the perforation size or configuration varied pronouncedly. The approach of assuming uniform perforation size is not as strained as it might first appear. Normally, a perforator contains charges equally spaced with the same number in each vertical (or horizontal) plane. If the perforating gun is not centralized, the holes in one plane will be smaller than average, while the holes in opposing planes will tend to be larger than average. The net result is that the two effects tend to balance. FACTORS AFFECTING CONTACT WITH PERFORATlON Ball sealers are injected into well treating fluids for the purpose of contacting and sealing those perforations which are accepting the fluid flow. The efficiency of the sealers is primarily influenced by: (1) the velocity of the balls down the pipe, and (2) the fluid velocity through the perforations. To divert the sealer to the perforation, the inertial force of the ball must be overcome by the drag force created by the fluid velocity through the perforation. BALL VELOCITY The final, or stable, velocity of the ball is the sum of the actual fall velocity and the fluid velocity. This will be

By R. M. Hudson

The removal of nitrogen from a nitrogenized low-carbon sheet steel that contained 0.011 wt pct N was determined during heat treatment in Hz-N, mixtures. TIze process followed a first-order rate law; that is, plots of the logarithm of nitrogen content in steel were linear with the time of treatment at a given temperature. The rate of removal increased with an increase in temperature from 900" to 1300°F. By 1400°F the rate in dry hydrogen had decreased to a value intermediate between the rates at 1200" and at 1300°F; in wet (2.47 vol pct water vapor) hydrogen the rate at 1400°F was less than the rate at 1300°F and nearly the same as the rate at 1200OF. The rate at a given temperature increased as the 3/2 power of hydrogen concentration in the atmosphere. While wet atmosplzeres were generally more effective than the corresponding dry atmosplzeres, the effect of water vapor was much less pronounced than the influence of hydrogen content. NITROGEN is the principal agent in the strain aging of ferrite, the effect of carbon being secondary.' To eliminate the return of the yield point after straining and aging, it is claimed2 that the amount of nitrogen in solution in steel must be reduced to 0.0002 wt pct. Strong nitride-forming elements (titanium, vanadium, zirconium, and aluminum) can act to eliminate strain aging by combining with nitrogen. It is extremely difficult to decrease the nitrogen content in commercial steels to the low level required by conventional coil annealing because of the poor contact between the strip surface and the reactive atmosphere. However, a variety of gas-metal reactions can be effected by use of the open-coil annealing method,3 in which the metal surface is fully exposed to the atmosphere. With this possibility in mind, the Applied Research Laboratory has studied the influence of time, temperature, and atmosphere composition on the removal of nitrogen from low-carbon sheet steel. MATERIALS AND EXPERIMENTAL WORK Samples from a commercial nitrogenized low-carbon steel (0.010 in. thick) in the cold-reduced condition were used. The chemical composition of this steel is given in Table I. The gas mixtures used are listed in Table 11. The moisture content in the "wet" annealing atmospheres was controlled at a +70°F dew point (2.47 vol pct water vapor) by passing the gas mixture through a glass tube packed with a solid mixture of 10 pct anhydrous oxalic acid and 90 pct oxalic acid dihydrate held at 127°F; this technique has been described previously.4 For "dry" atmospheres, the gas mixtures were passed through a cold trap immersed in liquid nitrogen. A hinged-top Hevi-Duty electric furnace was used with a Vycor-glass furnace tube. When the furnace was at the desired temperature, the gas mixture was passed through the furnace at a flow rate between 1.1 and 1.2 cfh; coupons (size 3 by 3/4 in.) of the steel were pulled into the center of the Vycor-glass

Jan 1, 1964

By D. A. Woodford

In a constant-load creep test, if the density of nlobile dislocations is assumed constant for strains exceeding that corvesponding to the minimum creep rate, it is shown that the creep rate may be approximated by the equation where E is the nominal strain, o0. is the initial stress, and a' the stress fov unit dislocation velocity. The constant C contains the mean density of mobile dislocations and n is a measure of the stress sensitivity of dislocation celocity. This equation is shoum to be applicable to published data on an alloy steel and on nickel. The degree of plastic instability and hence the creep ductility is dependent on the calue of n for these materials. When instability becomes gross and local macroscopic necking occurs, the assumptions are no longer valid. On the basis of this equation, and the strain-time relation derived from it, a method of predicting the creep behavior at different stresses is suggested. MOst analyses of creep data have been concerned with time-dependent transient creep or time-independ- ent secondary creep in constant-stress tests. The far more widely used constant-load test has been neglected in terms of a mechanistic approach. In general, since the strains involved are usually small, the same laws for transient creep may be applied to both types of tests. However, there is no steady-state creep in a constant-load test since the stress increases continuously. Any apparent steady state observed on a strain-time plot is either fortuitous or illusory, and is generally revealed as a continuously varying creep rate on a carefully constructed strain rate vs time plot.* Transient creep may be understood in terms of a simple differential equation representing the change in mobile dislocation density with time:' where p is the density of mobile dislocations. The first term on the right is related to first-order kinetics of dislocation multiDlication and the second to second-order kinetics of exhaustion. On the basis of this equation, several authors2-4 have found good agreement with experimental transient creep curves for a number of materials. When k1p = k2p2, a steady-state creep

Jan 1, 1968

By C. R. Criss, R. J. McCormick

ThiS paper .summarizes the development and perform. ance of the Coldwater Oil field, Isabella County, Mich. Production is obtained at a depth of 3750 ft from a dolomite reservoir, which is probably both Rogers City and Dundee. There appears to be no persistent barrier to vertical fluid movement between the Rogers City and Dundee, and both formations are believed to have a common original oil-water contact. No we1ls are open to production at the level of the Dundee. The discovery of the field in 1944 was followed by the drilling of 81 producing wells and nine dry holes. By the end of 1952, the field had produced 12,763,000 bbl of oil, at which time 69 active wells were producing 3600 B/D oil and 21,000 B/D water. The reservoir has an effective natural water drive, and bottom-hole pressure has declined 75 psi from an original pressure of 1453 psi. Oil is undersaturated at reservoir conditions with a solution GOR of 512 cu ft/bbl and a saturation pressure of 1190 psi. INTRODUCTION Although the Coldwater Field is now in its ninth year of production, it ranks seventh in cumulative recovery, and second in current daily oil production in the State. Following complete development of the field in 1946, it has consistently contributed approximately 11 per cent of Michigan's daily production. Coldwater appears to have a greater pay thickness than most fields producing from the Rogers City forma- tion in the west central part of the Michigan basin. Except as influenced by the extent of closure and the thickness of the oil column, reservoir performance is believed to be representative of Rogers City fields in this part of the basin. For this reason, it is felt that the following presentation of factual data for the field will be of general interest. HISTORY AND DEVELOPMENT Discovery of the Coldwater field during Aug., 1944, followed favorable subsurface geological correlations and core tests drilled to a shallow stratigraphic marker horizon. The field is located in the west central part of the Michigan Basin in Coldwater Township (T16N-R6W), Isabella County. It is 60 miles west-northwest of Bay City, and near the geographic center of the southern peninsula of Michigan. The discovery well flowed 200 bbl of oil the first 24 hours from the Rogers City dolomite at a depth of approximately 3750 ft. Field production is principally from the Rogers City with a minor amount assumed to come from the underlying Dundee dolomite, although none of the wells are open to production at the level of the Dundee. Both the Rogers City and Dundee formations belong to the Devonian system (See Geologic Column-Fig. I.) In addition to Rogers City-Dundee oil production, sweet gas is produced from the Michigan Stray sand of the Mississippian system at a depth of 1400 ft. The gas reservoir has approximately the same areal extent as the underlying oil reservoir. Although gas production is an important feature of the Coldwater field, this report is concerned only with the oil reservoir. The productive area is approximately 3200 acres. The pool is developed on a 40 acre spacing pattern with wells drilled in the center of the north half of 40 acre tracts, except for a few off-pattern wells drilled along

Jan 1, 1955

By P. Hazebroek, M. Prats, E. E. Allen

Well locations in water floods frequently do not coincide with the ideal well locations associated with the flood pattern which is used. A question of importance is. "How much oil is lost because of this?". This is the problem treated in this paper. It is assumed that each pattern in a five-spot flood has the proper number of production and injection wells but that the wells may be off-pattern. The distance by which a well is off-patern is given in terms of the pattern spacing, defined as the length of one side of a five-spot. The influence of off-pattern wells on the performance of a five-spot flood has been investigated mathematically for unit mobility ratio. All production and injection rates are assumed to remain equal. The loss in recovery resulting from pattern irregularitie: has been calculated at a cumulative water injection corresponding to a 98 per cent water-cut in a regular five-spot. Displacing a single production or injection well by about one-third the pattern distance reduces the total field recovery by 4.4/N per cent of the recovery obtainable with regular spacing, where N is the number of five-spots in the flood (assumed large). When off-pattern wells are separated by at least one regular five-spot and are displaced by less than one-third the pattern distance, the total loss in recovery in a large-scale flood is, at most, 1 per cent of the recovery obtainable from that field with a regular five-spot pattern. However, much higher losses may occur if the off-pattern wells are not separated by a regular five-spot, if the rates are imbalanced, or if the mobility of the injected water is higher than that of the crude. Although the loss in oil recovery due to pattern irregularity often may be low, the off-pattern case will always require injection of more water to reach the same final water-cut. The volume of water injected per unit volume of oil displaced has been calculated for each five-spot adjacent to a five-spot containing a single 08-pattern well. The cumulative water injection at the time of 98 per cent water-cut may be increased by as much as 37 per cent when a production well is displaced one-third the pattern distance toward an injection well. The existence of differences between actual subsurface locations and the idealized well patterns used in secondary recovery operations is well recognized. However, the methods commonly used for predicting waterflood behavior ignore such differences, even when subsurface locations are known. The reason for this is simple. The idealized well patterns are highly symmetrical and, as such, the production history of the pattern (and even of the field) can be determined from that of a few production wells—usually from only one. Consideration of the many irregular well spacings found in a specific field would entail a large amount of work, and then the results would be applicable only to that specific field. In an attempt to provide an answer to the more general problem, this paper considers a water flood having an idealized well pattern, except for one well which is not at its regular location. When several off-pattern wells are present, their contributions are assumed to be additive unless the off-pattern wells are close to each other. Only four positions of the off-center well (at x, y. of Fig. 1) are considered in this paper. These are shown

By W. B. Gogarty

With flow of non-Newtonian fluids in porous media, effective viscosities are needed for use in the Darcy equation. These viscosities depend on the rock parameters and flowing conditions. In this investigation, rheological and flow results were correlated to develop an expression for calculating effective viscosities. Surfactant-stabilized dispersions of water in hydrocarbon were used with consolidated sandstone cores of different permeabilities. The average shear rate in a core was related to the permeability and porosity of the core and the frontal velocity through the core. By using the correlation obtained for determining effective viscosity, experimental and theoretical values were compared for each fluid system by determining average and maximum errors. For the fluid system showing the largest average error, the correlation fit 38 experimental points with an average and maximum percentage error of 4.3 and 14.8, respectively. For the fluid system showing the least error, average and maximum percentage errors of 1.8 and 4.3, respectively, were calculated using 29 experimental points. INTRODUCTION Use of non-Newtonian fluids in the petroleum industry is not new. Fluids of this type have been used for many years as fracturing agents and drilling muds. Recently, attention has focused on the use of high molecular weight polymer solutions for secondary recovery. Results have been reported on studies relating to the flow behavior of polymer solutions in porous media.1-4 Each study gives the viscosity in the Darcy equation as a function of the rheological properties of the fluid, the characteristics of the porous medium and the pressure gradient. The functional forms of the reported expressions differ somewhat in each study. The first three studies used unconsolidated porous media while the fourth used a single consolidated core. Because of the limited information available on the flow of non-Newtonian fluids in porous media, further investigation was undertaken in this area. We selected non-Newtonian fluids that did not contain high molecular weight polymers in order to minimize core plugging. The over-all objective was to gain a better understanding of the flow behavior of non-Newtonian fluids in consolidated porous media. Specifically, our goal was to determine the relationship between the average shear rate in a core and the frontal velocity. Because of this goal, it was necessary to determine the effect of permeability on the shear rate-frontal velocity relationship. We wanted to replace the viscosity in the Darcy equation with an expression relating to the average shear rate in the core and the rheological properties of the non-Newtonian fluid. THEORY For a time-independent, non-Newtonian fluid, the apparent viscosity is a function of the shear rate. This relationship is given by µ = F(v')...........(1) With Eq. 1, a single value of shear rate determines the apparent viscosity at that shear rate. With flow in porous media, a spectrum of shear rates occurs at any average throughput. An average shear rate v' can be used to represent the spectrum of shear rates that exists within the core. By using v' and the rheological data given by Eq. 1, an effective viscosity is determined for the flowing fluid. If v' is the correct average, µe becomes the appropriate viscosity for use in the Darcy equation. Under these conditions, flow rate-pressure drop relationships can be determined for non-Newtonian fluids. HOW the correct average shear rate might be related to the frontal velocity through the core and the characteristics of the porous media will now be considered. Later, the experimental data are presented that indicate the validity of these

By John E. Carr

A bewildering variety of continuous thickeners and clarifiers are used in mineral industries and other heavy industries. General topes arc: ? Conventional thickeners ? Thickeners with flocculating feedwells ? Solids contactors ? Tray thickeners ? Lamellas ? Conventional thickeners with Lamellas ? High flow, fluid bed thickeners These units must be adapted to varied applications. They must provide operating flexibility to meet process needs. Such factors multiply the decisions which must be made prior to the selection of a thickener. The seven types of thickeners listed above, with their variations, share design concepts which limit their application and which can be used to evaluate their performance. Some of these arc: ? Feed velocities must be limited and/or controlled. ? Natural or reagent flocculation is necessary. ? Horizontal settling area is the basis for capacity. ? Overflow velocities must be limited and. or controlled. ? A controlled underflow is necessary. Thickener selection is the application of these needs to the basic process concepts. The basic function of a thickener, in the minerals industry, is the separation of a thickener sludge containing fine solids from water. In addition to this primary separation function, others include: ? Separation of solids from water ? Separation of flocculated solids from slimes ? Storage of solids ? Control of percent solids ? Storage of water ? Process control by absorbing fluctuations in feed ? Process control by increase in head clue to the depth and percent solids of the thickened sludge. Most thickener designs, suitable to minerals applications, are based on the separation of minus 65-mesh, 2.7 specific gravity solids containing slimes. These designs are routinely adapted to coarse and or denser materials. Materials of lower specific gravity such as coal, wood, char, some chemical precipitates and organics act Hike slimes if a thickener is used. Perhaps the most conservative approach to sizing and application is the use of comparative data from similar plants or similar industries. Thickeners are-routinely used in a great number of industries from which there is good historical information available. In the minerals industry, thickeners are used in: clay sizing, coal refuse, heavy media, copper concentrates, copper tailings, gold flotation concentrates, and countercurrent decantation for cyanidization in gold and CCD in uranium. Concentrate and tailings thickeners are used in iron ore plants, and concentrate and tailings units in lead-zinc plants. In addition, there arc thickeners designed to handle lime mud; limestone concentrates and tailings; phosphoric acid; potash; and rutile concentrates. Thickeners are, in addition, widely used in gravel plants for water reclamation. This gives excellent data on clay settling in some cases. Thickeners are used extensively for slurries generated by flue dust from wet scrubbers. Thickeners in flue dust applications are operating with considerable variations, treating blast furnace dust. BOF flue dust, and wood char. Similar applications are met in the power industry with fly ash and SO2 scrubber systems. Even though field data is preferred, such data has limitations as listed: ? Flowsheets are seldom identical. ? Data is often incomplete or limited. ? Ores vary significantly. ? Operating needs are changing. For these reasons, mathematical and theoretical methods are needed for application of field data to a specific project. In addition, laboratory data for similar projects and, if possible, laboratory data on a representative sample should be used to specify the thickener. There is a great volume of thickener literature. The references for this paper, along with their references, and past AIME papers provide excellent background. Older literature can be reviewed in light of current methods. It is interesting to note that the requirements for higher flow rate designs, more extreme flocculation systems, etc., can be logically introduced by reading Gaudin's Sections on Flocculation and Thickening, which was written before field installations could illustrate all of his ideas. The problem, then, is to select hardware which will take into consideration the functions of flocculation, separation of the solids, water clarity, control of the underflow, and control of the overflow. Reliable operation and simple control are customary.

Jan 1, 1979

J. B. Cohen (AVCO Mfg. Co.)-The model presented by the authors is only one of several possible mechanisms for low-temperature aging. It is true that the motion of dislocations to the copper atoms, followed by diffusion along the dislocation lines, is one such mechanism. However, the details of such a process which would :result in copper-rich platelets on (100) planes in the f.c.c. matrix are not clear. Furthermore, there is at least one other mechanism that may be used to e.xplain the authors' results, so that the data do not clearly favor the Turnbull model. The zones may form by "normal" diffusion. The diffusion constants would be higher at room temperature than extrapolated data would suggest due to vacancies trapped in the specimens in the quench. The diffusivity would then be multiplied by the ratio of the number of vacancies present at the solution temperature to that present at room temperature. These vacancies could remain in the alloy specimen for long times at room temerature, due to interaction with the copper atoms. ' The activation energy for diffusion is smaller than that for bulk diffusion at elevated temperatures for it is only that for the motion of vacancies existing after the quench; after these are used up, the aging process effectively ceases. It is somewhat questionable if the laws governing transformation kinetics can be directly applied to changes in elastic moduli, especially in the case of aging where the structure and the composition of the zones may be changing during aging, If such laws are assumed, it is possible to explain the exponential factor of % with this vacancy model. It is probable that the structure of the zones and the matrix match only on (100) planes. Certainly the precipitates that form in this system after various aging treatments show orientation relationships similar to those of the zones. Strains on the edges of the zone may set up fields which do not allow the zone to grow in an edgewise manner. The exponent in the growth of a thin plate in a direction perpendicular to its face would be %. It may also be that copper atoms are attracted to dislocations. If this is the rate-controllin factor in the growth process Ifthisthen an exponent of % or % may arise. The writer would like to know if the authors have tried plotting l/a; proportional to as might be expected for "dislocation drainage." R. H. Doremus (General Electric Research Laboratory)—An important new method for following the growth of Guinier-Preston zones is presented in this paper, and I wish to congratulate the authors on their experiments. Their interpretation of the results, however, is doubtful in certain respects. To determine the exponent m in Eq. [4] the authors plotted -log at against t to various powers (their Fig. 6). The initial value of frequency used for these plots was found by extrapolating the data to zero time. In Fig. A the data from their Fig. 2 are plotted against a linear, rather than logarithmic, time scale. To obtain graphs similar to their Fig. 6 for these data one must use an initial frequency of about 52720; such a plot for m = % is shown in Fig. B. The straight line in Fig. B fits the data in an intermediate range only. The curve drawn in Fig. A was mapped from this line; comparison of

Jan 1, 1960

By David C. Jonson, W. Bruce MacKenzie, Arthur A. Bookstrom, Vaughn E. Surface, Neil K. Muncaster, Stewart R. Wallace

In mid-Tertiary time a wet silici-alkalic magma penetrated the Precambrian rocks of what is now the Tenmile Range of Central Colorado and formed the Climax Stock. The stock is a composite one and was intruded in four separate irruptions, each giving rise to a major hydrothermal event. The first three of these produced large stockwork ore bodies that cap and flank the tops of their respective source intrusives; the fourth, and last, yielded almost no commercial mineralization. The ore bodies and their related zones of alteration are circular to ring-shaped in plan and arcuate in section. The different phases of the stock are so positioned with respect to each other that many of the circular and arcuate zones of mineralization and alteration overlap or are juxtaposed. Evidence of a time separation between the different ore bodies is found in certain dikes that were intruded between periods of mineralization and are well mineralized in one ore body but are barren in another. If it is assumed that the parent magma at Climax contained 10 per cent "water," that the "water" contained 0.1 grams per liter of molybdenum, and that the processes of extraction were 100 per cent efficient, then approximately 10 cubic miles of magma would be required for the formation of each ore body. The volume requirements, taken in conjunction with the cross-sectional areas of the different phases of the stock to explored depths, suggest to the authors that each magma chamber was columnar, extended to a depth of thousands of feet, and was connected with a much larger master reservoir. The repetition of similar intrusive, structural, and hydrothermal events, indicates periodic tapping of this reservoir. A regular chemical evolution of the parent magma is suggested by the systematic change in metal ratios and differences in the sites of deposition, relative to the source intrusive, in each of the four separate igneous hydrothermal stages. The preparation of ground was due to changes in magmatic and/ or hydrothermal pressures within the igneous-hydrothermal columns; small, repeated, up and down movements of the rock enclosing the tops of the columns formed the stockwork fractures into which the mineralizers penetrated. The forceful emplacement of each successive phase of the Climax Stock resulted in a slight doming and rotation to the westward of the earlier-formed geologic features. Postore normal displacement along the Mosquito fault is estimated at about 9000 feet. Part of one ore body was cut by the fault and lies at depth below the Paleozoic sedimentary strata on the hanging wall. On the footwall side of the fault, subaerial erosion and glaciation removed a large part of one ore body and uncovered the top of a second.

Jan 1, 1968

By Reinhardt Thiessen

In the general study of coal, all evidence points in the one direction —that coals had their origin in a manner analogous to that of peat. The best method of studying coal, whether it concerns its chemistry, composition, or physical condition, is to study peat. The essentials in a study of peat are a knowledge of the chemistry of plants, knowledge of decay and of the transformation process of plant-substances into peat. A number of facts must be emphasized, namely, (1) peat is formed under wet conditions only; (2) plants grow in the place where peat is formed; (3) all the plant substances go into the bog; and (4) all the plant substances are subjected to a series of phases of decay which are (a) in the air completely above the water level but in relatively moist conditions; (b) above the water level, but covered by debris; and (c) completely submerged by both water and debris. Plant Chemistry Plant chemistry as a whole is remarkably well understood. The number of compounds composing plants is large, and it is not possible here to give even a comprehensive outline, but a classification into definite groups is possible; this is as follows: Carbohydrates; glucosides; pigments; tannins; acids, alcohols and ketones, etc., and their salts; essential oils; resins; vegetable bases; proteins; enzymes. Plant substances may also be grouped according to the role they play in the life of the plant, such as: Framework materials, living materials, food materials, protecting materials, waste materials. While this classification groups them well for. certain purposes, it does not group them exactly chemically; but in a consideration of the composition of coal, this is an excellent classification for our purpose here.

Jan 1, 1925

By T. L. Chu, G. A. Gruber

Silica films hare been rleposited 011 silicon substmtes at 400° to 600°C by a chemical-transport technique using hydrogen fluoride as the transport agent ill a closed system. This transport takes place from a source materia1 1071: temperature to substrates at higher temperatures, as indicated by the thermochemistry of the transport reaction. The experimental variables of- the transport process, such as the substrate temperature, the pressure pi the transport agent, and so forth, have been studied. The rate -determining step of the transport process appears to he the ),ale of chemical reaction in the source region. The transported films are similar to thermally grown silica films in physical proper-ties with the exception of 'some what higher dissolrrtion rates. SILICA films deposited on suitable substrates serve many purposes in electronic devices. They are used for the fabrication of tunneling devices, the surface passivation of devices, and the shielding of devices from nuclear radiation: and as selective masks against the diffusion of specific impurities into semiconductors. Doped silica films can also be used as sources for the diffusion of impurities into semiconductors. Several oxidation and deposition techniques for the preparation of silica films have been developed to meet the requirements of these applications. The therma1 oxidation of silicon by oxygen or steam at temperatures above 900 C is commonly used in silicon technology. The deposition techniques are perhaps more advantageous since they usually require lower temperatures and are not limited to silicon substrates. Silica films have been deposited on silicon and other substrates by reactive sputtering and chemical reactions. The sputtering of silicon in an oxygen atmosphere is capable of depositing good-quality silica films on silicon' and gallium arenide. Many chemical reactions are known to yield silica at room temperature or higher. These reactions may involve intermediate steps. However, the final step yielding silica should take place predominately on the substrate surface in order to produce adherent films. When silica is formed in the gas phase by volume reactions, no adherent deposit can be obtained. Generally, the experimental conditions of a reaction can be varied so that the surface reaction predominates over the volume reaction. The chemical reactions which have been used successfully for the deposition of silica films are briefly as follows. The pyrolysis of alkoxysilanes in an inert atmosphere or under reduced pressure has been employed to deposit silica films on germanium3 and silicon4 at 650" to 750°C in a flow system. The deposition of silica films from alkoxysilanes has also been achieved at nearly room temperature by a low-pressure plasma. Device quality silica films have been deposited on germanium and gallium arsenide by the deposition of an amorphous thin silicon film followed by oxidation at 600" to 700" . Silica films for high-temperature capacitors have been produced by the hydrolysis of silicon tetrabromide at 950°C in argon and hydrogen atmospheres.7 We have developed a chemical-transport technique for the deposition of silica films on semiconductor substrates at relatively low temperatures. The thermochemistry of the transport reaction, the experimental variables of the transport process, and the properties of the transported silica films are described in this paper. THERMOCHEMICAL CONSDERATIONS The transport of solid substances by chemical reactions in the presence of a temperature gradient has been used for the preparation of films and crystals of many electronic materials. In this technique, a gaseous reagent is chosen so that it reacts reversibly with the solid substance under consideration to form volatile products. Since the equilibrium constants of most reactions are temperature-dependent, the transport of these products to regions of suitable temperature in the reaction system would cause the reverse reaction to take place. depositing the original solid. When the equilibrium is shifted toward the formation of the solid as the temperature is decreased, the solid is transported from a high-temperature zone to a lower-temperature region, and vice versa. This chemical-transport technique can be carried out in a closed or gas-flow system. In a closed system, chemical equilibrium is presumably established in the different temperature regions of the system, and the transport agent regenerated in the deposition region repeats the transport process in a cyclic manner. The local chemical equilibrium may not be approached in a flow system: however, this system offers a greater degree of flexibility. Silica reacts reversibly with hydrogen fluoride and this reaction was chosen for the transport process. The over-all reaction between silica and hydrogen fluoride may be written as: SiO2(s) + 4HF(g-) = SiF4Ur) + 2H2O(^)

Jan 1, 1965

By C. E. Mills

The Verde mining district is in Yavapai County, in north-central Arizona. Jerome, the principal town, has a population of 6000 and the two important mines of the district—the United Verde and the United Verde Extension—lie almost within its limits. Perched high on the southwest side of the Verde valley, at elevations of 4800 and 5500 ft. (1463 and 1676 m.) respectively, both mines have long tunnels from their lower levels through which the ore is hauled to the smelters. Clarkdale, the smelter town for the United Verde mines, lies in the Verde valley 4.1 miles (6.5 km.) distant in an air line from Jerome and at an elevation of 3560 ft. The two towns are connected by the standard-gage railroad of the Verde Tunnel and Smelter R. R., a subsidiary of the United Verde Copper Co. This road is 11 miles long and has a compensated grade of 4 per cent. At Clarkdale it connects with the Verde valley branch of the Santa Fe railroad. Clemenceau, the smelter town for the United Verde Extension mine, lies 3.5 miles (5.8 km.) in a southeasterly direction from Clarkdale, at an elevation of 3420 ft. It is connected to the Verde Valley branch of the Santa Fe railroad at Clarkdale by the Arizona Extension R. R., a subsidiary of the United Verde Extension Mining Co. The portal of the haulage tunnel, at an elevation of 3757.5 ft., is also connected with the smelter town by 4 miles of standard-gage track belonging to the same company. In the vicinity of Jerome, the great southern escarpment of the Arizona plateau forms the northeast side of the Verde valley. The general level of this escarpment, or "rim" as it is called, is about 4000 ft. above the Verde River. A corresponding elevation is reached only by the highest peaks of the Black Hills, which bound the valley to the southwest. Two lava-capped mesas, known as "Mingus" and "Woodchute mountains," form the culmination of the Black Hills. That part of the Old Black Hills mining district which lies between their crests and the Verde River is now known as the Jerome, or Verde, mining district. If the smelter towns are not included, a strip about 7 miles long by 3 miles (11 by 5 km.) wide, embraces practically all of the properties belonging to the Jerome district. T-bis strip lies parallel to and along the side of the Verde valley from First View, 2 miles northwest from Jerome, to the

Jan 1, 1925

By Sylvan Z. Beer

Aluminum phosphide was synthesized and grown in solution of excess aluminum using a modified two-temperature technique. An inversion in the density difference between ALP and molten aluminum takes place at about 1100°. Dispersed nuclei can act as sources for further crystal growth in a manner resembling ripening. Advantage was taken of this phenomenon by introducing a stirring motion into the molten liquid. This was done with a split-phase 10-kH2 rotating magnetic field produced by four horizontal coils placed symmetrically about the furnace at the level of the molten metal. The method also prevents the formation of a surface film which would impede the reaction. By this technique vastly improved yields were obtained and flat crystals 5 by 5 by 0.5 mm were grown at lower temperatures and at greater rates than heretofore. THE family of III-V intermetallic compounds has received much attention since the prediction of their semiconducting properties in the early 1950s. Of the family, A1P has perhaps the highest band gap of those compounds normally possessing the zinc-blende structure. But it has been least studied because it is difficult to handle and grow. The handling difficulties have been dealt with elsewhere and it is sufficient to say here that, by various techniques, many of the difficulties can be overcome.' The difficulties encountered in crystal growth can be related to the refractory nature of A1P and in turn to its high band gap. Because of the anticipated high melting point of the material and the accompanying high phosphorus vapor pressure, the reported work on synthesis and growth was done by epitaxial synthesis-growth via chlorine2 and iodine3 transport and from solution of excess aluminum by the two-temperature technique.4'5 The transport-grown crystals take on the dimensions of the substrate but do not grow easily in thickness. In the usual two-temperature technique as applied on the synthesis of Alp, the temperature of the molten aluminum is kept at 1000° to 1250°C while the phosphorus is maintained at 1 to 20 atm. A thin film of aluminum phosphide and oxide form immediately, impeding the reaction and affecting the yield. Attempts to grow the Alp from such solutions by the methods used to grow Gap and InP from excess gallium and indium have not been successful. As discussed in the preceding paper,5 the yield can be greatly increased

Jan 1, 1969

By O. Jay Myers

The war effort has furnished the necessary impetus for better magnesium foundry practice. Four or five years ago, there were but a few formulas in general use for core-sand mixtures for magnesium castings. Certain sands, binders, and inhibitors were specified and the proportions of these materials in each mixture were maintained between very narrow limits. As more and more war industries entered the field, much research was carried out and methods and practices were improved. Magnesium founding is still in a state of flux; therefore it is not uncommon to find one foundry spraying inhibitors on its cores, and another foundry using sand mixtures with incorporated protective agents. The basic core or dry-sand mold mixture for magnesium in use today is compounded with sand, core oil or resin binder, cereal, and moisture. Core oil or resin binder are added for baked strength while the cereal binder and moisture are for green strength. The normal mixtures (based on the weight of the sand) contain from o.5 to 1.5 per cent of both cereal binder and core oil, and the moisture content variesbetween 1.5 and 5 per cent. The ratio of core oil to cereal binder varies from 60:40 to 40:60, while the correct amount of moisture depends upon the method of coremaking. Protective Agents In all magnesium practice, protective agents are used in conjunction with the core and molding sands to prevent oxidation of the metal. The use of these inhibitors is not novel, but publications covering this field are not entirely adequate. Beck1 says: Magnesium alloys decompose water to form magnesium oxide, hydrogen being liberated in the process (Mg + H2O ? H2 ?+ MgO). This reaction results in the blackening of the skin and the appearance of areas of porosity on the casting surface, the cavities of which are filled with a grey oxide powder (these are termed 'burns'). Although sand cores for magnesium castings are thoroughly dried during the baking cycle, burning will take place on the casting5 unless the metal is protected properly. This type of burning is more difficult to define than the "water-magnesium" reaction cited by Beckl A possible explanation may lie in the following equation: 2Mg + O2—> 2MgO Here, the source of the oxygen is not water, but the air in the mold cavity, together with the chemically combined oxygen in the core-binding media. Generally, two methods are used to prevent this reaction from taking place.

Jan 1, 1945

By Carl F. Cline, Richard R. Vandervoort, Willis L. Barmore

THE objective of this investigation was to determine the high-temperature plastic deformation behavior of stoichiometric uranium mononitride as a function of stress and temperature. Interest in the properties of this material stems from its potential use in high-temperature nuclear reactor systems. The creep of other refractory compounds containing uranium (e.g., U02, UC) has been studied by various investigators.1"4 Fassler et al.4 have studied the creep of UN in vacuum from 1100° to 1350°C at stresses of 6000 and 8000 psi. In the present work, the creep of stoichiometric UN was investigated from 1500° to 1800°C at stresses from 2000 to 5000 psi in a partial pressure of 200 mm of nitrogen. The specimens were prepared by hot isostatic pressing of UN powder into cylinders of $ in. diam by about 1 in. high. After pressing, the specimens were heat-treated in nitrogen at 1900°C for 50 hr. The densities of individual specimens were determined by the water displacement method. All specimens were theoretically dense, based on a value of 14.32 g per cu cm.5 Principal metallic impurities in ppm by weight were: Ca, 50; Cu, 5; Fe, 30; Mg, 5; Ni, 10; and Si, 20. Oxygen content was 400 ± 50 pprn and carbon content was 100 i25 ppm. The nitrogen content was 5.56 ±0.05 wt pct. The average grain size for five specimens, as determined by the intercept method, was 0.14 i 0.01 mm. One specimen had a grain size of 2.0 mm. This large grain size is an anomaly, since all specimens had the same chemical and thermal histories. Specimens of 1/4 in. diam by 1/2 in. high were creep-tested in compression in a clam shell furnace heated by W-25 pct Re sheet elements. Temperature was measured to ilODC by an optical pyrometer which had been calibrated by a standard source. The distance between fiducial marks on the specimen was measured before placement into the furnace. The furnace chamber was evacuated to 10-5 Torr and back-filled to 200 mm N2. After heating rapidly to temperature, the load was applied and controlled to ±2 pct by an Instron testing machine. Upon initial loading, the specimen was deformed until a constant crosshead rate was obtained, then quenched to room temperature, remeasured, and replaced in the furnace. Upon subsequent reloading at temperature, the crosshead rate was constant for the selected condition indicating steady-state creep.

Jan 1, 1969

By D. S. Hutton, W. C. Leslie

Thermal etch patterns developed on poly crystalline 3.5 pct Si-Fe by heating in hydrogen or in argon have been examined. The most prominent feature of the etching is the development of striations on grains with (100) planes near the plane of the surface. These striations are probably produced by the resoution of a random, high-energy plane into (100) facets of lower energy. THE thermal etching of iron and iron-base alloys has a long history. The phenomenon was observed by Osmondl more than 70 years ago. The literature on thermal etching between that time and 1951 was reviewed by Olney,2 and a briefer review appeared in 1958. 3 The only articles which have been found dealing with the thermal etching of silicon iron are those of Dunn and Lionetti4 and of Dunn, Daniels, and Bolton,5 and they reported only grain boundary etching. EXPERIMENTAL PROCEDURES A cast 3.5 pet Si-Fe alloy was given a metallo-graphic polish and etch, then placed in flowing purified hydrogen for 6 hr at 2200°F. The same specimen was later repolished and etched to remove the thermal etching. The specimen was then held in flowing purified argon at 2200°F for 72 hr. In both instances the specimen was rapidly cooled by being pulled up quickly into the cold zone of the furnace. All photomicrographs shown are of the surface as removed from the furnace. Oblique illumination was essential for observation of the thermal-etching effects with a light microscope and was used for all the photomicrographs. RESULTS AND DISCUSSION Grain boundary etching, grain boundary movement, and contouring within grains are illustrated in Fig. 1. The contours within a single grain followed behind the advancing grain boundary. To determine the average contour interval, or step height, white light was used in an interference microscope. The steps were of the correct magnitude to separate while light into its spectrum of colors. A green light was focused at the top of a contoured area, shifting to red across the field. By using the difference in the dominant wave length of red and green light,6 and counting the number of steps across the area, it was possible to obtain a value of about 80A for the average step height. Laue back-reflection patterns of four grains with contour lines showed that the grains had a (100) plane slightly inclined to the plane of the surface (± 5 deg). Insofar as this could be determined from their irregular traces, the contour lines within a grain had a common direction, <100> ± 5 deg.

Jan 1, 1961

By Oliver Bowles

DISCUSSIONS of trade and commerce are generally more comprehensive today than in the past; the problems are approached with a vision unrestricted by national boundaries, and broad enough to comprise the entire world. The extent to which the limited viewpoint that has characterized past ages is yielding to an economy of world-wide scope is exemplified by the Atlantic Charter which blazes a trail in the direction of trade principles that aim to preserve the interest of each individual country in the commonwealth of nations. Its fourth article promulgated the principle that all nations should have access on equal terms to the trade and to the raw materials of the world which may be needed for their economic prosperity. Future developments in reciprocal international trade may have some effect upon the flow of nonmetallic minerals but such effects are not likely to be great because tariffs and trade policies have not affected that flow profoundly in the past. Nevertheless conditions may change and new problems may arise demanding important decisions. Sudden changes are not to be expected, but rather an orderly evolution in which national interests will merit due consideration in establishing broader policies.

Jan 1, 1945