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By H. Dykstra

Calculated wellbore pressures were obtained for parameters of radilcs ratio and permeability. In all cases bur two, after-production was allowed to occur for one day. The calculated pressure build-up data were compared with actual pressure build-up data from a condensate well. The paper discusses the comparison, gives reasons for, inability to match calculated (2nd actual data, and presents conc1usions derived from the comparison. INTRODUCTION Considerable information has been published on the decline in wellbore pressure for oil and gas fields resulting from production of fluids. Considerable information also has been published on pressure build-up for oil fields, but relatively little has been published for gas and condensate fields. Perrine' summarized the equations derived for pressure build-up in oil wells and showed how the different methods could be applied. On the other hand, very little theoretical information has been published on pressure build-up in gas or gas-condensate wells.2-4 Tracy,' by pointing out the similarity between the equation describing oil wellbore pressure decline and the equation describing gas wellbore pressure decline, showed how methods of pressure build-up analysis could be applied to a gas well. In analyzing pressure build-up data for gas or gas-condensate wells, it would be very desirable to compare actual pressure build-up data with calculated pressure build-up data. Such a comparison would lead to a better feeling for the quantitative picture of gas-well build-up curves and would help to establish a degree of confidence in a given build-up curve. This paper discusses the comparison and presents conclusions made from it. Calculated wellbore pressures are given for parameters of radius ratio and permeability. In all cases but two, after-production was allowed to occur for one day. The work was done in an attempt to evaluate the reserves of a gas-condensate field. As will be discussed later, it was not possible to make an evaluation. METHOD OF CALCULATION The method used for solving the depletion and pressure build-up behavior for a gas-condensate well was that developed by West, Garvin and Sheldon.5 or the IBM 704 computer program used, it was assumed that liquid condensing out of solution would have only a minor effect on the flow behavior. Therefore, the field was treated as having single-phase flow, with the gas saturation S, remaining constant at unity minus the connate-water saturation Sw. As will be discussed later, this may not have been a good assumption. It also was assumed that oil production could be considered as equivalent gas production by using a conversion factor based on an analysis of the liquid produced. An outer boundary condition of no-flow was assumed. BASIC DATA The data required for the study were reservoir properties, fluid properties and production data. Reservoir properties included the following: thickness h, 179 ft; porosity, 0.194; connate-water saturation, 0.43; gas saturation, 0.57; permeabilities k, 1.0, 0.5, 0.25 and 0.15 md; radius ratios re/rw, 800, 1,000 and 2,000; wellbore radius rw, 5 in.; initial reservoir pressure P, 6,529 psia; and reservoir temperature, 272°F. The selection of permeabilities was based on core-analysis data showing an average air permeability of about 2 md. With a relatively high connate-water saturation, the average effective gas permeability would be about one-half, or less, of the air permeability. The selection of radius ratios was based partly on the observed rapid decline in wellbore pressure during production and partly on the fact that the well was believed to be located in a relatively small fault block. Reservoir fluid properties were obtained from a reservoir fluid study on a recombined sample of gas and condensate. Gas formation-volume factors were calculated from pressure-volume measurements made at reservoir temperature. Gas viscosities were calculated by the method of Carr, et al,G from an analysis of the re-combined sample. These data are shown as a function of pressure in Table 1. The production schedule from the gas-condensate

By T. H. Alden

A correlation has been found in rock-salt structure single crystals between the latent hardening, measured by the direct stress activation of oblique slip systems, and the stress-strain behavior in simple compression. Materials with high latent hardening, like LiF, strain-harden at a low rate (Stage I) even when severely constrained. KCl, in contrast, shows low latent hardening and a tendency to strain-harden at a high rate (Stage 11). This correlation suggests that oblique slip is essential for Stage II hardening of these materials. THE role of secondary slip in the strain hardening of metal single crystals is a topic of lively controversy. On the one hand are theories in which secondary dislocations participate directly in Stage II hardening in the fcc metals, for example through the production of sessile dislocations,1 forest intersections, or jog formation. Much of the experimental evidence on which these theories are based has been reviewed by Clarebrough and Hargreaves.~ On the other hand, a recent theory5 denies that secondary slip has an essential role in Stage II hardening or in the transition from Stage I to Stage 11. In the latter view, Stage I is not terminated by an increase in the activity of secondary systems but by the exhaustion of undeformed material.6 The experiments reported in this paper will not resolve this controversy since the materials being studied are cubic ionic crystals rather than metals. However, the results do show in an unusual way a direct connection between "secondary" (nonortho-gonal or oblique) slip and strain hardening in these materials. Specifically, a correlation has been found between two independently measured properties, first the latent hardening of oblique (110)(1i0) slip systems as measured by direct stress activation of these systems, and second the stress-strain behavior at small strains. From prior work, it was known that in most cubi-cally oriented rock-salt structure crystals, two orthogonal slip systems operate and exclude the other equally stressed pair, oblique to the first pair.7'8 This observation apparently indicates that a significant interference exists between slip on oblique (110) planes and a relatively small interference between orthogonal (110) planes. The present experiments were begun with the intent of obtaining a quantitative measure of this difference by means of a study of latent hardening in these crystals. I) EXPERIMENTAL METHODS The experiments were basically of two types, first the determination of stress-strain curves by compression along a single (100) axis, and second the measurement of latent hardening by compressive prestrain along one cube axis followed by the determination of the yield stress in a second (latent) cube direction. All tests were done at room temperature in an Instron machine by compression between lapped, parallel steel faces. Three specimen shapes were used. For long crystals (nominal dimensions, 1/8 in. square by 1/2 in. long) the ends were lubricated with an oil-graphite mixture. Superior results with short crystals (about 1/8 in. cube) were obtained using 0.003-in. teflon film.' Thin crystals (1/4 in. square by 3/32 in.) were used for latent-hardening measurements and similar results were obtained with either lubricant. Test specimens were cleaved from Harshaw single crystals which had been irradiated to a dose of lo8 roentgen using a cobalt-60 source. The irradiation raises the yield stress and tends to prevent plastic deformation during sample preparation.10 Prior to testing, the irradiation hardening was removed by an anneal at 400°C. Ideal compression specimens have flat, parallel faces. In short specimens particularly, satisfactory results demand a close approximation to this ideal. In the present work, cleaved surfaces were often used directly as compression faces. The degree of success using this method depends on two factors: 1) the smoothness of cleavage faces, and 2) the extent to which the crystal is deformed or crushed by the chisel during the cutting of a long crystal into short pieces. Unfortunately, only one material of those studied, LiF, was completely satisfactory. NaF, NaC1, KC1, and KBr behaved less well so that

Jan 1, 1964

By L. R. Plitt, E. O. Lilge

Tests carried out with both kaolin and silica slurries show that flocculants of the polyacrylamide type can be used to improve the thickening performance of hydrocyclones. This thickening improvement demonstrates that contrary to previously held theories, flocs can be formed which are capable of resisting the shear forces in a hydrocyclone. For the 1.25-in.-diam cyclone used, optimum thickening occurs when the flocculant solution is injected into the slurry stream at or near the feed inlet. Hydrocyclones offer many distinct advantages over gravity thickeners. These advantages include simplicity, low initial and operating costs, small space requirements, and flexibility of operation. In spite of these advantages hydrocyclones have not been widely used as thickeners. The main reason for their lack of application is that hydrocyclones are unable to efficiently remove semicolloidal particles (less than 5 microns) from the suspending solution. In gravity thickeners, the fine particles can be induced to form particle aggregates, or flocs, which have the settling characteristics of large particles. In the hydrocyclone, however, it was always assumed that the existence of shear would prevent the formation of flocs.1-3 Thus, if no floc structure is retained, the thickening hydrocyclone must be designed so that its separation size is below the size of the smallest particle to be recovered. To obtain a very small separation size requires the formation of very high centrifugal forces, which necessitates the use of small-diameter cyclones. Small hydrocyclones have, in turn, very low throughput capacities which render them impractical for many industrial thickening applications. Thus, if the effects of flocculation cannot be utilized, the usefulness of hydrocyclones as thickeners remains limited to pulps which contain no very fine particles. It is well established that most substances acquire a surface electric charge when brought into contact with an aqueous medium. The repulsive interactions between similarly charged particles act to prevent flocculation. One method of flocculating a dispersion is to neutralize the repulsive surface charges by the addition of an electrolyte. The reduction of the electrostatic surface charge (Zeta potential) then permits the universal van der Waals attractive forces to operate between the atoms of the various particles and form particle aggregates. The lime additions used by thickener operators promotes flocculation by this mechanism. A second method of flocculating a dispersion is by the addition of long-chain macromolecules. In this case flocculation is brought about by a bridging mechanism in which the molecules are adsorbed with part of their length on two or more particles, thus forming a molecular bridge between the particles.4,5 The molecules also form bridges between themselves when a single particle is bonded to several polymer molecules. The type of bonding between the flocculant molecule and the particle may be hydrogen bonding, chemical bonding, or electrolytic attraction.6 The flour and glue which are used as thickener additives are believed to promote flocculation in this manner. In the past decade synthetic long-chain polymers with extremely high flocculating capabilities have been developed. The flocs formed by these new polymeric flocculants are larger and more shear-resistant than those formed by the presence of electrolytes.7 The advent of these flocculants raises the question: Are the flocs formed by these synthetic polymers stable enough to resist the liquid shearing forces in a hydrocyclone? The investigations reported in this paper were carried out in order to provide some answers to this question. EXPERIMENTAL WORK For the bulk of the test work a 5% slurry of commercially available kaolin with an average particle size of 5 microns was used. An initial evaluation of the available flocculants was carried out to determine which flocculant formed the most shear-resistant flocs. A combination of the techniques used by Healy7 and Booth8 was used for this purpose. This initial study revealed that the neutral high-molecular weight polyacrylamides produced the most shear-resistant flocs. One of these flocculants, Separan MGL*, was selected and then used for all the hydrocyclone tests. The flocculant was dissolved in water and added to the hydrocyclone as a dilute solution.

Jan 1, 1968

By D. W. Mitchell

INE operators have a choice of several classi- fications of mechanical loaders. Within each classification there are many types and makes available. Table I lists loaders on which manufacturing data as to operating characteristics are available. This paper discusses the conditions met in a mine as they affect these characteristics. It is assumed that management will provide satisfactory engineering, supervision, power, maintenance, loader service within a concentration of workings, and a balanced working cycle served by balanced production equipment. These are factors which affect the optimum operational efficiency of a loader. The conditions which determine loader choice are: Height of Vein—The main limitation to the use of a loading machine is the height to which the vein is mined; i.e. a loader cannot be higher than the place in which it is to work unless rock is taken. Since there are several low vein loaders being developed and successfully applied, this does not appear to be a requisite of an efficient mining operation. The maximum useable height of a loader should be equal to the working seam thickness less a working clearance for travel and operation. A—Working seam thickness = B—Artificial roof support thickness = C—Safe headroom below support = (generally about 6 in.) D—Height of roadway = E—Total of B + C f D =_______________________ A—E = maximum loader height F—Distance from top of roadway to bottom of roof support = G—-Height of loader's coal or ore line (see Table I) = H—Difference between F and G = Size of largest broken particle + a safety factor of 2 to 3 in. H is a loadability factor and is important because the clearance over the top of the conveyor chain to the roof or roof support must be greater than the largest broken particle or else the particle and/or the conveyor chain may be broken. From this standpoint it might be desirable to use a lower height machine even though it may have a smaller capacity, though this is warranted only when increased lump realization offsets lower man-day and machine pro- duction rates. Ivan Given has stated, "Loading should not be handicapped by securing lump only to grind it in the breaker." Width of Working Place—The width of a working place is the greatest width a place may be safely driven. The working place includes not only the face but the roads the loader must tram when mucking out more than one face. The width is limited by the system of placing props with sufficient room between them for the machine runner (about 2 ft). Maximum width of place in which the loader will operate at maximum efficiency is determined by the type of mounting. With track-mounted loaders, maximum width of place is determined by maximum angular swing of the loading head and proximity of track to the face. The use of double track leads to added expense and operational complexities. Several mines that have used double-track systems have found that a substantial saving is made by the use of machines that load out wider places. Trackless loaders may work in rooms of any maximum width. Minimum width of place in which a loader will operate is determined by width of the loader plus a safe movement area for the operator. Often a barodynamic study of the mine will show that either an increase in room width and/or a change in the system of propping may be made by using roof bolting, full or part-width room timbers, removable aluminum I-beams at the face, etc. Increasing the width of a working place will, in general, increase loader operating efficiency by providing more material per fall and by decreasing the preparation and moving time per ton. A change in the system of propping that would increase the minimum width might permit the use of a higher capacity loader with safer working conditions. Proper face tirnbering is necessary to insure safety from roof falls and because the speed of preparation and loading generally increases since the men work with greater assurance and there is less chance of kicking out posts. Maximum Room Length—With the exception of the scraper and the duckbill, the limit to room

Jan 1, 1952

By E. G. Woods, A. G. Comer

A mathematical model is presented and solved for determinution of the saturation distribution and pressure in a radial gas-storage reservoir. The model consists basically of two parts: (I) the growing gas-bubble core, and (2) the surrounding aquifer. Since the total pressure at the injection well is a function of the two-phase flow in the gas bubble and the unsteady single-phase flow in the aquifer, the resistance to flow in both zones was taken into consideration. The assumptions involved for both the radial equivalent of the Buckley-Leverett two-phase-flow equation and the injection-pressure equation are as follows: (I) the geometry is radial, (2) the gas bubble is free to expand or contract, (3) compression or expansion of the gas within the bubble may occur at the beginning of a time step, (4) the fluids are immiscible, (5) water is incompressible within the gas-storage region whereas it is compressible outside of this region, (6) a stable gas-water interface exists and (7) gas injection occurs at a constant rate or a series of constant rates. The mathematical model was solved numerically using an IBM 650 computer. A comparison is presented between the predicted results of the model, the results assuming steady-state flow and the actual initial injection-pressure history of an operating reservoir. Using the initial field pressure for a basis, the average deviation between the predicted pressure and the actual field pressure was less than 4.3 per cent. INTRODUCTION Underground storage of natural gas in abandoned oil fields, in abandoned coal mines, in caverns and in aquifers has had varying degrees of success. The lack of these first three facilities in the vicinity of most major gas marketing areas is leading more and more to storage in virgin aquifers. For the most part, this storage in aquifers has led to the study upon which this paper is based. Several excellent papers have been published discussing the problems involved in the underground storage of natural gas; however, to these writers' knowledge, none of them considered the two-phase flow of fluids in the gas bubble and the fact that the gas bubble will grow or shrink in size depending upon the injection and withdrawal history of the reservoir. Not only will both of these factors influence the required injection pressure, but also they will have a definite bearing upon the amount of water production occurring upon withdrawal from the storage area. To solve this problem on an IBM 650 computer, several simplifying assumptions were made. Only the drainage portion of the relative-permeability curve was considered, thereby neglecting any hysteresis effects introduced during an imbibition cycle. The quantity of gas withdrawn during the period of the field study was only a small percentage of the total gas in place; therefore, this assumption is justified. For the problem studied in this case, the combined effects of capillarity and gravity were assumed to be negligible. This assumption becomes less valid as the formation thickness or the average pore diameter increases markedly. The justification of these assumptions should be studied in each case. THEORY This mathematical model for the prediction of saturation distribution and pressure for a radial gas-storage aquifer is based upon the equations for radial two-phase fluid flow'.' and for radial, unsteady-state, single-phase fluid flow.' The two-phase flow is considered to take place in a "core" whose radius is equal to the maximum radius that the gas zone will attain, as indicated in Fig. 1. The injection-withdrawal history is approximated by a series of constant flow rates. Within the "core", gas is assumed to behave as a semi-compressible fluid; that is, the gas is assumed to have a constant density based on the average gas-zone pressure for the flow period. Between each constant-rate time increment, the gas density is allowed to change. This involves an iterative solution of the pressure equation. The liquid phase in this zone is considered to be incompressible, whereas it behaves as a compressible liquid outside of this region. The equations of incompressible flow in the "core" may be written for the gas phase

By J. R. Hauber, N. R. Borch

A study uras made on the creep behavior of cast and extruded SR grade beryllium. It is shown that, for stresses below about 1000 psi in the temperature range 760" to 85o° c, the creep behatior is nearly exactly described by the Nabarro-Herring mechanism. The activation energy is apparently that for self-diffusion, 42 2 kcal per mole, below 1000 psi, but it rises to 88.6' kcal per mole at higher stresses. The slress exponent is 4.5 at the higher stresses. Tertiary creep in this material is clearly related to void formation apparently caused by grain boundary sliding. BERYLLIUM is becoming an increasingly important technological material. A search of the literature has revealed a lack of fundamental studies on the creep of beryllium. This investigation was therefore undertaken to gain insight into the creep behavior of this material. EXPERIMENTAL PROCEDURE Tensile creep samples were prepared from cast and extruded SR grade beryllium. The vendor's chemical analysis of the beryllium tested is shown in Table I. The test specimens were machined as shown in Fig. 1 from i -in.-diam rods. The machined creep specimens were annealed to remove surface damage and to establish a variation in grain size. The heat treatments and their resulting grain diameters are shown in Table 11. The average grain diameters were determined by the intercept method. True average grain diameters were estimated by multiplying the measured average grain diameters by 1.5.' The creep tests were performed at temperatures from 700" to 850°C in a vacuum of 105 Torr or better in a tantalum-element resistance furnace. Loads were applied by an Instron testing machine such that the stress was held constant to within 20 psi. The test temperature was measured by thermocouples on the sample. With one exception the deviation from the desired test temperature was 2"C, and in that case the deviation was 4"C. Elongations were measured by an extensometer within the vacuum chamber which was fastened to the creep specimens at the grooves in the grip ends, as shown in Fig. 1. The precision of measurement of elongation was 1 X loe4 in. The creep tests were begun only after thermal equilibrium had been established in the sample and the extensometer to insure that there was no strain rate component due to transient thermal effects. Two kinds of creep experiments were performed. First, at constant grain size, the effects of varying stress and temperature were studied. In the second set of experiments, the temperature was held constant and the grain size was varied. The activation energy for creep was determined by varying the temperature at constant stress, as described by orn, during the first set of experiments. The variable grain size experiments revealed that creep at low stress apparently occurred by the abarro-errin' mechanism. In all of the creep tests, the stress was held constant only until sufficient strain had occurred to accurately determine the creep rate. The stress was then raised to a new value and the new creep rate determined. This process was reported until tertiary creep occurred. In this manner several data points were obtained from each specimen. The assumption was made that the structure was not changing appreciably between the incremental stress levels. This was verified by reducing stresses to previously tested levels and comparing the creep rates with the creep rates obtained at the lower strains. The re-producibility was within experimental error over strains on the order of 1 pct. EXPERIMENTAL RESULTS A typical series of creep tests is shown in Fig. 2. Primary creep was not observed in any test. Transient creep, which we define as creep rates that are nonlinear with time, was not observed for any change in stress except where tertiary creep occurred. The absence of both primary and transient creep has been previously reported for hot-pressed powder beryllium.= The data for the creep behavior at constant grain size are summarized in Fig. 3. The data show two distinctly different stress dependencies. At stresses below about 1000 psi, in the equation:

Jan 1, 1969

By P. J. Spencer, J. N. Pratt

The vapor pressure of manganese over liquid Mn-Sn alloys has been determined by a high-temperature torsion-effusion technique. Alloys containing from 8 to 100 at. pct Mn were investigated in the temperature range jrom 1280" to 1580" and the measured pressure values were used to calculate the partial and integral thermodynamic properties of the liquid alloys. The activities show small negative departures from ideality while the integral heats and excess entropies of mixing are asymmetric inform, changing from positive to negative with increasing manganese content. The possible contribution of various factors to the observed thermodynamic properties is discussed. COMPARATIVELY few thermodynamic data are available for manganese alloy systems.' Therefore, as part of a continuing program of studies of the thermodynamic properties of transition metal alloys, measurements have been made on various binary alloys involving this element. In recent publications,2~3 investigations of liquid Mn-Cu alloys and of the Mn-Au system in both solid and liquid states have been reported. For the first-mentioned system the work suggested that magnetic interactions may be responsible for the observed form of the thermodynamic properties, while in the second the influence of the electrochemical factor appears to be dominant. The present paper describes a similar study of liquid Mn-Sn alloys. Again the thermodynamic properties have been obtained from vapor pressure measurements made by use of a high-temperature torsion-effusion technique.4 A detailed description of the apparatus and of the experimental procedures used in alloy preparation and pressure measurement may be found elsewhere.2'4 EXPERIMENTAL RESULTS Sixteen alloys, ranging in composition from 8 to 100 at. pct Mn, were prepared from spectroscopically standardized manganese of 99.99 pct purity and tin of 99.999 pct purity, both supplied by Johnson-Matthey and Co., Ltd. One-gram samples of the alloys were obtained by carefully weighing appropriate amounts of the pure components into an effusion cell; this was then suspended in the apparatus and the metals melted together in situ by heating under vacuum to approximately 1550°K. After allowing sufficient time for a homogeneous liquid alloy to be formed, vapor pressure measurements were commenced. These were determined as rapidly as possible at a series of steady temperatures within the range of interest. The duration of experimental runs on individual samples was kept sufficiently short to ensure insignificant varia- tion of alloy composition during investigation. After completing pressure measurements, the alloys were rapidly cooled and their compositions checked by weighing or chemical analysis. All experiments were conducted using effusion cells machined entirely from boron nitride. Measurements were made using a variety of cells with orifice areas ranging from 0.0032 to 0.0075 sq cm and lengths of the order of 0.04 cm; the usual effusion correction factors for orifice geometry and molecular distribution were calculated using Freeman and Searcy's equation5 and had values between 0.6 and 0.75 for the orifices employed here. The vapor pressures of manganese over the alloys were measured at approximately 20°K intervals in the temperature range 1280" to 1580°K. In view of the close approximation of the measured pressures to Clausius-Clapeyron behavior in the experimental temperature range, the data for each alloy have been expressed by equations of the form: logp(atm) =-A/T + B A least-squares computer treatment was applied to the vapor pressure values in order to obtain the coefficients A and B with their associated error. The resulting equations are listed in Table I, together with the equation for pure solid manganese obtained from a previous study.4 To minimize the effect of possible apparatus calibration errors, the activities and partial free energies of manganese in the alloys were calculated by initial reference to the latter equation, obtained from identical torsion-effusion measurements. The immediately resulting thermodynamic quantities, based on a solid manganese reference state, were then converted to refer to the more appropriate supercooled pure liquid manganese standard; tabulated values of the free energies of solid and liquid manganese from Hultgren et al.' were used for this purpose. Partial entropies of solution of manganese were calculated from the temperature coefficients of the free energies and partial heats from the Gibbs-Helmholtz relationship.

Jan 1, 1969

PURPOSE OF UPDATED ESTIMATE FOR MINERAL INVENTORY BLOCKS During the production stage of an open pit porphyry copper mine it was observed that the expected production grade, as determined from the block inventory estimates, often differed greatly from the head grade of ore delivered to the mill. It was determined that, for purposes of production scheduling and monthly forecasting, better in situ grade estimates for mining blocks were necessary. Because all of the bench blastholes were being sampled, and periodic holes were being drilled into the next underlying bench, much more sample data existed than was being used for estimating the grade of nearby mining blocks. It was reasoned that, by periodically updating the mineral inventory block file over the benches scheduled for mining in the next time period using all existing data, better estimates and forecasts for production grade could be made. BLASTHOLE SAMPLE DATA MANAGEMENT The collars of all blastholes in each mined bench were surveyed and assays run on the cuttings representing the full 12-m (40-ft) bench height. The blastholes range from about 5 to 6 m (16 to 19 ft) apart along the front of the bench as well as perpendicular to the front. Overbreakage often left larger spacings between successive blasts. Fig. 17-1 is a plan map of blastholes on a typical mine bench. All blasthole data were keypunched to a format resembling that of the 12-m (40-ft) composite assay data file as follows: [Collar Coordinates Compite Assoy Hole ID Northing East Elewotion Total Copper Oxide Copper] Because of the many blasthole samples available, and in order not to use excessive computer time for running kriged estimates for 30.5 X 30.5 X 12-m (100 X 100 X 40 ft) blocks adjacent to and beneath the mined area, the decision was made to average all the blastholes falling with each 15.2 X 15.2-m (50 X 50-ft) mined block, and use the mean value of the samples as a regionalized variable for purposes of assigning kriged estimates and estimation variance to adjacent unmined blocks. In other words, instead of using individual blasthole samples for making kriged estimates, the holes were grouped by blocks and assay values were averaged and assigned to the centroid of the holes within the block, which was then treated as a single regional variable for purposes of kriging. See Fig. 17-2. VARIOGRAM COMPUTATIONS AND KRlGlNG RESULTS With the many blasthole samples it was possible to compute directional and vertical experimental variograms for both sulfide and nonsulfide copper assays falling within the enriched mineral zone for the full 12-m (40-ft) sample support. Due to the close spaced drilling, excellent definition of the experimental variograms was possible, and the spherical model exhibited good fits. A three-dimensional kriging program was then run over the two or three mine benches involved in the inventory update, and estimated grades reassigned to all mining blocks falling within the range of the new blasthole assay data according to the anisotropisms of the deposit. Better confidence limits could then be assigned to scheduled mining blocks and better short- range forecasts made. An interactive kriging computer program was also applied for the purpose of determining the kriging variance or estimation of error for larger, irregular mining blocks representing the monthly production from a particular bench. The interactive program permitted the operator to enter the limits of the irregular block onto the screen of a cathode ray tube (CRT) as a series of points around the perimeter of individual gridded blocks making up the larger irregular block. The computer then was programmed to calculate the kriging variance of the larger block using all samples fall- ing within range. Thus the limits of estimated grade could be established at any confidence level. Fig. 17-3 illustrates the output from the interactive kriging program showing the sample points entering into the grade and kriging variance computations, and also the kriging coefficient assigned by the computer to each sample.

Jan 1, 1980

By J. Washburn, R. Drouard, E. R. Parker

Temperature dependence of the rate of recovery in zinc single crystals after a simple shear deformation at low temperature was investigated. Some tentative suggestions regarding the annealed and strain-hardened states of a crystal are discussed. RECOVERY may be defined as the gradual return of the mechanical and physical properties of strain-hardened metal to those characteristic of the annealed material; an increase in temperature increases the rate of recovery. The annealing process in strain-hardened polycrystalline metals is complicated by the inhomogeneity of strain which always exists in aggregates. Polygonization in bent regions of the crystals and growth of new almost strain-free grains starting at points of severe local distortion1-:' make it almost impossible to isolate and study the recovery process. Homogeneously strained single crystals, however, do not polygonize or re-crystallize and hence they can be used advantageously to study recovery. In such crystals strain hardening is completely removed by recovery alone. Since recovery is a process whereby certain lattice disturbances introduced by plastic flow are gradually reduced, a knowledge of the rate and temperature dependence of this process for various conditions of prestrain might be helpful in formulating a model of the strain-hardened state. For simplicity it seemed desirable to limit the type of prestrain to the simplest obtainable, i.e., simple shear strain. In the experiments to be described, recovery was studied by observing changes in the stress-strain curve of prestrained zinc single crystals held for various times at temperatures above that employed for straining. Single crystals were grown from the melt by a modified Bridgeman technique from Horse Head Special zinc 99.99 pct pure, and from spectrographically pure zinc 99.999 pct pure. They were grown as 1 in. diameter spheres and acid-machined' to the final specimen contour. The test section was a cylinder about 1/8 in. high and 3/4 in. in diameter. The conical sections adjacent to the test section were cemented into the grips so the load could be transmitted to the crystal as uniformly as possible. The specimens were oriented so that in testing the maximum shear stress was applied along one of the slip directions, [2110], in the (0001) plane. Details of the production and testing of such specimens have been presented.' Each test was carried out according to the following schedule: 1—The crystal was strained at — 50°C until it reached a maximum shear stress, ,,,. The strain rate was approximately 5 pct per min in all cases. 2—After straining, the crystal was unloaded before the temperature was changed. Unloading required about 3 min. 3—The temperature of the specimen was then increased from — 50°C to the temperature, T, of recovery. This change in temperature was completed in a time of less than 2 min. The specimen remained at temperature, T, for a time, t, which differed for the various specimens. 4—Thereafter the temperature was again reduced to — 50 °C in approximately 3 min. 5—While at —50°C, the stress-strain curve after recovery was obtained. 6—The specimen was then unloaded and annealed for 1 hr at 375 °C in a helium atmosphere to bring about complete recovery. Cooling to room temperature after anneal required 90 min. 7—The same crystal could be re-used for another test because the plastic properties after annealing closely duplicated those of the original crystal. The specimen was immersed during the test in a bath of methyl alcohol which, through a system of tubes, could be pumped through either of two heat exchangers to regulate the temperature; this was accomplished by circulating the liquid through coils immersed in a bath of acetone and dry ice for cooling or in a bath of warm water for heating. Test temperatures were thus maintained constant within ±1°C. The — 50°C temperature was low enough so that no measurable recovery occurred during unloading and reloading. The stress-strain curve continued after recovery along a path below, but approximately parallel to, the path of a curve obtained in an uninterrupted test. Fig. 1 shows some of the results from a specimen of 99.999 pct Zn. The amount of downward displacement of the curve due to recovery was a

Jan 1, 1954

By M. Bevis, E. O. Fearon, P. C. Rowlands

Fe-Ni and Fe-Ni-C martensite specimens have been deformed in compression at room temperature and the habit planes of operative deformation twins determined by two-surface optical trace analysis. The full orientations of the martensite crystals were determined from divergent X-ray beam diffraction patterns. The experimental results are in excelled agreement with predicted twinning modes. In particular, the habit planes of some deformation twins in bcc martensites are consistent with a "Type XI compound'' twinning mode with Kl, Kz, 71, 77~ elements given by {5, 8, 11) {ioi}, (33) (ill) Tetragonal derivatives of this mode are operative in bct martensites. UnUSUAL deformation twinning modes have been reported by Richman' to occur in Fe-Ni-C martensites with bcc and bct structures. The twin habit planes were determined by single-surface trace analysis (pole locus method) and the remaining twinning elements were determined from the geometry of twin-twin intersections. The indices assigned to the observed habit planes are (3 101, "(089)" and "{0, 1,13)" or "{1,2,7} ", and only in the first case do the twinning elements correspond to a predicted twinning mode. This is mode 1.4 in the paper by Bevis et al. The results presented in Ref. 2 indicate that previously unpublished bcc and bct modes should be operative in preference to the (130) mode and anomalous modes reported by Richman. In view of these results and the uncertainties involved in determining habit planes from single-surface trace analysis and twinning elements from twin-twin intersections5 a two-surface trace analysis of deformation twins in Fe-Ni and Fe-Ni-C martensites has been carried out. EXPERIMENTAL PROCEDURES Two alloys with compositions Fe-23 pct Ni-0.6 pct C and Fe-30.4 pct Ni were prepared from 4N pure materials by induction melting under a vacuum of 10"5 mm Hg. The alloys were homogenized at 1350'~ for 5 days. Both of these alloys are austenitic at room temperature with M, temperature - — 50"C. The aus-tenite grain size of the Fe-Ni-C alloy was approximately 300 to 400 p. The Fe-Ni alloy was remelted in a vertical tube furnace and the melt lowered slowly from the hot zone of the furnace to produce s ingle -crystal austenite specimens. Specimens approximately 10 by 5 by 5 mm were cut from the ingots and quenched to various temperatures below the Ms temperature. The specimens were elec-tropolished in a 10 pct perchloric acetic electrolyte before being deformed in compression at room temperature. Martensite plates which exhibited profuse deformation twinning were selected for analysis and the specimen polished on a second surface such that the two surfaces which contained the martensite plate enclosed an obtuse angle of approximately 145 deg. The specimens were then electropolished to reveal the traces of the deformation twins on both surfaces. The full orientations of the martensite crystals were determined using a divergent X-ray beam technique (Kossel line technique) employing an AEI SEM2 electron probe microanalyzer. Details of this technique which include a detailed description of the Kossel camera attachment to the microanalyzer used in the present experiments have been discussed elsewhere.3 Only additional details relevant to this investigation are discussed here. The specimens were mounted with one surface normal to the incident electron beam as illustrated schematically in Fig. 1. The martensite plates to be analyzed were located using the normal scanning equipment of the microanalyzer. The position of the electron beam and hence the position of the source of divergent X-rays generated within the crystal could be located to within 1 p. Exposure times of approximately 8 to 10 min were required for back-reflection Kossel patterns and it was found that useful diffraction patterns could be obtained consistently from heavily deformed martensite plates. A reference line (carbon contamination mark) produced on the two surfaces of the specimen by scanning the electron beam in a direction having a known relationship with the reference !ine in the X-ray camera enabled the full orientation of the crystals to be determined. Martensite plates with widths as small as 8 p could be oriented using this procedure. The Kossel line patterns were interpreted using the charts developed by Rowlands and ~evis~ as generally

Jan 1, 1969

By D. R. Hay, E. Scala

STUDIES of structure-sensitive properties, especially mechanical behavior, have shown that grain and subgrain structure play an important role. The mechanical properties of tungsten, in particular, are sensitive to the nature of the intergranular structure. Substructure and dislocation networks in single-crystal and polycrystalline tungsten have been studied by Nakayama et al.' Various orders of substructure were observed ranging from a microscopic first order (grain diameter: 2 to 8 mm) to a microscopic second order (grain diameter: 50 to 300 p), and, within the latter, dislocation networks forming an even smaller order of substructure. In their single crystals, grown by arc fusion, the degree of misorientation in each order was small: 16'3OU, -11, and -10" for the first-, second-, and third-order substructure, respectively. To study the properties of polycrystalline tungsten, powder metallurgy tungsten is generally used. However, in a mechanical property investigation, the zone-melted or arc-fusion crystals are more desirable than the powder metallurgy product due to their higher purity and absence of porosity and other defects inherent in consolidation by powder metallurgy. Grain boundaries can also be produced in melted stock by working and recrystallizing. However, material with subgrain mis orientations of the order of several degrees (high-angle substructure) has not been reported previously and is the subject of this communication. Crystals were grown by electron-beam, floating-zone melting. The starting material, Sylvania Pure-tung welding rod, was given one zone pass at a traversal rate of -2 mm per min. Through control of the zone temperature, it was possible to influence the degree of crystal perfection. By maintaining the zone at a high degree of superheat, high-perfection crystals could be grown. However, at temperatures only slightly above the melting point, the zone-melted crystals contained a high-angle substructure. A sensitive control of the zone temperature was not possible due to the difficulty of estimating the temperature of the zone and of providing a constant supply of power to the sample. Therefore, an empirical method, using the shape of the molten zone as a criterion, was adopted as an indication of temperature. At high degrees of superheat, the surface tension of the molten zone decreases and a neck forms at the top of the zone, whereas at low zone temperatures the diameter of the zone remains reasonably uniform. Although it was not possible to obtain a continuous variation of misfit angle, the conditions could be directed toward the growth of either high- or low-angle substructure by maintaining only a slight neck in the zone (sufficient to establish that it was molten) or a well-necked zone, respectively. Mass spectrographic analyses of both types of material revealed no significant differences in the concentrations of their impurities. The degree of misorientation at high angles was obtained by measuring the angular spread of spots corresponding to a single reflection on a Laue back-reflection photograph. Fig. 1 shows a typical Laue back-reflection photograph of a crystal with a 3-deg spread. By measuring the angular deviation of the spots corresponding to a single reflection from the mean center of the spots around which constant angular deviation contours were drawn, an average angular spread of misfit could be calculated. The angular average was weighted by the number of spots observed in each angular interval. At angles greater than 5 to 6 deg the spots from different reflections begin to overlap, and cannot be associated with a particular reflection. Laue back-reflection photographs taken at different locations on samples .with approximately 3-deg spreads showed only a small difference in angular misorientation, less than 8' of arc, within individual specimens. The microstructure was examined using Berg-Barrett X-ray extinction contrast microscopy. Berg-Barrett photographs taken directly on the as-grown surface, Fig. 2, show an essentially equiaxed subgrain structure of -0.1 mm in average grain diameter in both high- and low-angle crystals. Fig. 2(a) is a photograph of a sample with a low misfit angle and Fig.

Jan 1, 1968

By J. D. Testerman

A statistical technique to identify and describe naturally occurring zones in a reservoir and to correlate these zones from well to well is described. The technique is particularly useful in describing a reservoir where cross flow between adjacent strata is important in determining reservoir behavior. Although it has been used primarily for permeability zonation, the technique is general and can be used to correlate any reservoir property or related data, such as the information contained in well logs. INTRODUCTION One of the first problems encountered by the reservoir engineer in predicting or interpreting fluid displacement behavior during secondary recovery processes is that of organizing and using the large amount of data available from core analysis. Permeabilities pose particular problems in organization because they usually vary by more than an order of magnitude between different strata. Due to the sheer volume, it is almost always necessary to group data and to use an average value to represent a number of measurements. Perhaps the most common method now used to group permeability data is the capacity-fraction technique, which ranks permeabilities in order of magnitude, regardless of the physical location of the permeabilities within the reservoir. The cumulative per cent capacity is plotted against cumulative per cent thickness. This plot is divided into an arbitrary number of zones, generally of equal thickness. Five zones (or averaged groups of data) usually are obtained, each of which is treated as homogeneous in subsequent calculations. The division so obtained has no physical meaning; strata in the same zone, calculation-wise, are usually not adjacent in the reservoir. Reservoir engineering techniques being developed will handle crossflow that occurs between adjacent communicating reservoir strata because of imbibition and gravity segregation. Since crossflow occurs between physically adjacent layers within the reservoir, a new zonation technique recognizing the actual location of strata within the reservoir is necessary. Similarly, the recognition of natural zones is important for predictions of oil recovery by processes involving diffusion. One such process is miscible displacement, where predictions of lateral diffusion within the reservoir must recognize the actual location of the invaded zones in relation to the rest of the formation. Natural zones must also be adequately recognized to account for heat transfer within the reservoir during thermal exploitation. Because of the complexity of the problem, statistics appear to offer the only practical hope of dividing a reservoir into physically-meaningful natural zones. This paper presents a statistical technique for identifying these natural zones and for ascertaining which ones are likely to be continuous between adjacent wells. The zones defined have minimum variation of permeability internally and a maximum variation between zones. The technique is general and can thus be applied to reservoir properties other than permeability. The method will guide the reservoir engineer in estimating which zones are likely to be continuous between wells. However, a statistical correlation based on permeabilities in two different wells is no guarantee that the zones so defined are, in fact, continuous. Rather, the assumption of continuity must be consistent with geological data concerning the depositional environment, as well as justified on the basis of engineering judgment in combination with statistics, just as judgment is required with conventional zonation methods. CALCULATION PROCEDURE The reservoir zonation technique is a two-step operation. The steps are individually described, and a sample calculation is presented in the Appendix. ZONATION OF INDIVIDUAL WELLS First, the set of permeability data at a single well is zone, into Zones. These zones are selected so that variation is minimized within the zones and maximized between the zones. The equations4,6 used to zone the data are where B = the variance between zones, , = the number of zones, i = the summation index for the number of zones, j = the Sumation index for the number of data within the zone, mi = the number of data in the ith zone, k,. = the mean of the permeability data in the ith zone, k . = the over-all mean of the data in the well, W = the pooled variance within zones, N = the total number of

By J. T. Norton, Pekka Rautala

The phases and equilibria in the W-Co-C system have been studied by X-ray diffraction methods, metallographic technique, and thermal analysis. In addition to the 7 phase, two double carbides, called 8 and have been revealed. The compositions correspond to CO3 W6C2 and Co3-W10C4. The reactions leading to these phases have been explained and tentative diagrams of stable and metastable equilibria proposed. The basic reactions in sintering cobalt cemented tungsten carbides are discussed. THE W-Co-C system is of fundamental importance in practical carbide manufacturing as well as for the understanding of the sintering mechanism. Surprisingly little is known about this system, for the probable reason that all the important alloys are of two-phase structure and that the diagram Co-WC has been treated as a quasi-binary. This obviously is incorrect, because WC decomposes before melting. One ternary phase, 7, of composition Co3W3C has long been known. It was first studied by Adelskold, Sundelin, and Westgren,1 although the isomorphous iron-tungsten carbide was known earlier. There have been in the literature several reports of two 7 phases.' " Also the 7 phase has been considered unstable by Takeda4 and Westgren.1 The Co-WC diagram has been studied by Wyman and Kelley5 and a quasi-binary diagram has been published by Sandford and Trent.2 Takeda has published a tentative Co-W-C diagram, considering both metastable and stable equilibria. However, the lines of two-fold saturation are shown only partially and it seems impossible to complete the diagram without violating the phase theory. Therefore it seemed desirable to examine the system in more detail. Experimental Procedure The alloys used in the present investigation were made of powders of tungsten, tungsten monocarbide, cobalt, and carbon and were of the grade used in manufacture of commercial cemented carbides. The powders were ground and mixed in small stainless steel ball mills, using balls of the same material. Benzene was used as a dispersing agent. The mixing period was 1 hr, since this was shown to give suffi- ciently good mixing of the powders without too great a contamination from the mill. After ball milling, the specimens were pressed in cylindrical or rectangular dies. No paraffin or other lubricant was used and the small compacts had sufficient green strength to be handled without difficulty. Several sintering furnaces were employed. The most satisfactory arrangement was a vacuum furnace based on the Arsem principle which employed a graphite helix as the resistance heating element. Specimens were placed on graphite stands and there was generally a slight carburization or decarburiza-tion of the specimen surface, depending on the carbon content of the alloy. The evaporation of the cobalt at a sintering temperature of 1400°C was not significant, but became severe at 1500°C and higher. The sintering time was 1 hr at 2000°C and 2 to 4 hr at lower temperatures. It was not possible to quench the specimens, but the cooling rates were rather fast, greater than 300°C in the first minute. In the system under investigation, the reactions are sluggish, and it is believed that the high temperature structures are satisfactorily retained. The principal method of investigating the sintered specimens was X-ray diffraction by the Norelco recording spectrometer. Approximate determinations of the phase boundaries were made by the disappearing phase method. Ternary Phases To study the phase formation in W-Co-C system, a series of specimens was sintered at 1400°C. In this experiment two ternary phases, called here ? and k were formed in addition to the well-known 7 phase. The 7 phase, which has been completely described by Westgren: showed a range of homogeneity from 7 to 20 pct C and from 38 to 48 pct Co. At 1400°C the 7 phase was found to be in equilibrium with monotungsten carbide, 8, tungsten, 8, #?, and liquid. The boundaries toward #? and liquid were difficult to determine and appeared to be very temperature sensitive. The other boundaries are believed to be well fixed. The homogeneity range of 7, as measured in this work, is considerably smaller than the one

Jan 1, 1953

By J. W. Leomrd, B. A. Donahue

Results of research are presented examining the extent to which the analytical characteristics of the relatively distinct coal bands from a variety of coal seams can be related to each other. This paper dis-cusses an approach for developing a practical coal petrographic quality control program based on conventional analyses, most of which is part of the standard A.S.T.M. procedure. The work is a final follow-up to Part I of this series which was prepared by the authors as an approach to applying conventional coal petrography to single coal seams. Recent published work by the authors entitled Petrography for Coal Mining and Coal Prepration: Part I dealt with interrelating various chemical and physical properties of coal1 measured using conventional analyses made on distinct petrographic bands taken from single coal seams. Since most coal production facilities process coal from a single coal seam or from very closely related coal seams in the same area,2 emphasis on interrelating the properties within a single seam appeared appropriate. The distinct petrographic bands were analyzed on the assumption that such differentiated data would be more representative of a heterogeneous coal seam than the single analytical value commonly used to characterize each property of an entire seam.34 Effort was directed at demonstrating the extent to which the interrelated chemical and physical properties 5,6 could be developed into nomographs or petrographic standardization graphs. Thus, one analysis, determined on a series of petrographic fractions separated from a single sample, was used to estimate numerous other properties in each fraction by referring to the previously established petrographic standardization graphs. This conventional approach to coal petrography was undertaken as a suggested feasible means by which a few coal analyses could be employed to develope a more penetrating knowledge of the properties of coal from any given seam in order to monitor more extensively its performance at the point of utilization. Such procedures can support development of the type of in- formation commonly sought through automated testing and through the use of computers.7 The broad knowledge which can be developed through these procedures is intended for application in the generation of an analytical profile or broad characterization of coal. These estimates were not intended as replacements for individual coal analytical tests. In this expanded second part of the research program, distinct petrographic bands from nine coal seams in the Central Appalachian Region were physically and chemically analyzed to elucidate the extent to which this concept of conventional petrography could be broadened for application to numerous coal seams. In presenting this second phase of work, the relationships developed are presented individually and not in a connecting series of nomographs or petrographic standardization graphs as in the previous work, thus leaving open the combinations of possibilities to individual interpretation and application. MATERIAL AND EXPERIMENTAL WORK Nine coal seams, representing a wide range of rank, from the Central Appalachian coal fields were used in this study. The distinct petrographic bands from the Kittanning, Pond Creek, Jawbone, Tiller, Poca-hontas No. 3, No. 2 Gas, Eagle, Winifrede, and Pittsburgh coal seams were separated by carefully removing a portion of each band at the face of the seam. The following were determined: ash, sulfur, free swelling index, heating value, bulk specific gravity, volatile matter, Hardgrove Grindability Index, and Gieseler Plastometer measurements. Determinations, where procedures were available, were carried out using ASTM standard procedures.8 Bulk specific gravity was determined using a kerosene volume displacement procedure modified from a method applied by Headlee and McClelland of the West Virginia Geological survey,9 Those bands with a bulk specific gravity greater than 1.60, which is generally above the practical specific gravity cleaning range of bituminous coals, were excluded and no analyses were performed. Much of the initial organization of this second phase of work was developed through the extensive use of a computerized statistical monitoring program (see Ref. 4). However, in order to achieve the closest possible interpretation of results, the final organization of data proceeded mainly from exhaustive trial

Jan 1, 1968

By C. B. Daellenbach, T. D. Tiemann

The prevention of quartz flotation by chelation of activating ions with the tetrasodium salt of EDTA in oleic acid flotation was investigated using a small vacuum flotation cell. It was found that flotation of quartz could be entirely suppressed in the presence of activating ions during complete flotation of hematite. It was further shown that the concentration of activating ions liberated from Wisconsin Gogebic taconite is sufficient to float quartz in an oleic acid system. Large tonnages of low grade siliceous iron ores occur on the iron ranges of the Lake Superior district. Although the lower grade nonmagnetic types are currently not of economic importance, they constitute a large future potential source of iron and steel, and hence have been the subject for extensive research on their beneficiation. TACONITES Of particular interest to the Dept. of Minerals and Metals Engineering at the University of Wisconsin have been the low grade nonmagnetic taconites of the Wisconsin Gogebic Range. These occur as five members of the iron formation and have been described in detail elsewhere.' Essentially they consist of an intimate mixture of hematite, goethite and quartz, with minor amounts of siderite, magnetite, iron containing silicates, and manganese minerals. A typical mean analysis based on the Bureau of Mines analyses' is: SiO2-52.50%, Fe2O3-43.40%, (Fe-30.38%), A12O3-1.15%, P2O5-0.07%, Mn2O3-0.29%, CaO-0.07%, (S-0.03%), Loss on ignition-2.00%. The quartz in these ores is of a microcrystalline variety,2 and so intimately associated with the iron oxide minerals that extremely fine grinding, in the order of minus 325 mesh, is required for liberation. During grinding and subsequent flotation, the concentration of quartz activating ions in the pulp becomes sufficiently high to activate quartz which floats along with the iron minerals in the presence of oleic acid. cook3 and co-workers concluded that oxidized iron ores released appreciable quantities of quartz-activating ions in water pulps. This is shown to be true in the present investigation. As a matter of fact, application of this phenomenon, as well as the intentional addition of activating calcium ions, is made use of in the an ionic flotation of silica from the iron oxide minerals.4,5 In view of the above, it becomes almost impossible to effect a sharp separation of quartz in the oleic acid flotation of the iron oxide minerals from these taconites, even with satisfactory liberation. This fact led to the current investigation to find a means of linking the activating ions with a chelating agent. The aim was to establish basic data for the quartz-water-oleic acid system which might not only be applicable to iron ores, but also to the flotation of other siliceous ores as well. EXPERIMENTAL METHODS Vacuum Flotation Cell: The vacuum flotation used in this investigation is similar to that used by previous investigators.6,7,8 The cell consisted of a 100 ml graduated cylinder with the lip removed. Vacuum from a water aspirator was applied to the cell through a trap; suitable tubing, and a rubber stopper inserted in the top of the cell. Constant absolute pressure was maintained by means of a manometer connected to the trap with a tee. Flotation: The required amount of activating ion solution was pipetted into a beaker. This was then diluted to 99.0 ml with water having a pH below that desired for the test, or so adjusted with HC1. After addition of 1.0 ml of oleic acid solution (2.0 mg oleic acid per ml), the pH was readjusted to the desired value with NaOH, and the entire solution transferred to the cell containing 1.5 gm of quartz. After vigorously agitating the cell and its contents for 2 min, the vacuum was applied to the cell and the estimated degree of flotation observed for a 3-min period. Activating ions studied included Ca++, Mg++, Al+++, and Fe+ + + added as chloride solutions. In addition,

Jan 1, 1964

By Strathmore R. B. Cooke, Eugene L. Talbot

THE perfluoro acids and derivatives show unusual surface-active properties that qualify them as possible flotation reagents. They lower the surface tension of water from 15 to 20 dynes below that obtainable with the corresponding hydrocarbon compounds.1, 2 Fluorochemicals adsorb very strongly on solid surfaces to give films that exhibit larger contact angles than films of the corresponding hydrocarbons."' * The large contact angles probably result from the terminal —CF3 group. The perfluoro acids are made by electrolysis of the corresponding carboxylic acid in anhydrous hydrogen fluoride.5 From the perfluoro acids many derivatives may be obtained, such as amides, amines, alcohols, xanthates, ethers and esters and others. Since the fluorinated analogues of the conventional hydrocarbon flotation collectors possess enhanced surface properties, a few were selected for testing. Because a survey of all possible minerals and reagent combinations would be out of the question, hematite was chosen to represent a nonsulphide system and pyrite to represent a sulphide system. The fluorinated reagents used in these experiments were prepared in the research laboratories of Minnesota Mining & Mfg. Co. Some were synthesized especially for this research. They are not available cokmercially. Separation of Nonsulphide Ores: The separation of oxides from silica has always been a challenge to the flotation industry because differences in surface properties of the minerals are normally insufficient to produce clean concentrates. Oleic acid," rosin acids,' and amine salts% ave been used to considerable extent to effect separation of metal oxides and silica. The system hematite-silica was chosen to represent the nonsulphides both because of its difficulty of separation and because large tonnages of easily obtainable material are available, such as gravity concentration tailings and nonmagnetic taconites on the Mesabi Range. The wash-ore tailings used here contained approximately 35 pct iron after desliming. Samples of the material used in this work were part of the same lot used by Chang, Cooke, and Huch9 and were prepared in an identical manner. Reagents for Nonsulphide Ores: Since one of the purposes of this investigation was to compare hydrocarbons with fluorocarbons, reagents of known behavior such as oleic acid, and the alkali metal salts of certain resin acids (Dresinates), were established as standards. Hydrocarbons and fluorocarbons of comparable chain length and other experimental fluorocarbons were tried as collectors for hematite. A list of the materials used and the concentrations of their stock solutions are given in Table I. Since silica can be selectively floated from hematite by conventional reagents," a few fluorocarbon reagents were also tried for this purpose. Their composition and concentrations are given in Table 11. Most of these reagents served the dual function of collector and frother. In the case of F-11 flotation did not occur but it served as a frother when F-6 was employed as a collector. Reagent grade sulphuric acid and sodium hydroxide were used to regulate the pH. Deionized water containing less than 0.1 ppm of salts expressed as NaCl was used for all solutions and flotation tests. The pneumatic flotation cell consisted of a 350-ml fritted glass Buechner funnel with a source of filtered air which could be controlled by a needle valve." A 50-g sample of ore and 250 ml of deionized water were added to the flotation cell and stirred slowly. The reagents were added and the pulp was conditioned before air was admitted to the cell. Approximately 15 ml of the pulp were removed for pH determination before flotation was started and were then returned to the system. The pH was again measured after flotation. Air was admitted to the cell until no further flotation occurred or until the character of the float changed markedly. Both the float and the nonfloat products were filtered, dried, weighed. and assayed for iron. The cell was washed in hot water and rinsed with deionized water after each test. Occasionally the cell was cleaned with concentrated hydrochloric acid to remove iron oxide particles from the glass frit. Experimental Results: Above a pH of 8, sodium oleate was an effective collector for hematite. The emulsification of equal parts of heavy fuel oil (20"

Jan 1, 1956

By M. H. Shumate

Rope-type haulage has had many applications in the mining and allied industries. Records have indicated favorable results both from a standpoint of efficiency and investment. The Truax-Traer Coal Co. has used some variations of rope haulage at their mines and preparation plants. They have built a system which solves their particular problems, and have an investment which has indicated an annual savings in operating costs. Rope haulage, as applied to the mining industry, goes back many years for both underground and surface mining, or a combination of both. The Truax-Traer Coal Co. has used gravity retarding hoists as well as several variations of rope haulage, including electrical and combinations of both, but each was limited in its use and application by natural conditions and economies of the operation. Several systems of rope haulage equipment are offered by manufacturers today for handling railroad car movement on a limited or continuous basis. The portal and railroad loading facilities of Truax-Traer Coal Co.'s Burning Star Slope mine, located in Jackson County, Ill., were moved in 1960. The old location was abondoned, eliminating 3% miles of underground track haulage. The mine was converted to an all-belt system, and coal is loaded at a new raw coal plant and shipped by railroad cars to a central cleaning plant. The company wanted to operate the surface facilities as efficiently as possible, employing a minimum number of workers, using the latest type railroad car movers. The existing rope haulage facilities at several locations throughout the country were examined and considered for the Slope mine location. The application of each appeared favorable but lacked flexibility, and it was difficult to justify the capital investment. The company decided to investigate the possibility of building a system that would apply to their problem, and have an investment that could be amortized in a relatively short period. SPECIFICATIONS They employed the services of Allen and Garcia Co. of Chicago, Ill. Through combined efforts, a railroad car rope system was designed to specifications as shown in Fig. 1. The Falk Corp. of Milwaukee, Wis. built the hoist to the specifications as shown in Fig. 2. It has an all welded base and pedestals. The all welded drum is not grooved. A single helical gear was used in lieu of herring bone type. A Falk speed reducer, Unit 90Y3-A, is driven by a 25-hp 1800-rpm, 440-V ac type 'C' (high starting torque) drip-proof, Frame 324-U motor. The speed reducer shaft is equipped with a solenoid operated ac spring set shoe brake, operating on a 7-in. diam. brake wheel. The dolly car, shown in Fig. 3, was field constructed, using the trucks and frame of a railroad tank car. Truax-Traer did not alter the frame but added plates and anchors for hoist ropes and frames for 8.5 tons of concrete to be used as ballast on the car. The limit switch operating shoe was also installed and the car coupler latch mechanism overhauled. The hoist rope selected was 1% in. in diam., 6x37 improved plow steel extra flexible, right lay, regular lay, with independent wire rope core, and preformed. Wedge sockets were used to connect rope to the dolly car as shown in Fig. 4. The system employs two 30-in. and three 16-in. diam. sheaves. All are bronze bushed and equipped with grease fittings. Larger sheaves are used for directional change of hoist rope and the smaller ones as snub sheaves to correct fleet angle of rope as it approaches the hoist drum. The Trench lay cable, buried between the two tracks, is used for electrical distribution and controls between hoists and operator's cab. Foundations for the system required 187 cu yards of reinforced concrete using approximately 60 cu yd each at three locations. Four hoists are employed in the system, two for each track. A pair is interconnected electrically and when one operates, moving the cars, the tail hoist idles with brake released. The process is repeated for the reverse direction. A limit switch, mounted in the track near each end of the system, is tripped by the dolly car as it approaches the hoist. The limit switch controls movement in one direction only, protecting the dolly car and establishing positive con-

Jan 1, 1962

By A. H. Daane, B. J. Beaudry

The Sc-Y and Sc-Zr systems were studied by thermal and X-ray methods. Both systems are characterized by complete solid solubility in the low temperature hexagonal form and in the high temperature bcc form. In the Sc-Y system, there is a minimum in the solidus at 50 at. pct and 1365°C, while the solidus in the Sc-Zr system follows a nearly straight line relationship between the melting point of scandium and zirconium. There is a minimum in the temperature of transition from hexagonal to bcc in the Sc-Y system at 43 at. pct Y and 1175°C; while the temperature of transition is raised in the Sc-Zr system to a maximum of 1415 °C at 30 at. pct Zr. INTEREST in the metals of the first transition series has usually stemmed from their useful properties; however, there is now a great deal of interest in determining the fundamental nature of these metals. Since scandium is the first of these transition metals, a study of the preparation and Properties1 and the alloying behavior of scandium2 was initiated. In a continuing study of the alloying behavior of scandium, the systems of scandium with zirconium and yttrium have been established. Extensive solid solubility in both the Sc-Zr and Sc-Y systems was expected from application of the classical rules of Hume-Rothery. Also, the modified Darken and Gurry plot as suggested by Gschneid-ner3 showed ideal conditions for solubility in the Sc-Zr system with less favorable conditions in the Sc-Y system. The effect of scandium on the transformation temperature of zirconium and yttrium was of interest, since a recent empirical observation by Uly and Burr4 predicted that the solute scandium would raise the transformation temperature of zirconium and lower the yttrium transformation. In addition to noting the validity of the above predictions, the SC-Y and Sc-Zr systems were established. EXPERIMENTAL METHODS Materials. The metals employed in this investigation were crystal bar zirconium, distilled scandium prepared by the method described by Spedding, et al.1 and yttrium prepared by the method described by Carlson, et a1.5 The major impurities present in these metals are listed in Table I in ppm. Alloy Preparation. All the alloys examined were initially formed by comelting the two metals in a nonconsumable electrode arc-melting furnace under an atmosphere of purified helium or argon. The buttons were inverted at least five times and re-melted each time to ensure homogeneity. During preparation of Sc-Zr alloys, approximately 1 wt pct was lost which was attributed entirely to the loss of scandium by distillation. When preparing Sc-Y alloys, approximately 1.5 wt pct was lost, but it was assumed that the intended composition was maintained, since the relative weight lost when arc melting the component metals was nearly the same. Samples weighing 15 to 20 g were prepared for time-temperature thermal analysis, while only 1- to 2-g samples were prepared for the optical pyrometer and X-ray diffraction studies. Thermal Methods. The solidus and the melting points of the metals were determined by an optical pyrometer method described previously.2 The temperatures at which the transformation from hexagonal to bcc occurs were determined by differential thermal analysis. Several points on the solidus and liquidus in the Sc-Y system were also determined by this method and are in good agreement with those obtained by the optical pyrometer method. The procedure followed in the preparation of samples for thermal analysis and the furnace used have been described elsewhere.2'6 Since a limited quantity of scandium was available, most of the alloys were not melted during thermal analysis, thus avoiding contamination by the crucible. The alloy could then be reused and the composition changed by adding the desired quantity of solute to obtain the next alloy. Heat Treatment and X-Ray Methods. In order to ensure homogeneity, the "as arc-melted" alloys Were wrapped in tantalum foil, sealed in quartz capsules and heated at 1100°C for 15 hr and then cooled at a rate of 8 deg per min. Samples for X-ray diffraction were filed from these heat-treated alloys, sealed in 1/8 in. by 1/2 in. tantalum capsules under

Jan 1, 1963

By H. L. Teichman, E. M. Sipprelle

ENACTMENT' of Public Law 290 by the 78th Congress authorized the U. S. Department of the Interior, Bureau of Mines, to conduct an experimental program to develop the technology for obtaining oil from oil shale. In adopting and later extending this legislation, the Congress recognized the impending necessity of supplementing ground petroleum reserves with synthetic fuels. Under the provisions of this legislation, the Bureau of Mines, among other things, was charged with the responsibility of developing mining techniques, methods, and equipment for mining the oil shales of the Green River formation of Colorado, Utah, and Wyoming. The oil shales of western Colorado are apparently richer, more accessible, and more amenable to exploitation than elsewhere in the Rocky Mountain region. The site chosen for the Bureau's Experimental mine is about 10 miles west of Rifle in northwestern Colorado. It is within a 1000-sq-mile area from which, it has been estimated, 300 billion barrels of shale oil could be produced from a 500-ft measure near the top of the formation. One hundred billion barrels of this amount could be produced from the Mahogany ledge, a 60 to 100-ft section near the bottom of the 500-ft measure. This ledge is considered to have economic importance at present. The Green River formation was laid down as sediment in the bottom of vast, shallow inland lakes during Eocene time. The deposit is flat-lying, and there are no faults, fissures, or local rolls. Oil shale is actually a strong, tough magnesium marlstone, which will stand unsupported over relatively wide spans. These and other natural physical characteristics favor mechanized, low-cost mining, which is essential for establishment of an oil-shale industry. It was realized from the outset that an extensive research program would be necessary to develop mining methods, equipment, and techniques for a mechanized, low-cost operation. The program was designed to include research. into all the productive phases of mining, such as drilling, blasting, loading, transportation, and maintenance of the mine structure. The methods, equipment, and techniques developed as a result of this research have established a production of 116 tons per man-shift total labor at a direct cost of $0,292 per ton. Another important phase of the research program that has received little publicity because of its theoretical nature is study of the roofstone behavior and determination of mine structure stresses. This paper purposes to discuss this phase of the research program. Preliminary studies of the physical properties of the Green River oil-shale formation were made in the Barodyramics Laboratory at Columbia University during the latter part of 1945 and the early part of 1946.* The purpose of these studies was to determine the maximum size of unsupported underground openings that would be commensurate with safety and still permit the use of large, efficient mining equipment. Also to be determined were the pillar support to extraction ratio and the shape, size, and spacing of supporting pillars. Selected samples of possible roofstones near the top of the Mahogany ledge, as well as representative samples of different rock types found within the ledge, were obtained from the Bureau's oil-shale mine for these studies. The maximum safe unsupported roof span calculated from this work was 200 ft. Using a safety factor of four, it was theoretically determined that openings 60 ft wide could be advanced under a roofstone at the top of the Mahogany ledge. To support the overburden, 60-ft-sq pillars would be left in a checkerboard pattern. From visual observations made of core samples through the selected roofstone at the oil-shale mine, it was determined that the roofstone was actually a plate 6 to 8 ft thick. Because the calculations were theoretical and allowance had to be made for unknown cracks and fractures in the formation, openings 50 ft wide and pillars 60 ft sq were originally contemplated in the Bureau's Experimental mine. This would be the minimum allowable width that would permit use of large underground mining equipment. For lower mining costs and greater efficiency larger openings were desirable. Different but analogous approaches were made to the problem at the Bureau of Mines Applied Physics

Jan 1, 1951

By J. T. Norton, H. Blumenthal, S. J. Sindeband

The interstitial phases formed by the transition elements with carbon, nitrogen and boron constitute a unique class of substances which are of considerable technical interest because of their well developed metallic properties and their high hardness and melting points. They are also of interest from the point of view of structure. It was pointed out by Hagg1 some years ago that the principal factor determining these structures was the relative sizes of metal and metalloid atoms. He predicted that if the ratio of the radii of metalloid to metal atoms was less than 0.59, the metal atoms would be arranged in a close-packed fashion of relatively simple type. This prediction has been amply confirmed. It appears, however, that this specification applies most generally to those structures in which the metalloid atoms occupy isolated positions in the lattice and there is no tendency for strong binding between the metalloid atoms themselves. The series of borides of the type MeB2 formed from the transition elements of the fourth (Ti, Zr) and fifth (V, Cb, Ta) groups of the periodic table provide an opportunity to investigate this situation further. If one takes as a basis the radius of 0.87 A for the boron radius and the Goldschmidt values for the metal atoms in 12 coordination, then the radius ratio varies from 0.54 for zirconium to 0.64 for vanadium, which latter is considerably greater than Hagg's limit of 0.59. It was of interest, therefore, to see if these five elements would form borides of the MeB2 type and have simple isomorphous structures. When this investigation was initiated, relatively little information had been published on the structure of this group of borides. McKenna2 reported the preparation of ZrB2 by a carbon reduction process. Its structure was hexagonal and the approximate lattice constants were given as a = 3.15 A, c = 3.53 A. Ehrlich3 reported the structure of TiB2 as being of the C 32 type with a = 3.02, c = 3.21 and c/a = 1.06 A. Recently, Kiessling4 published the results on ZrB2, showing it to be one in which the metal atoms are arranged in a simple hexagonal lattice with the boron atoms in flat sheets, midway between the layers of metal atoms. The structure is C 32 type with a = 3.169, c = 3.530 and an axial ratio =1.11 A. He also states that CbB2 and TaB2 are isomorphous with ZrB2. Preparation of Borides The borides of titanium, zirconium, columbium and tantalum were made by the electrolysis of fused salt baths after the method described by Andrieux.5 The bath, totalling about 6500 g in each case had the following general composition: Metal Oxide + B2O3 + CaO + CaF2. The actual proportions of the ingredients were determined for each individual case. Although Andrieux reports the preparation of vanadium boride by the same electrolytic method, several attempts proved unsuccessful. However, it was possible to prepare VB2 by the carbon reduction method used by McKenna to produce ZrB2. The mixture consisted of V2O5 + 6B2O3 + 11C and the reduction was carried out in an induction heated graphite crucible. This method proved satisfactory for ZrB2 and TiB2 and undoubtedly the others could be made in the same way. The borides, which were all in the form of fine gray metallic crystals from the electrolytic bath or gray powders from the reduction process, were carefully separated from other constituents and analyzed chemically for metal and boron content. The densities of the boride powders were measured using a standard 10 cc pyenometer at 18°C and ethyl benzene proved to be the most satisfactory liquid for this purpose. X Ray Technique The boride crystals, as prepared, were too small for single crystal examination so that powder techniques were employed. Patterns of the finely ground borides were prepared, using the Norelco recording X ray spectrometer. The lines on these patterns were indexed with the aid of Hull-Davy charts and the approximate dimensions

Jan 1, 1950