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By D. C. Seidel, M. C. Fuerstenau, R. J. Roman

The role of surface charge in soluble salt flotation, which was developed in Part I, is extended to relate the theory to the specific phenomena of KCI-NaC1 separations. Temperature-collector solubility relationships, metal ion activation, and particle size effects are discussed. The initial paper in this series developed and presented the hypothesis that one of the mechanisms of soluble salt flotation may involve electrical attraction between the collector and mineral surface. This hypothesis was developed from a combination of experimental data and free energy calculations, and details of the logic are presented in this first paper.* The studies have indicated that KC1 has a positive surface charge and NaCl a negative charge. KC1 can therefore be floated with sulfonate ion (RSO;) or with an aqueous polar species such as the aqueous amine chloride, RNH3C1(,,). The chloride end of the RNH3C1(,,) molecular dipole is probably negative and will be attracted to the positive surface of the KC1 particles and absorb (actually probably fit into a vacant chloride site) on the mineral surface. The amine end of the collector molecule would extend into the solution phase and provide the air avid surface required for flotation. NaCl particles are floated by such collectors as aqueous molecules of fatty acid salt, RCOONa(,,), in which the positive inorganic end of the dipole is attracted to the negatively charged surface of the NaCl and, in this case, adsorb and probably fit into a vacant sodium site on the surface. The aminium cation, RNH~, should also be a collector for NaC1. For certain collectors, actual precipitates of the collector must be formed before a sufficient amount of the polar aqueous molecule is present to effect flotation. In a system of this type there is a three-way equilibrium between: Aqeous Molecular Solid Precipitate - A of the Collector (Not Dissociated) . Ionic Species (Dissociated). The controlling equilibrium is probably between the precipitated form of the reagent and the aqueous

Jan 1, 1969

By testing rotary-drag bits in granodiorite it was found that an increase in bit clearance angle from 241 0 to 33° decreased insert wear. Severe wear has precluded economic application of rotary-drag drilling in abrasive rock even though fast penetration rates have been achieved.From a limited number of tests and from theoretical considerations, the insert wear was inversely proportional to the thrust on the bit This effect follows the marked reduction in the linear distance traversed by the inserts, for a given depth of penetration, as thrust increases...

Jan 1, 1969

By D. O. Hobson

Zirconium single crystals of various specific orientations were fabricated by rolling or drawing. The resulting textures were determined and are discussed with respect to the deformation modes that produced them. The crystals deformed in a predictable manner by combinations of up to third-order twinning with three twinning modes and by slip. Twinning was found to play a major role in initial texture formation. Texture changes produced by slip occurred only at the higher reductions. The twinning sequences that produced each intensity peak during the initial reductions could be identified. Schmid factor criteria were found useful in predicting which deformation modes to expect for each crystal orientation and fabrication procedure. The possible application of these data to poly-crystalline material is discussed. PREFERRED orientation or texture has a significant effect on the properties of most materials, causing anisotropy in fabricated cubic metals and enhancing the natural anisotropy of noncubic metals. This study evaluates the effects of several fabrication methods on the textures formed from specific starting orientations of zirconium single crystals and, it is hoped, gives an insight into the effects of the same operations on poly-crystalline material. BACKGROUND In fcc and bcc metals, texture changes take place by gradual lattice rotations caused by the operation of one or more slip systems. Deformation twinning plays an insignificant role in the deformation of such metals. In zirconium and its alloys, however, and in many other hep metals the ability to twin allows very rapid texture changes to be made with very small amounts of deformation. The deformation systems found in zirconium and its alloys are prism slip and three twinning modes.1 Slip occurs on the {1010}< 1120) system. There is little or no appreciable basal slip in zirconium. The twinning planes, illustrated in Fig. 1, are {1012}, {ll2l}, and {1122}. Two twinning modes, the {1012} and the {ll2l} operate for a tensile stress along the basal pole. A compressive stress parallel to the basal pole is required for {ll22} twinning. These twinning operations cause a 35- to 85-deg reorientation of the basal pole. The {1012} twin is the predominant tensile twin at room temperature. The twinning shears, S, are shown in the figure. A criterion for predicting which deformation system will operate when a grain is subjected to a known stress state is the Schmid (orientation) factor. This factor gives the fraction of the applied stress that computer program was written2 to calculate the Schmid factors for the four deformation modes in zirconium. It assumed three orthogonal stress axes and considered ninety-one different orientations of the basal pole in one octant of this stress space. At each basal pole position the Schmid factors were calculated for seven positions of rotation at 10-deg increments of the unit cell about the basal pole. Schmid factors were determined for a total of 637 orientations and for twenty-four deformation systems in each orientation. The program listed the Schmid factors for uniaxial stress parallel to each axis and, to approximate rolling, or-thonormal biaxial stress was also considered. Fig. 2 shows the range of orientations over which the various types of deformation would tend to predominate in biaxial plane strain with the stresses, equal magnitude. The exact boundary position between regions of different deformation modes depends, however, on the relative values of the critical shear stress for each deformation mode. Fig. 2 is drawn on the assumption that they are equal and it therefore may be only approximately correct. It is also recognized that the biaxial stress analysis may not be applicable in certain crystal orientations. EXPERIMENTAL PROCEDURE Single crystals of zone-refined zirconium, produced by Wilson of this Laboratory,3 were electrical-discharge-machined to form specimens for rolling, tube-drawing, and rod-drawing studies. Specimens were rolled at room temperature on 2-|--in.-diam hand-powered rolls from three different starting orientations: 1) the basal plane parallel to the rolling plane and the [1120] in the rolling direction, (0001)[ll20]; 2) the (1120) plane parallel to the rolling plane and the basal pole in the rolling direction, (1120)[0001]; and 3)_the (1120) plane parallel to the rolling plane and the [1100] in the rolling direction, (1120)[ll00]. Drawing specimens were cut with the [0001] direction as the drawing direction in the tube blank and [1120] as the drawing direction in the rod specimen. The drawing

Jan 1, 1969

By James V. Luxner

The airflow and methane distribution patterns developed in an equipment-free entry 6.5 feet high and 12 feet wide, ventilated by line brattice operated blowing to or exhausting from the face, were determined by the Bureau of Mines for varying conditions. Results of these studies show that blowing line brattice systems of face ventilation are more effective than comparable exhaust systems. The face ventilating efficiency of any line brattice system is dependent upon the method of ventilation, the face distance, the tight rib distance, the volume of air delivered to the end of the line brattice, and the volume of methane released at the face. Experimental results indicate that maximum face ventilation efficiency is achieved when the inby terminus of the line brattice is installed 5 feet from the face and at a distance less than one-third the entry width from the nearest rib. Analyses of data are based upon the ability of a face ventilation system to dilute methane in the immediate face area.

Jan 1, 1969

By P. R. Jones

A computer program was written for design and cost of a shell and tube heat exchanger in which the total cost, which includes annual fixed charges and annual operating costs, was minimized. The program was written for the type of heat exchanger in which only the tube side pumping costs were significant and for triangular pitch, single or multiple pass, heating or cooling, and no change in phase. Tube diameter was not optimized since the tube dimensions do not affect the cost very much. However, the tube dimensions do affect the shell diameter, number of tubes, and length of tubes; and price optimum design was obtained for four standard tube diameters. Standard heat exchangers having at least the required area are also listed. The program was made adaptable to various fluids and to various tube dimensions by including many of the required data such as physical properties of the fluids, tube data, and standard shell data as input data.

Jan 1, 1969

By R. D. Daniels, T. G. Oakwood

A study was made of the effects of small quantities of hydrogen on the mechanical properties of colum-bium. Tensile specimens, hydrogenated to concentrations of 20 to 200 ppm, were tested at temperatures of 300°, 191°, and 77°K. Although hydrogen was found to have little effect on the strength of columbium, the ductility of Cb-H alloys was found to be quite sensitive to both hydrogen concentration and temperature. At 300°K, an abrupt loss in ductility occurred at a critical hydrogen concentration, although some ductility was observed beyond the tolerance limit. A similar result was found at a lower hydrogen concentration at 191°K. At 77°K, however, a more gradual loss in ductility with increasing hydrogen concentration was observed. Hydrogenated columbium was thus observed to undergo a ductile-brittle-ductile transition. Metallographic examination of fractured specimens revealed extensive porosity at both 77° and300°K which was a distinct function of hydrogen content. At 191°K, although some secondary cracking was noted, the amount of observed porosity was minimal. These observations are interpreted in terms of hydrogen solubility and mobility as a function of temperature and in the role of hydrogen in promoting growth of microcracks. lHE effect of hydrogen on the mechanical properties of the refractory metals is not, at present, completely understood. A number of studies have shown these materials to be susceptible to hydrogen embrittlement. Roberts and Rogers1 have found that vanadium can be embrittled by hydrogen. It was further demonstrated that fracture undergoes a ductile-brittle-ductile transition as the temperature is lowered from 150° to -196°C; i.e., there is a ductility minimum observed at a certain temperature. The ductility is increased by either raising or lowering the temperature from this point. A more complete study by Eustice and Carlson2 on vanadium containing 10 to 800 ppm placed the ductility minimum at about -100°C with variations reportedly due to hydrogen content and strain rate. Ductility minima have also been found at certain temperatures for tantalum containing 7 ppm H3 and 140 ppm H.4 At hydrogen concentrations above 270 ppm, however, the ductility return at low temperatures was considerably reduced.4 In the case of columbium, some disagreement exists in the literature. Eustice and Carlson,5 Wilcox et al.,6 and Imgram et al.4 failed to find a ductility minimum although a composition-dependent ductile-brittle transition was observed. Hydrogen concentrations in these investigations were 20 ppm,5 1 to 30 ppm,6 and 200 to 390 ppm.4 However, Wood and Daniels7 observed a rather pronounced ductility minimum at hydrogen contents ranging from 19 to 252 ppm. Those theories of hydrogen embrittlement involving the precipitation of diatomic hydrogen which have been applies to ferrous metals8-12 do not seem to be applicable to the case of columbium and other exothermic occluders. Such theories propose that extensive crack formation and propagation occurs by the precipitation and expansion of diatomic hydrogen at internal voids and microcracks. However, photomicrographs of hydrogenated columbium do not show any evidence of damage introduced by the sorption and precipitation of diatomic hydrogen; rather, at high hydrogen concentrations, a hydrogen-rich second phase is precipitated.13&apos;14 In addition, a number of these theories require the development of high hydrogen pressures at voids in the structure.8&apos;10&apos;12 This does not appear to be feasible in the concentration ranges discussed in the aforementioned paragraphs. The possible interaction of atomic hydrogen with microcracks resulting from dislocation pile-ups15,16 remains in doubt since pile-ups have not been observed in bcc metals17 including columbium.18 Wood and Daniels7 have put forth the possibility that a hydride precipitation could be responsible for crack nucleation in columbium. Work by Longson19 has shown that hydrogen embrittlement of columbium parallels the bulk solubility limit; i.e., as the solubility increases, for instance with temperature, the amount of hydrogen necessary to cause embrittlement also increases. Although a hydride precipitation appears attractive as a means of nucleating microcracks in columbium, what require more intensive study are the low-temperature anomalies which have been observed, i.e., the ductile-brittle-d&apos;ictile transition characteristics. Also, the hydrogen concentrations where embrittlement occurs are often below the bulk solubility limits determined by Albrecht et al.13,14 and Walter and Chandler.20 This work is an attempt to determine more definitively the effects of concentration and temperature on the mechanical properties of dilute Cb-H alloys. EXPERIMENTAL PROCEDURE Ultrahigh-purity columbium rods, obtained from the Wah Chang Corp., were cold-reduced by rotary swaging. A chemical analysis is given in Table I. The material was cut into cylindrical blanks 1.50 ±0.005 in. long. Individual specimens were either given a stress relief anneal at 750°C or recrystal-lized at 1200°C. Resulting microstructures were either a "bamboo" structure characteristic of a wrought material or a recrystallized structure with a grain diameter of approximately 100 n. All heat treatments were carried out in a vacuum of 10-5 Torr or less.

Jan 1, 1969

By G. R. Love

i\ program has been written which allows fully automatic conversion of data for X-ray intensity, as a function of time, to finished conventional pole figures. The program accepts input data in the serial order in which they are taken and is therefore immediately compatible with automatic data-acquisition devices. From these data taped instructions are prepared for the Calcomp plotter to construct ink-on-paper drawings. Because both Siemens and Norelco pole figure goniometers are used in this laboratory, the program was written for pole figure data obtained from one or more interpenetrating spiral scans during which both the polar angle, @, and the equatorial angle, a, are varied simultaneously and continuously. The reference direction for a scan, that is the point @ = 0 deg, may be chosen coincident with either the normal direction (N.D. figures) or the rolling direction (R.D. figures). In either case the plotted figures are drawn with the transverse direction (a = 0 deg) at the right and the rolling direction at the top. The full, circular, pole figure is drawn as two semicircular figures labeled "front side" and "back side". As presently constituted, the program will also accept data from circular scans taken at constant values of @. In every case the angular coordinates of each intensity entry are generated in the computer from a relatively small number of auxiliary data. The X-ray intensity data are corrected for background scattering by direct subtraction of the intensity measured with 28 set appropriately "off" the Bragg angle. It is possible to enter this correction as an additional spiral scan through the a, @ space; because the background correction does not normally vary rapidly enough to warrant this detailed a determination, the background corrections are entered as one or more auxiliary data. All data are normalized to a multiple of random intensity. The data taken in this laboratory for N.D. figures are normally taken in a reflection geometry from from sheet samples and do not extend beyond <p = 75 deg; for these data random intensity must be determined from separate experiments and entered as auxiliary information. When the auxiliary information is not available, a number is chosen to give intensity values normalized to a scale of 1 to 10. In this laboratory, R.D. figures are based upon hemispherical samples for which data are taken out to @ = 90 deg; for these data random intensity is calculated by direct numerical integration of . sin @ d@ using the trapezoidal rule and the background-corrected values of the input data. Points necessary to the construction of the pole figure are identified by simple linear interpolation between adjacent data points to determine the loci of contour lines. Points lying on a given contour are connected to one another with straight-line segments and the search-calculation-drawing sequence is patterned to assure that different contour lines do not cross, that a single line does not branch, and that lines do not end in space. However, so that there be no ambiguity in the data presentation, all contour lines end at the limits of the input data. Since the curves are constructed of straight-line segments, they are not continuous in their derivatives. However,

Jan 1, 1969

By Paul R. Smith

The theoretical requirements for the flotation d large particles are discussed. A flotation machine is described which has components which meet many of the theoretical requirements for the flotation of large particles. The machine&apos;s salient features include multiple fine-bubble attachment, froth level feeding, quiescence, shallow depth, and short flotation time. Test conditions and results are presented for the laboratory flotation of 10 mesh phosphate, 4 mesh potash, and 1/2 inch coal. In addition, test conditions and results of pilot plant flotation of minus 14 plus 35 mesh phosphate and minus 14 plus 150 mesh phosphate are also presented.

Jan 1, 1969

By Shiro Ban-ya, John Chipman

Equilibrium in the reaction was investigated at temperatures of 1500°, 1550°, and 1600°C for sulfur concentrations up to 7.2 wt pct. Multisample crucibles contained the liquid alloys in a resistance-heated furnace using a technique especially designed for the study of more complex alloys to be reported separately. Modern free-energy data are used to correct the H2S:H2 ratio for dissociation of H2S and calculalion of the partial pressure of S2. Published data on the equilibrium are similarly corrected. Thermodynanzic treatment of the data employs the composition variable zs = nS/(nFe — nS) and the activity coefficient Gs = as/zs The data at 1500" and 1550°C are fitted by the equation log s = —2.30zs. Within the limits of experimental error the same coefficient is applicable to the data at higher temperatures. Equations are given for the free-energy change in Reaction [I] as well as for the solution of S, gas in the metal. The heat of solution of 1/2 s2 is -32.28 i2.5 kcal. Uncertainty in the free energy is very much smaller. For dilute solutions of interest in steelmaking, the activity coefficient of sulfur is unchanged from that listed in Basic Open Hearth Steel-making. DETERMINATIONS of the thermodynamic properties of sulfur in liquid iron by Morris and williams1 and by Sherman, Elvander, and chipman&apos; provided a basis for control of sulfur in steelmaking processes. From the standpoint of understanding the chemistry of metal plus nonmetal in liquid solution they left several questions unanswered. The activity of sulfur in dilute solution at about 1600°C was well-established but temperature coefficients were uncertain, due at least in part to the use of the optical pyrometer and uncertainty regarding the effect of sulfur on emissivity. It appeared that deviation from Henry&apos;s law increased with increasing temperature, a most unusual behavior requiring either confirmation or disproof. These studies were based on experimental determination of equilibrium in the reaction: At high temperatures H2S is partially dissociated so that the gas mixture contains HS, S2, and S in addition to HS. At the time of the earlier studies the free energies of these constituents were unknown and it was therefore impossible to make adequate correction for dissociation. Observations on the effects of alloying elements by Morris and coworkers1, 3 and by Sherman and Chip-man4 enable us to assess the effects of alloying elements on the activity and to make corrections for incidental impurities in the binary liquid. These studies as well as a number of more recent investigations will be reviewed in detail after out own experimental results have been presented. It was our purpose in planning this study to avoid uncertainties regarding the emissivity of alloys and the errors of thermal diffusion which plagued some of the early attempts,5 by using a resistance furnace and thermocouple in preference to induction heating and optical pyrometer. Modern data on free energies of the gaseous species are to be applied to our data and to those of other investigators to obtain corrected values of K1 and of the activity coefficient and ultimately to relate the sulfur content of the bath to the equilibrium partial pressure of S,. Extension of the study to include ternary and complex solutions will be described in a later section. EXPERIMENTAL METHOD a) Preparation and Calibration of H2-H2s Gas Mixture. The source of hydrogen sulfide was a preparer mixture of 43 pct H2S, balance hydrogen, contained in a large aluminum cylinder. This was passed through anhydrone and through a microflowmeter. Hydrogen was passed through platinized asbestos, ascar-ite, and anhydrone, and through a capillary flowmeter. Argon was passed through copper wool at 500°C, then through ascarite, anhydrone, and a flowmeter. The flow rate of hydrogen was kept constant at 200 ml per min, to which an arbitrary amount of the hydrogen-hydrogen sulfide mixture was constantly added and then the prepared gas mixture was introduced into the reaction tube through a gas mixer. In certain experiments 200 ml per min of argon was added to the hydrogen-hydrogen sulfide gas mixture to increase the total flow rate of gas. The ratio of hydrogen-hydrogen sulfide in the inlet gas was checked for each run by chemical analysis. A sample of the gas taken from a bypass was bubbled through zinc and cadmium acetate solution (4 pct zinc acetate, 1 pct cadmium acetate, and 1 pct acetic acid) to remove hydrogen sulfide from the gas mixture, and the flow rate of the remaining hydrogen was measured by a soap bubble method to determine the volume of hydrogen. The amount of hydrogen sulfide absorbed in solution was determined by titration with iodine against sodium thiosulfate, with starch used as the indicator. The ratio of hydrogen sulfide to hydrogen in the inlet gas could be kept within ±2 pct in the range from 10-2 to 5 x 10"4 which corresponds to from 0.2 to 7.0 wt pct sulfur in liquid iron. b) Furnace Arrangement. Fig. 1 shows the furnace arrangement and the shape of the alumina crucible used in this experiment. A vertical-tube silicon carbide electric resistance furnace contained the reaction tube which consisted of two parts, the gas-tight

Jan 1, 1969

By M. J. Salkind

In order for fiber composite materials to find extensive use in structures, it is necessary to develop techniques for joining these materials. Riveting and adhesive bonding are two possible techniques which have been investigated although the former is less desirable because the low shear strength of most matrices makes this type of joint subject to bearing failure. Welding is an effective means of joining, especially for high-temperature applications where ad-hesives are weak; however, there are significant limitations placed on welding composite materials. The commonly used fusion welding techniques will find less use for joining composites because the two phases are often unable to stand exposure to such a stringent environment. In the case of eutectic composites, fusion welding will completely destroy the controlled microstructure. Solid-state techniques such as diffusion bonding offer potential success with certain design requirements placed on such joints. Since the primary mechanism of load transfer from matrix to fiber is shear parallel to the fibers, little load can be transferred across a butt-welded interface perpendicular to the aligned fibers. Successful joint designs must have a component parallel to the fibers to allow a shear area for load transfer. Configurations such as lap and scarf welds are likely to be successful. This note describes some results of experiments with diffusion-bonded joints in A13Ni whisker-reinforced aluminum. The composite material, prepared by unidirectional solidification of the A1-A13Ni eutectic, is described elsewhere.&apos;-&apos; It consists of aligned micron size whiskers in a matrix of aluminum. Since it has been shown that the microstructure of

Jan 1, 1969

By J. C. LaScola

Development of methanometers and anemometers for underground use in coal mines is reviewed. The first semicontinuous recording methanometer was developed in 1961 in West Germany. The Bureau of Mines developed an instrument using; pellesters that was a continuous recording methanometer. Expansion of freon gas created a vacuum which pulled the methane-air mixture through a tube to an electrically heated, catalyst-impregnated pellester where the mixture was burned. The National Coal Board of England developed a continuous recording methanometer based on the principle of the Davy flame safety lamp. A thermo-pile was used to sense the hurt output of the flame. Finally the Bureau of Mines improved its methanometer by eliminating the freon gas and using a diffuser head to a monitor methane-air mixtures. Development of recording anemometers proceeded from the use of a photo¬cell and light source to sense rotation of the Biram-type anemometer blades to the use of a Hall detector to sense, rotation by measurement of electromagnetic pulses.

Jan 1, 1969

By William J. Gillich, Gerald L. Moss

PREVIOUS studies of the shock loading of randomly oriented polycrystalline aggregates have firmly established that, after rather short load duration, hydrostatic compression closely approximates the shocked state.&apos; However, McQueen deduced from pressure measurements with good time resolution that, during shock loading, metals begin to undergo a stress relaxation at the yield stress. He suggested that the relaxation is due to plastic deformation accompanying the change from a one-dimensional compression to a three-dimensional, hydrostatic, compression.&apos; Stress relaxation may occur faster as stress is increased above the yield stress, but the existence of unidirectionally compressed states for finite times suggests that the concept of a unidirectionally distorted lattice should furnish considerable insight into the mechanical behavior of materials subjected to shock loading. Here, a crystallographic analysis is presented for the hypothetical situation where atom motion may be considered as unidirectional which, as indicated above, is a useful extension of the macroscopic concept of shock loading to the microscopic domain. Only motion caused by the com-pressive forces is treated; i.e., lattice vibrations upon which this motion is superimposed, as discussed by Fitzgerald, are ignored.3 The purpose of the analysis to be presented is to develop a description for single crystals of the lattice rotations that occur for idealized uniaxial strain deformation. The usefulness of such an analysis in realistic deformation is to give a method of specification of those properties of an initially distorted lattice which would affect the subsequent deformation. Non-axial complications that arise experimentally, such as off-axis rarefaction waves, must be treated in proper context. Consider the material element shown in Fig. 1 and let the compression be uniform at all regions of the element. Then, any interior point of the element is displaced in proportion to its distance from the base of the element. Accordingly, if the top of a unit element is displaced by an amount, (-K), with respect to the base, a point P(X, Y) will be displaced by (-KY). Crystal planes are, therefore, rotated by the compression. Analysis of this rotation may be accomplished from the geometry shown in Fig. 1 where the line OP is the edge of the plane {hkl} and N is its normal. The orientation of the crystal plane with respect to the shock direction is specified by the angle, before deformation. After deformation the edge of plane {hkl}

Jan 1, 1969

By G. E. Warner

This paper presents a review and analysis of a highly stratified Burbank sand waterflooding project in Osage County, Okla. Permeability values in this reservoir range from less than 0.1 md to nearly 3 darcys, and 90 percent of the permeability capacity is contained in approximately 26 percent of the reservoir volume. To date, the project has recovered 103 bbl/flood-acre-ft since waterflood initiation, which represents 50 percent of the total preflood cumulative and 12 percent of the original stock-tank oil in place (OSTOIP). The outstanding feature of this project has been the economical recovery of a sizable quantity of oil at water-oil ratios higher than those normally considered prohibitive. Nearly 70 percent of the recovery to date has been achieved at water-cut values greater than 95 percent. An ultimate waterflood recovery of 138 bbl/flood-acre-ft, or 67 percent of the preflood recovery and 16 percent of the OSTOIP, is predicted. The ultimate primary and secondary recovery will be 302 bbl/acre-ft and approximutely 40 percent of the OSTOIP. The actual performance is compared with the predicted performance by both the Stiles and the Dykstra-Parsons methods, and applicabiliry of these methods to this particular reservoir is evaluated. The performance of this project indicafes highly stratified reservoirs can be successfully and economically waterflooded when either reservoir or economic conditions preclude the use of mechanical and chemical means of mdbility control. Introduction The concept of the stratified reservoir has been used by reservoir engineers for many years to describe the vertical variations in permeability within a reservoir. Numerous techniques have been advanced to predict the expected waterflood performance of the stratified reservoir, and in most cases they prove reasonably accurate. The advisability of undertaking a prospective waterflooding project is determined, based on these predictions. This paper presents a review of a waterflood project in a highly stratified reservoir that normally would be considered a marginal prospect, at best, when evaluated with any prediction technique properly adjusted for reservoir conditions. This kind of project can be successful if the predictions are used to design a waterflooding system capable of economically recovering an oil cut of 1 to 2 percent. Experience gained in the early stages of the project&apos;s development was profitably applied in the later development of the entire reservoir and could prove beneficial to other projects with similar reservoir stratification or fracture characteristics. The East Burbank pool waterflooding operations have been developed in three separate stages, each of which has been a separate project: Mid-Burbank Unit, Flood A, and Stanley Waterflood. When referred to collectively, these projects will be called the Composite Project. The Skelly Oil Co.&apos;s Barber lease — the only portion of the pool not included in the three projects — is operated as a separate facility with a cooperative injection-well agreement. It contains less than 80 productive acres and would not significantly affect the over-all performance picture.

Jan 1, 1969

By John Nagy

The Bureau of Mines examined explosion development in a closed spherical vessel, mathematically correlating flame travel, pressure, and time with parameters defining the reaction. The model assumes that burnt and unburnt zones are separated by a thin, radially moving flame front. Isothermal and adiabatic systems are considered. Correlation with gas and dust explosion data is better for the adiabatic system, but the isothermal development is simpler and in reasonably good agreement. Interpretation of the explosion phenomena is facilitated by expressing the rate of mole change in the flame front in terms of elementary parameters. This expression is developed by examining the components of spatial-flame velocity.

Jan 1, 1969

By K. Takahashi, I. Iwasaki

it is well known1 that racemic mixtures of optical isomers can be separated by passing their solutions through a column packed with r- or 1-quartz powder so that one of the isomers becomes adsorbed selectively on the asymmetric quartz surfaces. Although the natural occurrence of r- and 1-quartz is more or less equally distributed, some localities show enough deviations toward a higher proportion of l-quartz2 to suggest that optical isomerism might influence quartz flotation. Beta-amines have an asymmetric carbon atom, and therefore optical activity may be expected. Beta-amines are reported to behave quite differently from alpha-amines in the flotation upgrading of certain oxidized iron ores.3 It is of interest, for both practical and theoretical reasons, to determine whether or not optical isomerism plays a role in the amine flotation of quartz. In this article the results of Hallimond tube flotation tests and of adsorption measurements using d-beta-phenylisopropylamine on both r- and 1-quartz are compared. D-beta-phenylisopropylamine was chosen for the tests because it is commercially available in optical isomers. MATERIALS AND METHODS Brazilian quartz crystals were hand-sorted according to the difference in trigonal trapezohedral faces, and each crystal was further checked by the Airy&apos;s spiral.4 The respective crystals were then crushed, and the -150 + 200-mesh fractions were screened out for the Hallimond tube tests. The samples were cleaned by brief leaching with warm, dilute hydrochloric acid, and then by repeated rinsing with distilled water. In preparation for the adsorption measurements, they were then dry-ground in a pebble mill for several hours, washed a few times with distilled water, and finally dried in a vacuum desiccator. By means of the Krypton gas adsorption method, the specific surfaces of r- and 1-quartz samples were determined to be 27,700 and 19,800 sq cm per gm respectively, the difference being due mainly to the decantation procedure rather than to the inherent difference in their grindability. D-beta-phenylisopropylamine was the only collector used in the study. It was solubilized by neutralizing with 110% of the stoichiometric requirement of 0.1 N hydrochloric acid. The specific rotation of the d-beta-phenylisopropylamine was determined with a polari-meter using sodium D line to be, Although the d-beta-phenylis~prop~lamine showed absorption maxima in the wave length region of 250 to 270 millimicrons, due presumably to the phenyl group, these peaks were too sensitive to be used for colorimetric determination of the residual concentration in the adsorption measurements. The amine-picrate method, used in the colorimetric analysis of dodecylammonium chloride,&apos; was found to work satisfactorily for the d-beta-phenylisopropylamine. The adsorption densities were thus determined after equilibrating 40 gm of the ground quartz sample with 300 ml of solution by tumbling in separate glass-stoppered Erlenmeyer flasks for one hour. EXPERIMENTAL RESULTS Fig. 1 presents the adsorption densities of d-beta-phenylisopropylamine on the r- and 1-quarts in the pH range of 6 to 7.5. In agreement with data reported in the literature, the adsorption density of d-beta-phenylisopropylamine was slightly higher on the r-quartz than on the 1-quartz, although the difference was not as pronounced as one might expect from the capacity of r-quartz and 1-quartz to separate racemic

Jan 1, 1969

By Forrest T. Moyer

The safety record of the metal mining and milling industries in 1965 is reviewed by the Bureau of Mines. The overall injury-frequency rate of 23.77 per million man-hours was 5 percent lower than in 1964 and was the lowest annual rate in a statistical history beginning with 1931. The injury-severity rate of 3,521 days lost per million man-hours in 1965 represented a 5-percent improvement over 1964. However, the total of 3,825 disabling work injuries comprised 61 fatal and 3,764 nonfatal injuries, one and 92 more, respectively, than in 1964. At primary nonferrous smelters, refineries, and reduction plants, the injury-frequency rate of 8.97 per million man-hours in 1965 was 13 percent lower, but the severity rate percent higher than in 1964. these plants in 1965, 4 more of 1,173 days lost per million man-hours was 17 There were 12 fatal and 971 nonfatal injuries at and 28 fewer, respectively, than in 1964.

Jan 1, 1969

By Verne E. Hooker

In situ stresses, based on isotropic and anisotropic relations, were evaluated using computer techniques from overcoring data obtained in dimension stone quarries along the Appalachian Piedmont, the Ozark Uplift, and the Ouachita Tectonic Belt. Stresses in the horizontal plane near the surface are compressive and range from 100 to 4,500 psi. The direction of maximum compressive stress seems to be alined with the general tectonic structure for most of the determinations. The ratio of the maximum to minimum elastic parameters in the horizontal plane ranges from 1.05 to 2.46 for these competent rocks. Isotropic versus anisotropic stress determinations show differences only as great as 25 percent in stress magnitude and 25° in orientation.

Jan 1, 1969

By E. J. Wasp

The transportation of mine products incurs a cost which can have a significant bearing on the competitive position of the manufactured product. Clearly, the engineer who is responsible for selecting a mode of transport must base his decision, at least in large measure, on economic comparisons. And today, the engineer usually finds that he has to choose between several modes, including slurry pipelines. For the purpose of an initial economic screening, it is not necessary to go deeply into the technical details of a slurry system. What is usually needed, however, is a method with which the engineer can make a quick economic assessment to determine whether a slurry pipeline should be included in the detailed final analysis. This paper presents a rapid method for making such a preliminary appraisal. Experience with commercial slurry pipeline systems in several countries and with a variety of solid materials has shown that if several assumptions pertaining to critical design variables are made, it is possible to roughly estimate the transportation cost of a slurry system on the basis of only three factors: the specific gravity of the solid material, the length of the system, and the quantity of slurry to be pumped each year. It is assumed that conditions pertaining to field construction, corrosion inhibition, and the like, will be favorable. This assumption is critical because any factor which analysis shows to be particularly unfavorable will raise the total transportation cost estimate which this paper establishes. If the engineer employs this estimating procedure and decides that the use of a slurry pipeline is economically unattractive, his chances of being wrong are small. Conversely, if his quick appraisal indicates that the use of a slurry system is economically favorable, the engineer is justified in committing the time and money needed to make a more detailed investigation of the slurry pipeline potential.

Jan 1, 1969

By Wesley T. Holmes

In this final stage of a three-part investigation of the smelting of titania-bearing iron materials, the Bureau of Mines conducted semicontinuous smelting tests in a laboratory electric arc furnace on four concentrates and one are. The objective was to substantiate the significance of liquidus temperature measurements in predicting satisfactory slag compositions in electric furnace smelting of titaniferous magnetites to produce pig iron. Previously obtained liquidus temperature data were used in determining flux requirements. Self-fluxing pellets of either ore or concentrate plus fluxes and reductants were made to produce pig iron and slags containing 0.2 to 0.6 percent titanium. Individual constituents of the slags generally agreed within 5 percent with the value of the corresponding constituent of target composition. Liquidus temperature of furnace slags generally agreed within 50° C of the value obtained from corresponding nominal synthetic slag. The results of the three phases of the investigation may serve as guide-lines for determining flux requirements in smelting a wide variety of titaniferous magnetites and other titania and iron-bearing materials.

Jan 1, 1969

By S. K. Asunmaa, W. D. English, N. A. Tiner, W. A. Cannon

This paper discusses the reaction of metal surfaces with fluorine. Fluorination reactions result in the formation of metal fluoride films which are "passive" toward further reaction of the metal with fluorine. These films are very adherent, and do not easily detach from the substrate metal by mechanical flexing or thermal shock. Exposure of passive films to a humid atmosphere produces hydrated metal fluorides which cause secondary fluorination reactions upon reexpo-sure of the metal surface to fluorine. The surface films formed range from 10 to 30A in thickness and they pow at the expense of surface oxide films. The apparent film formation is completed rapidly in 15 to 30 min on stainless steel and nickel surfaces. On copper and on Monel surfaces, the film at first grows rapidly, then increases slowly over an extended period of time. Passive films are formed at all fluorine pressures in the range from 0.1 to 1.4 atm at room temperature. ALL metals react when exposed to fluorine. These reactions generally produce surface films which consist of metal fluorides. The rate of reaction is largely determined by the extent to which these films are protective. Although there is an extensive literature concerning reactions of oxygen with metals, there are very few investigations reported concerning fluorine-metal reactions. Brown, Crabtree, and ~uncan&apos; investigated the kinetics of the reaction of gaseous fluorine with copper metal which had been freshly reduced in hydrogen. The reaction rate was independent of pressure over the range from 6 to 60 torr. A logarithmic rate law was obeyed in the temperature range from 25" to 300" ~. There was some deviation at higher temperatures which could have been the onset of a parabolic law. The calculated film thicknesses ranged from about two molecular layers, 10A, for 5 hr exposure at room temperature to thirty-five molecular layers for 5 hr exposure at 200" . The authors concluded that no single mechanism could explain all the observations. O7Donnell and spatkowski2 studied the reaction of fluorine with copper at 450°C at pressures from lo to 133 torr. The reaction was found to be pressure -dependent and followed a logarithmic rate law. It was not entirely diffusion-controlled, and fluorine was thought to be the migrating species in the reaction. Miscellaneous metal-fluorine reactions were investigated by Haendler et ~1.~ Reaction products were identified but no rate data were determined. Air Prod- ucts and Chemicals, Inc., have conducted an investigation of reactions between fluorine and various metal powders at room temperature and 85° C. Fluoride film thickness as a function of time of exposure was reported on the assumption that the reaction takes place between fluorine and metal to form the normal metal fluoride. Surface areas of the powders were only estimated so the relative film thicknesses may not be exact. The data showed reaction rates which were generally logarithmic in character, the rate of film growth virtually ceasing after a few hours exposure time for some alloy powders. The effect of moisture on fluoride films was also investigated by measuring additional reaction with fluorine after exposure of passivated powders to atmosperic moisture. The fluorination of iron was studied by 0&apos;~onnell~ at temperatures from 225" to 525" ~ and at pressures ranging from 20 to 200 torr. In all ranges, the reaction followed a logarithmic rate law and was dependent on the square root of the gas pressure. The author concluded that fluorine gas passes through pores in the film. As the film grows, the blocking of pores leads to a rapid decrease in reaction rate; hence a logarithmic rate law is observed. Jarry, Fischer, and Gunther&apos; investigated the mechanism of the reaction of fluorine with nickel at about 600" to 700°C. On the basis of the metallographic examination of fluoride scales growing on the nickel and from separate radioautographic data, it was claimed that fluorine is the migrating species in the reaction. This is in sharp contrast to the growth of oxide films on nickel where it has been shown that nickel ions migrate through the scale to the gas-solid interface to react with oxygen. Few investigations have been reported of the reaction of fluorine with metal oxides. Such investigations should be of great significance for a better understanding of passivation in view of the ubiquitous oxide films on technical alloys. Haendler et al.3 studied the reaction of fluorine with oxides of copper, tin, titanium, zirconium, and vanadium. Copper (I) oxide reacted as follows in the temperature range 150" to 300"~: temperature above 300" ~ was required for the CuO to react to form additional copper fluoride. Ritter and smith7 also investigated the reaction of fluorine with copper (11) oxide. An oxide powder comprised of spherical particles with a fairly high surface area was reacted with fluorine, starting at room temperature and increasing to 100° C over a period of 3 or 4 hr. The initial reaction was slow until the fluoride film thickness reached about to or 15R at which time the reaction rate accelerated, then decreased again. Most of the kinetic data was obtained during this final phase of reaction. The authors conclude that the film grows slowly at first until the stresses developed in the distorted lattice are sufficient to rupture the initial

Jan 1, 1969