Search Documents

By George A. Komadina

Pima Mining Company has recently completed their expansion tripling the plant capacity to 18,000 tons per day and now is in the process off expanding to 30,000 tons per day with completion scheduled for the summer of 1967. This paper briefly discusses the additions to the mining department and support areas with a more detailed report on the complete new crushing plant and additions to the concentrator. The crushing plant includes a 54-inch gyratory crusher, three 7-foot standard and seven 7-foot short head crushers along with necessary screens, feeders, and conveyor belts to produce a minus 1/2-inch rod mill feed. The concentrator consists of ten milling sections, each containing one 10-foot by 16-foot rod and two 10.5-foot by 13-foot ball mills, classification is done with cyclones. Pulp from each section is floated in 50 cells of 66-inch Fagergren flotation machines to produce a rougher concentrate which is cleaned in six stages of Denver cleaners to produce a final concentrate The various mill products are thickened with disposal made in conventional manner. Plant instrumentation is discussed in the paper.

Jan 1, 1967

By James H. Aase

Shales from 10 locations in Michigan were sampled, tested, and evaluated to determine their suitability as raw materials for producing lightweight aggregate by rotary-kiln methods. Sampling procedures and the geology of the shale units tested are discussed. Preliminary testing in a muffle furnace preceded extensive testing in a l6-inch by 14-foot rotary-kiln. Rotary-kiln products from these shales ranged in weight from 35.5 to 61.2 pounds per cubic foot (pcf). Concrete test specimens made pith selected aggregates were evaluated to determine the qualities of the concrete. Compressive strengths of the concrete ranged from 2,830 to 4,240 psi after 28 days of curing. Unit weight of the concrete ranged from 94.8 to 101.5 pcf. Lightweight aggregate suitable for use in structural concrete meeting ASTM standards was produced by the rotary-kiln method using shale samples from two locations.

Jan 1, 1967

By A. Lubinski, J. E. Hansford

Rotating drill pipe passing through dog-legs suffers fatigue damage due to cyclic bending stresses. Curves of the cumulative fatigue damage incurred in either steel or aluminum drill pipe going through Such dog-legs are presented. These curves provide means for properly planning the rate of angle build-up in directionally drilled wells and allow discarding of drill pipe which has been fatigue-damaged in dog-legs. INTRODUCTION Drill pipe which is subjected to bending as it rotates, experiences a cyclically varying bending stress. If this bending stress is sufficiently large, the drill pipe is fatigue-damaged by each revolution, and ages as fatigue damage accumulates. Drill pipe can be bent intentionally, as in the case of directionally drilled holes, or unintentionally due to unde-sired changes in hole direction caused by variations in formation properties, weight on bit, etc. These changes in hole direction, whether intentional or unintentional, are called dog-legs. The theoretical limits of dog-legs which are permissible before the drill pipe begins to fatigue can be calculated.' However, in wells where the maximum permissible dogleg is exceeded, the concept of cumulative fatigue damage can be used to estimate damage suffered by the drill pipe. This concept has already been used to estimate the cumulative fatigue damage of drill pipe due to drilling vessel roll.' The purpose of this paper is to extend the usage of the cumulative fatigue damage concept to drill pipe in doglegs, and to draw conclusions which may be beneficial in preventing numerous frustrating and expensive drill pipe failures. FATIGUE OF STEEL DRILL PIPE IN IDEALIZED GRADUAL AND LONG DOG-LEGS It is taken for granted that, if necessary, the reader will become familiar with the definitions and concepts which follow by examining the reference cited in each case. For Ref. 1, it will suffce to read only through the section Abrupt Dog-Legs. 1. Concept of the two extreme kinds of idealized doglegs: gradual and long dog-legs and abrupt dog-legs,' 2. Concept of why the bending moment in drill pipe un- der tension is the largest in the vicinity of the tool joint,' 3. Concept of why dog-leg severity which drill pipe can withstand decreases with an increase in tension,' and 4. Definition of the rate of change of over-all hole angle (dog-leg severity)." Figs. 1 and 2 indicate the aging (fraction of life expended) of steel drill pipe passing through a gradual and long dog-leg. Both figures have a left-hand ordinate scale labled Length of Drill Pipe Below Dog-Legs. This scale can be used for cases in which the drill collar weight is applied to the bit and does not contribute to the tension in the drill pipe. It can be used for either 3 1/2-, 4 1/2- or 5-in. drill pipe. This is due to the fact that, if the drill collars do not contribute to the drill pipe tension, then the effect of pipe tension on bending due to a change in pipe size is nearly compensated for by a corresponding change in pipe rigidity. On the other hand, if drill pipe is rotated off bottom, then drill collars contribute to the tension in the drill pipe and this increase in tension is not compensated for. In this case, one of the three right-hand ordinates must be used (the one which corresponds to the correct drill pipe size). In the right-hand ordinates, tension should be understood as the weight in mud of the portion of the drilling string below the dog-leg, minus the weight on bit.

Jan 1, 1967

By Jack L. Henry

The monocarbide region of the ternary system U-C-O has been investigated at 1,700° C as the first phase of a more extensive study of a portion of the four-component system U-C-O-N. An area bounded by the following compositional limits in atomic percent was studied: U, 44 to 55; C, 30 to 60; 0, 0.2 to 20. Compacts composed of mixtures of uranium, graphite, and uranium dioxide powders were sintered at 1,700° C under an equilibrium pressure of carbon monoxide to produce uranium oxycarbide specimens having a variety of compositions. Sintered specimens were evaluated by X-ray, chemical analysis, and ceramographic techniques. Solid-solution boundaries and phase relations have been established, and the effects of composition on the lattice parameter as well as the decomposition pressure have been investigated. Oxygen can be substituted for carbon in stoichiometric uranium monocarbide to the extent of about 17 atomic percent at 1,700° C. The composition range of the oxycarbide solid solution extends from about 48 to 51 atomic percent uranium in the low oxygen region. Above 10 atomic percent oxygen the composition range narrows to less than 1 atomic percent uranium. Carbon monoxide exists as a gaseous phase in equilibrium with all compositions which contain oxygen. Five separate phase fields were found bounding the solid-solution area. Other phases within this portion of the system include uranium, uranium dioxide, uranium dicarbide, and uranium sesquicarbide. Decomposition pressures of oxycarbide compositions at 1,700° C have been found to vary from a few microns for stoichiometric and uranium-rich compositions to 35 torr for carbon-oxygen-rich specimens. Lattice parameters were found to depend upon the U to C + 0 ratio as well upon the extent of substitution of oxygen into the stoichiometric monocarbide lattice.

Jan 1, 1967

By Richard F. Link

The objective of this report is to explain a statistical method for the summarization, organization, and classification of multivariate assay and other data from the mineral industry. Multivariate data are those characterized by several measurements at each data point, such as assay data from a mixed metal mine, or blast furnace data. A specific method of linear discriminant analysis, the Mahalanobis d2 procedure, is explained, starting from elementary principles; the d2 procedure enables many measurements at many data points to be studied by investigating the interrelationships among the data. The relation of linear discriminant analysis to other statistical methods for treating multivariate data, in particular the eigenvalue technique of factor analysis, is also explained. Example analyses are made on data from the Frisco mine, San Francisco del Oro, Chihuahua, Mexico. The data comprise assay values for silver, lead, copper, and zinc taken at some 19,000 sample points distributed into 91 groups.

Jan 1, 1967

By D. H. Forbes, I. B. Cadoff, H. M. Manasevit

Single-crystal silicon films have been obtained on several natural crystal faces of BeO using the thermal decomposition of silane and the hydrogen reduction of silicon tetrachloride. From an analysis of X-ray diffraction data it was determined that the following film-substrate orientation relationships exist: (111) Si 11(0001) BeO, (111) Si 11(1011) BeO, (100) Si 11f1010) BeO. and (110) Si 11(1010) BeO. An analysis of the crystallographic relationships between the film and substrate indicates that a match occurs between the silicon atoms in the film and the berylliuni ion sites in the substrate. This correspondence is in agreement with previous work on the deposition of silicon on sapphire.1-3 silicon on spinel: and tungsten on sapphire. The high resistivity, thermal conductivity, and radiation resistance of beryllium oxide make it an important substrate material for the deposition of thin films of silicon or other semiconductors. The importance of semiconductor-insulator composites to the field of integrated microelectronics has been well-documented in the case of silicon on sapphire.'-' The successful growth of large-area single-crystal silicon on an insulator, sapphire, was first reported in 1963.1,2 Since that time studies have been made of the crystallographic relationships between the deposited film and the sapphire substrate. On the basis of the observed relationships, a model has been proposed relative to the crystallographic requirements for epitaxy between the semiconductor film and the metal oxide substrate.3 It is proposed in this model that epitaxy is the result of a match between atoms of the deposited film and the metal ion sites of the substrate plane. This match is not limited to a 1 to 1 correspondence between sites in the two lattices. Sub- sequent studies of the deposition of silicon on spinel4 and tungsten on sapphire5 have yielded data which support this model. On the basis of this previous work it was felt that silicon on BeO should also fit this model. In the present study, the choice of substrate orientation was limited to the natural faces of synthetic BeO crystals. Of the faces available, the (0001) plane seemed the most favorable for epitaxial growth. EXPERIMENTAL PROCEDURE Silicon films were deposited from silane and silicon tetrachloride in the apparatus shown in Fig. 1. The hydrogen ambient gas was purified by passage either through a DEOXO unit, molecular sieves, and a liquid nitrogen cold trap, or through a heated Pd-Ag thimble. The gas was then mixed with the silicon source materiai and passed over the substrate which lies on a spacer above an inductively heated silicon pedestal. The following deposition conditions were used: a hydrogen flow rate of 3 liters per min with silane and silicon tetrachloride concentrations of 0.2 mole pct and a pedestal temperature of 1175" * 5°C as observed with an optical pyrometer assuming an emissivity of 1.0. Deposition was preceded by a 15- to 30-min hydrogen-etch period conducted at a temperature of 1275°C (obs). Adherent silicon films from 2 to 10 u were grown on the various BeO faces. The substrates were synthetically grown beryllium oxide single crystals ranging from 5 to 10 mm in

Jan 1, 1967

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

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

Jan 1, 1967

By Wei-Kao Lu, G. Bitsianes

An improved general rate equation for a one-ditnensional gas-solid system has been derived. Fov the veversihle interfacial chemical reaction, there are concentrations of gaseous reactant and product at the reacting zone to be considered. They have been calculated with the velations fuvnished by the constraints on the system, namely, quasi-steady state and equimolal counterdiffusion of the gases. The results of the diffusiori study of Evans, Watson, and ,Mason based on the "dusty gas" model have been applied here. The interfacial chemical reaction is taken as first-order with respect to the concentration of the gases involved. The equation has proper dependence on gas composition and on solid structure through the relative values of Knudsen and normal diffusivities. The existence of the total pressure gradient inside the specimen has been predicted and confirmed experimentally. In a previous communication' we introduced a general rate equation for gas-solid reactions by considering the contributions of chemical reaction at inter- phase boundaries and diffusion through the solid product layer simultaneously. These equations, for one-dimensional and spherical specimens, take care of the whole range continuously from purely diffusion control to purely chemical reaction control. In this paper we study only the one-dimensional system. The corresponding rate equation is reproduced here: Of the two terms on the right-hand side of Eq. [I], the first represents the contribution of interfacial chemical reaction and the second that of gaseous diffusion. The shortcomings of Eq. [I] are that in its derivation the interfacial chemical reaction was assumed to be irreversible and the diffusion rate of gaseous product was not considered. Any pressure effects building up within the porous media were also neglected. Evidently. these simplifying assumptions will limit the general applicability of these equations. The rate of reduction of iron oxide by hydrogen, for instance, is very sensitive to the concentration of water vapor in the main gas stream, as has been reported by cewan' and by Quets et a1.3 Furthermore, the gaseous phase at the reacting interface will contain an appreciable amount of the gaseous product of reaction. If this were not true, a sufficiently high concentration gradient for the outward diffusion of the gaseous product could not be maintained. With these shortcomings in mind, Eq. [1I cannot be rigorously ap-

Jan 1, 1967

By Thomas C. Wilder

The concentration and activity of oxygen in liquid copper has been measured by the reversible galvanic cell: at 1100°and 1200°C for the concentration range of oxygen of 3 to 5600 ppm Measurements for approximately thirly alloys at each temperature indicate that the activity of oxygen roughly follows Henry's law, the activity coefficients of oxygen being 0.12 and 0.205 at 1100° and 1200°C, respectively. These results compare javorably with the results of seven other electrochemical and gaseous equilibrium studies on this system, the free energy of the solution reaction 1/2 O2 = O (7 at. pct in Cu, liq) being -18.10 * 0.30 kcal per gfw at 1200°C. Estimates of the standard molar free energy of formation of CupO(S) are also made. Praclicul consideration of this cell as an oxygen sensor for liquid metals is discussed briefly. SOLID mixed-oxide electrolytes which have a defect structure in the anion sublattice have recently become a very popular means by which the chemical potential of oxygen is measured at high temperatures. Since the pioneering work of Kiukkola and Wagner1 such electrolytes have been used in numerous cell studies for determining the thermodynamic properties of metallic oxides and oxy compounds, the partial pressure of oxygen in vacuum systems and other atmospheres, and the properties of oxygen dissolved in metals and alloys. The use of a solid electrolyte in a cell for a fast reliable method of oxygen determination in liquid metals would be a very important tool to the process metallurgist. In copper, for example, the oxygen content of the molten metal in the cathode furnace is a prime factor in determining the "set" or solidification profile of cast wire bars. In this investigation the activity of oxygen in liquid copper was measured by an electrochemical cell employing the electrolyte ZrO2 + 7 1/2 wt pct CaO. The cell used at 1100° and 1200°C was

Jan 1, 1967

By Leroy Dockter

The grinding characteristics of lignite in a ball mill were investigated. The variables studied were initial lignite moisture content, degree of in-the-mill drying, and lignite source. The mill tested was a pilot-p1ant-size conical ball mill which had a maximum output of from 80 to 180 lb/hr pulverized product depending on the lignite and test conditions. The capacity of the test mill ranged from 82 to 103 lb/hr depending upon mine source, in pulverization of as-mined lignite with minimum drying, The capabilities of the ball mill could not be correlated to Hardgrove index of the individual lignites or other observed physical properties. Predrying lignite from its 35 to 40 percent raw moisture content to about 10 percent moisture before grinding improved the mill capacity 87 percent, compared to an increase in capacity of 74 percent with in-the-mi11 drying to the same product moisture.

Jan 1, 1967

By Elton L. Litchfield

The Bureau of Mines determined minimum energies for direct initiation of expanding gaseous detonation waves in acetylene-oxygen mixtures. Composition limit ranges for the initiation of detonation with fixed energies have been compared to data in the literature. Assuming that the stored electrical energy is completely converted to thermal energy, the agreement between the energy of primary explosive initiators and the energy of electrical discharge initiators was good. Minimum energies for initiation of detonation in the most sensitive composition (40 percent C20 plus 60 percent 0 2) were: 0.64 joule at an initial pressure of 1/4 atmosphere, 5.0X10-2 joule at 1/2 atmos¬phere, and 3.7X10-3 joule at I atmosphere. Fuel concentrations in mixtures initiated to detonation by 4.9X102 joules ranged from 10 to 65 percent C2H2 at 1/4 atmosphere, 10 to 67 percent C2H2 at 1/2 atmosphere, and 9 to 68 percent C2H2 at 1 atmosphere.

Jan 1, 1967

By Jr. Hazen

Two statistical techniques, the mean-square-successive-difference test and correlation, are used to investigate the problem of assigning an area of influence to an assay. Data from five hydrothermal deposits, Climax molybdenum, Cebolla Creek titaniferous iron, San Manuel copper, Piedra Hueca copper, and Butte copper, are studied. Two groupings of the assays are used for the mean-square-successive-difference tests. One group involves an increasing sample volume by reaveraging assays to represent a longer sample intervals, the other by regrouping assays to represent longer sample intervals without a change in sample volume.

Jan 1, 1967

By W. B. Hickman, J. J. Pickell, B. F. Swanson

Many physical properties of the porous media-immiscible liquid system are dependent upon the distribution of fluids within the pores; this in turn, is primarily a function of pore structure, liquid-liquiri interfacial tcnsion and liquid-solid wetting conditions. The cnpillary pressure hysteresis process provides a means of investigating the influence of pore structure upon fluid distribution for consistent sur/acc conditions. Invcstigntiot2s indicate that residual non-wetting-phase saturations /ollozuir,g the imbibition process (i.e.,wetting phase displacing nor2-wctting phase) are dependent upon both pore structure and initial non-raetting phase saturation and suggest that residual fluid is distributed as Discontinuous ,globules, one to a few pore sizes in dimension, thrnugh the entire range 01 pore sizes originally occupied. It clppears that air-mercury capillary pressure dala adequntely rellect the distribution of fluiris in a water-oil system when strong wetting condition preliczil. An oil-air counter-current imbibition technique has also been found to provide a rapid rneans of obtaining residual-initial saturation data. In a majority of cnses, rcsidual saturations detf-rniinecl from the oil-air or air-mercury process reasonably approximate residual oil saturation following water drive of a strongly water-wet medium. INTRODUCTION A reliable estimate of recoverable reserves depends not only on the amount of original oil-in-place but also on pore geometry and distribution of fluids within the pores. A critical parameter determining the recovery from a reservoir under waterflood, for example, is the amount and distribution of residual oil within the various rock types present. The purpose of this paper is to investigate the mechanism of capillary trapping and assess its importance in laboratory measureqents of residual oil saturation. The degree of wettability of a reservoir rock is recognized as an important factor in waterflood or imbibition experiments. In this paper, however, only the water-wet case has been considered. Considerable experimental evidence1 suggests that for water-wet rocks, capillary forces predominate in tile distribution of fluids and that viscous forces in the range normallv of interest in the reservoir have a minimum influence on residual oil saturation. It follows that if the ultimate recovery is controlled by pore geometry, a unique residual non-wetting phase saturation should exist for a given set of initial conditions. Two laboratory procedures.found to be extremely useful in the study of pore structure and degree of fluid interconnection at various saturations are decribed. Although air-nercury capillary injection curves have been used2 previously to characterize the drainage case, the withdrawal or imbibition case can provide valuable supplementary data. The air-mercury process, however, has several disadvantages; it is difficult to run in a sufficiently accurate manner, mercury does not always act as a strongly non-wetting liquid and in the air-mercury process the sample is rendered unsuitable for future analyses. An alternative process is described in which air is the non-wetting phase and naptha, hentane, octane or toluene is the wetting phase. INTERFACIAL TENSION AND CAPILLARY PRESSURE Interfacial tension between immiscible fluids is due to the difference in attraction of like molecules as compared with their attraction to molecules of the neighbouring fluid. This net attraction results in a tension at the interface. To extend the interface; thus, interfacial tension s can also be thought of as free surface energy. Interfacial tension is normally expressed as dynes/cm, and interfacial energy is measured in ergs/cm2 hence, both have dimensions ml A 2 and are numerically equal.

Jan 1, 1967

By T. J. Smolik, Harman, D. W. Fuerstenau

By means of electrokinetic measurements, the surface properties of the aluminosilicate polymorphs (sillimanite, andalusite, and kyanite) and also mullite have been found to depend on the ratio of A10 bonds to SiO bonds in the surface. The Al-toSi ratio in the surface is dependent upon the crystal lographic properties of the mineral, which in turn determine coordination numbers of A1 and of Si, cleavage characteristics, and density of the various solids. Mullite with a greater bulk Al-toSi ratio has the highest zpc of the aluminosilicates. By treatment in dilute acids or by cycling between acidic and basic solutions, alumina is selectively dissolved from the surface of these orthosilicates. This shifts the apparent zpc to lower pH values as the fraction of SiO groups in the surface increases. Thus, surface properties can be altered by procedures that alter the A l-to-Si ratio in the surface. Flotation of these aluminosilicates results from electrostatic interaction of the collector ions with the mineral surfaces. As a result, flotation response shifts in accord with any shift in apparent zpc by pretreatment. Separation of minerals by flotation is based on differences in the physicochemical properties of their surfaces.'-3 For many minerals, adsorption of flotation collectors results from their functioning as counter ions in the electrical double layer at solid-water interface. In such systems, separation depends on differences in the zero point of charge (zpc) of the various minerals. The zpc is defined as the concentration of potential determining ions in solution at which the surface is uncharged. The potential determining ions for inorganic oxide-water interfaces are hydrogen and hydroxyl.4,5 This work is concerned with the effects of crystal structure, composition, and surface preparation on the surface properties and flotation behavior of aluminosilicates. Differences resulting from crystal structure were studied by measuring electrokinetic potentials and determining the flotation behavior of three different aluminosilicate materials having the same chemical composition (Al2O3 SiO2), namely andalusite, kyanite, and sillimanite. Furthermore, the effect of the Al2O3-to-SiO2 ratio on flotation behavior and surface properties was investigated by including synthetic mullite, 3A12O3 .2SiO2. Gaudin and co-workers 6,7 have clearly shown how crystal structure determines the native floatability of certain minerals. Those solids in which the surface is comprised mainly of broken residual bonds possess naturally hydrophobic surfaces. It was found by Bakakin8 that for a number of oxidized lead minerals, differences in floatability were due to the distance of Pb atom from the surface. Only limited work has been done on relating electrical properties of surfaces to crystal structure and composition. Healy et. a1.9 found that the zero points of charge of various manganese dioxides ranged from about pH 1.5 to pH 7.5, and these differences in the zpc's were interpreted in terms of the atomic packing in the various crystals. The research presented here clearly shows that crystal structure and chemical composition do affect the surface properties of aluminosilicates and, in addition, that these effects can be altered by changing conditions under which the surfaces are prepared. CRYSTAL STRUCTURE OF THE ALUMINOSILICATES Sillimanite, andalusite, and kyanite are composed of regionally metamorphosed rocks differing mainly in degree of metamorphism. All three minerals have the same chemical composition, Al2O3 - SiO2, of which sillimanite is the high temperature polymorph and kyanite and andalusite the lower temperature polymorphs. Andalusite and sillimanite crystallize in the orthorhombic system while kyanite crystallizes in the triclinic system. The structure of these three minerals is essentially chains of aluminum-oxygen octahedra linked laterally by silicon and aluminum. The arrangement of these chains in the three minerals is shown in Fig. 1.l4

Jan 1, 1967

By W. M. Yim

Experimental results are presented which indicate that transverse striations in horizontal zone-leveled Bi-Sb alloy crystals are due to irregular growth rate resulting from thermal fluctuations in the melt (Iring gowth. Thc thermal fluctutations arose from two different sources. The first type was brought about by periodic fluctuations in the furnace temperature. The second type can be attributed to turbulent therrrol conlcclion in the trzelt near the solid-liquid inteyace. Tile arrzplitlcde ond fvequency of the tetiperaticre fluctlrations vesultity from llle lhevnal con1,ecrrell. The striation spacings in Lhe crystals covvelale well with the periodicity 0.f the tempevature flueluatiors. Altliough the strialiors represenl corrlpositiozul inhoiHogeneity oh a rzicroscule, less than f.z cil. be1 S6 in Best's as deterrirzed by electron-pro be chalq'sis, the slriations roerre fbund to ILUL' no rrleusuanble effect on electical vesistirity rwr on weak field macgnetoresistance of. the Bi-Sb a1lu.y in the ternpevutue ),unge 4.Polo 300°K. DURING the course of an investigation on the horizontal growth of semimetals,' it was found that crystals of Bi-Sb alloys contained many closely spaced parallel arrays of striations. These striations occurred perpendicular to the growth direction and parallel to the solid-liquid interface. We shall refer to them as transverse striations, or just striations'', to distinguish them from lineage substructures or longitudinal striations which form parallel to the growth direction and have been known to be associated with cellular structures.' Similar transverse striations have been reported previously to occur in other materials prepared by horizontal growth: metals,4 semiconductors,5 as well as their alls. - Various methods of crystal preparation have apparently little effect on the occurrence of the transverse striations. They form whether the crystals were grown by the vertical Czochralski technique, withe1' or without'3- rotation, or by the horizontal zoning methd.- Thus, the transverse striations are not limited to any one class of materials, nor to any particular method of preparation. It is likely, therefore, that all of the observed transverse striations may have some common cause. Previously, workers agreed that periodic changes in the growth rate bring about the striations. However, no agreement exists as to the origin of the growth-rate fluctuations. Some attributed the discontinuous growth to a purely external cause, such as fluctuations in the furnace temperature, jerky motions in the crystal pulling mechanism, or a nonsymmetrical temperature distribution in the melt (in the case of crystals grown by the Czochralski technique with rtation). Others looked for the cause in some fundamental property of the growth process itself. For instance, a certain degree of supercooling is required to initiate growth from the melt. But, with further growth, the degree of supercooling decreases because of the liberation of the heat of solidification at the solid-liquid interface. Thus, crystal growth would be brought to a halt until sufficient supercooling is resotred and the cycle begins again.3'11 According to this model, periodic fluctuations in the melt temperature should exist at the solid-liquid interface. Since the periodic fluctuations in growth rate would result in changes in the segregation coefficient of solute atoms, crystals containing the transverse striations may, in some cases, show a periodic impurity fluctuation along the length, resulting in a degradation of electrical properties. The resistivity striations in doped germanium'9-10 or lnsbB are well-known examples of this microsegregation. The present work was undertaken to explain the exact origin of the transverse striations, and to assess the extent of their effect on chemical homogeneity as well as on electrical properties of Bi-Sb alloy crystals. Results from our previous study of the crystal growth of Bi-Sb alloys1 indicated that the transverse striations may arise from the temperature fluctuations in the melt during growth. This paper will show that the melt temperature fluctuations are indeed responsible for the occurrence of the transverse striations. I) EXPERIMENTAL Although the transverse striations have been observed in all slow-grown Bi-Sb alloys across the entire compositional range, we selected a composition, Big3Sbs, for the present study in view of the extensive data available on the crystal growth of this alloy from a previous study.' High-purity bismuth and antimony, both a 6-nine grade by the manufacturer's emission spectrographic analysis, were used throughout. Independent mass-spectrographic analysis showed, however, that the starting materials were more nearly a 5-nine grade. each containing metallic impurities of approximately 10 ppm atomic. In zone-leveled Big5Sb5 alloys, the total metallic-impurity content was slightly lower, about 7 ppm atomic, indicating that some degree of purification was achieved during the growth. None of the electrically active impurities, such as tin and lead (acceptors) and tellurium and selenium (donors), were present in significant quantity in undoped Bi95Sb5. Typical analysis of the undoped Bi95Sb5 alloy is shown in Table I. Nonmetallic impurities, such as carbon and oxygen, were detected, sometimes as much as 100 ppm, in both the starting materials and the zone-leveled alloys: but the data were only qualitative. Temperature fluctuations in the melt were monitored over 1 or more days by means of a 5-mil chromel-

Jan 1, 1967

By N. Mungan

Laboratory imbibition and displacement experiments were performed using crude oil and cores drilled with water and preserved under anaerobic conditions. The purpose of these tests was to determine reservoir rock wettability and to find out if more oil could be recovered by use of NaOH solution than by conventional waterflooding. The preserved cores were found to be oil-wet. Contrary to work in the literature, these cores changed to water-wet upon contact with air. After exposure to air for a week, the cores yielded more oil by waterflooding than when preserved under exclusion of air. At reservoir temperature of 160F, flooding the preserved cores with 0.5N NaOH solution recovered more oil than an ordinary wa-terflood, and additional oil when following a waterflood. When the caustic solution was used from the beginning, all the extra oil was obtained before breakthrough; when the caustic followed a conventional waterflood, the extra oil was produced in the form of an oil bank ahead of the injected caustic. The increase in oil recovery resulted from wettability reversal. Also, use of caustic reduced the volume of injection required to flood out the cores. At room temperature, however, the caustic solution did not reverse the wettability and gave no additional oil recovery. Cores which had become water-wet by air exposure or caustic flooding were restored to their original oil-wet state when saturated with crude oil and allowed to equcilibrate at reservoir temperature for two weeks. Therefore, in the absence of preserved cores, it may be possible to restore weathered cores to their original wettability for use in laboratory floods. INTRODUCTION Waterflooding has been in use since 1865, and is by far the simplest of secondary recovery methods. Unfortunately, most waterfloods are inefficient in recovering oil, often leaving half or more of the original oil in place un-recovered. The low oil recovery generally results from low sweep efficiency and low displacement efficiency. Consequently, to increase oil recovery by waterflooding, sweep and displacement efficiencies should be improved. Sweep efficiency is primarily affected by reservoir heterogeneities and mobility ratio, while displacement efficiency is affected by the capillary forces between fluids and rock surfaces. For petroleum reservoirs, the capillary forces are expressed in terms of interfacial tension and wettability. If oil recovery is to be improved significantly in water- flooding, the capillary forces holding the oil in the raervoir porous matrix must be reduced or eliminated. One way to reduce capillary forces is to inject commercial surfactants ahead of the injection water into the reservoir. Laboratory tests of this method have shown no promise of an economical process yet, and no increase in oil recovery was obtained in the field trials which have been reported. Work is continuing in many companies to find surface-active agents which, in workable concentrations, can yield substantial added oil recovery. Another way to change capillary forces operating in petroleum reservoirs is by changing the pH of the injected water. Wagner et al.' showed that change in the pH sometimes activates the surface-active materials natural to some crudes and brings about gross wettability change. Since pH alteration can be obtained with cheap chemicals, such as hydrochloric acid or sodium hydroxide, the process shows promise of being economical in a field application. Pan American Oil Corp. reported oil recovery by use of caustic solution from a flooded-out reservoir.' Their test, conducted at a small additional cost, yielded results which were so sufficiently favorable and encouraging that the wettability reversal flood was expanded to portions of the field not previously flooded.13 It is important to bear in mind that changes in the pH of the water not only can reverse wettability but also can lower the interfacial tension between water and crude oil. Reisberg and Doscher4 have studied the pH dependency of the interfacial tension of Venture crude using sodium hydroxide solutions of various concentrations. Their data show that the interfacial tension was lowered from 23.0 to 0.02 dynes/cm by increasing the NaOH concentration from 0.005 to 0.5 per cent by weight. Thus, the use of NaOH may lead to additional oil recovery due to both wettability reversal and lowering of interfacial tension. Whether alteration of pH results in wettability reversal from oil-wet to water-wet and increases oil recovery depends on wetting properties of the reservoir rock and the crude. This necessitates delicate laboratory experiments, with suitable core and fluid samples from a field. Although many investigators have studied wettability reversal floods in the laboratory,1,2,5,6 these studies have been carried out with synthetic porous media, refined laboratory fluids and surface-active chemicals to simulate the process. The study presented in this paper is the first time that wettability reversal by pH alteration has been accomolished in laboratory core floods using carefully preserved natural cores, live crude and with experiments performed at reservoir pressure and temperature.

Jan 1, 1967

By K. P. V. Lei

The Bureau of Mines investigated molten-salt electrorefining as a practical method for reclaiming vanadium from vanadium scrap. An electrolytic process utilizing a KC1-LiC1-VC12 electrolyte at 615° C was developed for producing ductile vanadium with a purity over 99.9 percent. The recovery of the vanadium in the cell feed ranged from 88 to 93 percent with a current efficiency from 83 to 95 percent.

Jan 1, 1967

By G. A. Brady

Laboratory tests were conducted to determine the technical feasibility of separating anthracite particles from a water-anthracite slurry by atomizing the water and removing the resulting mist in an air current. Products containing 21 percent or less moisture were obtained from slurries made with minus 60-mesh anthracite. Typical recoveries ranged between 67 and 79 percent of the feed when the slurries were atomized in air currents with velocities below 70 ft/min.

Jan 1, 1967

By J. E. Hanlon, J. D. Wolf

The relaxation peaks observed in plastically deformed materials at low temperatures have been reviewed by sack1 and Niblett and wilks. 2 In particular, the dislocation-relaxation in columbium has received considerable study.3-6 The present work deals with the lower-temperature dislocation-relaxation peak (referred to by Chambers and Schultz as the a peak) in columbium and Cb-5 pct Zr. The columbium and Cb-5 pct Zr specimens were machined to 3/8-in.-diam by 7-in.-long rods from bars hot-extruded at 1200°C. The internal friction and resonant frequency of the samples were measured in torsion at kilocycle frequencies at a maximum strain amplitude of -10-6. The interstitial content of both materials was approximately 70 ppm N and 200 ppm 0. The dislocation-re laxation peaks were measured in the hot-extruded state and after successive anneals. Fig. 1 is a compilation of the data. The resonant frequencies for the columbium and Cb-5 pct Zr samples were, respectively, 5.5 and 6.5 kc. Other workers have noted that the dislocation-relaxation peaks in columbium are not characteristic of a single relaxation time. As can be seen in Fig. 1, the zirconium addition further broadens the spectrum of relaxation times. The magnitude of the modulus defect as computed from resonant-frequency data also reflects this extension. The occurrence of the low-temperature a peak at a position 20°K higher in Cb-5 pct Zr as compared to pure columbium, in the hot-swaged state, suggests a decrease in the average dislocation mobility for the alloy. The authors do not feel that these data are sufficient to permit an interpretation in terms of any detailed models.

Jan 1, 1967

By Peter Joralemon

I want to limit my remarks to epigenetic ore deposits, but do not necessarily subscribe to the classic theories of hydrothermal ore deposition. I will consider an epigenetic deposit as a primary deposit in which the economic minerals have been introduced subsequent to the formation of the enclosing rock, regardless of the source. Past ore discoveries have been made to a great extent by prospecting techniques that have remained relatively constant over the last many decades. In many cases the discoveries have been enlarged or enhanced with the use of technical tools such as geophysics, but theoretical geology, which should serve as a foundation for exploration, has shown little progress of practical importance since the turn of the century.

Jan 1, 1967