Search Documents

By D. W. Smith, Robert F. Mehl

It has been shown by numerous studies that the orientations of new metal crystals are determined by the orientations of the crystals in the original matrix, whether these new crystals are formed by recrystalliza-tion, by precipitation from solid solutions, or by transitions in the solid state. The orientations of crystals formed by recrystallization of cold-worked metals that bear preferred orientations are occasionally simply related to the initial preferred orientation; often, however, the relationship is not simple, but complicated and obscure in origin.1 The orientations of crystals formed by precipitation from solid solutions have been shown by many studies in this and other countries to be determined by the orientation of the crystals of the solid solution stable at the higher temperatures, though here again complicated cases have been found and no general theory is available.2 Related to this latter class are the relationships found in crystals formed by suppressed transforma-

Jan 1, 1935

By W. A. Burns

Vertical flow is an important mechanism in many petroleum reservoirs. Yet no adequate method has heretofore been proposed for determining the in-situ vertical permeability in a reasonable length of time. Core measurements of vertical permeability do not necessarily represent effective in-situ values. Cores may be representative of only localized pockets of high or low permeability, and total reliance on cores might cause one to overlook the presence of vertical fractures altogether. Conventional single-well tests, interference tests, and pulse tests commonly are used to determine horizontal transmissibility, khh/u, but generally are not designed to measure vertical trans-missibility or other groups containing vertical permeability, ku. A new well test described here provides a measure of in-situ vertical permeability as well as the previously measurable horizontal permeability. This "vertical test" determines the vertical diffusivity, kv/gcu, and horizontal transmissibility, khd1/u (where dl is the length of injection or production perforations). The test is basically a short-term interference or pulse test normally lasting less than a day. Conventional down-hole equipment is used between two isolated sets of perforations in the same well, as shown in Fig. 1. A "layer-cake" description of a reservoir can be obtained by running two or more vertical tests in the same well, each over different vertical intervals. Each test can be analyzed for the effective vertical and horizontal properties of the interval tested. In addition, a vertical well test can determine the effective- ness of a shale barrier or tight zone by testing across it. Field use to date of vertical testing has confirmed its utility in reservoir description. Mathematical Basis Interpretation of vertical tests for ku and kh is based on comparison of measured pressure response with computer-generated response. Pressure behavior during a vertical test in a homogeneous, anisotropic, infinite-acting reservoir (infinite in radial extent and bounded in both directions vertically) is given by the diffusion equation for slightly compressible fluids with negligible gravity effects.l A schematic diagram of the problem is presented in Fig. 2, and an analytic solution, based on the image

Jan 1, 1970

By J. C. Martin

Equations for three-phase, three-dimensional, compressible flow (including capillarity) are reduced to two-dimensional relations by a partial integration. This reduction allows three-dimensional flow problems to be treated with mathematics for only two spatial dimensions. The results can be used to formulate flow equations for two-dimensional reservoir simulators in which the effects of capillarity and fluid segregation in the third dimension are represented. Such reservoir simulators would retain many of the aduantages of two-dimensional simulators while simulating three-dimensional effects. The principal restriction of the method is that the thickness of the reservoir should be small, compared to the distance across the reservoir. INTRODUCTION In recent years, computers have been used to calculate the performances of many reservoirs. Most of the detailed calculations, however, are based on finite difference solutions of the flow equations, and present day computers are seldom able to handle a sufficient number of cells to produce entirely satisfactory solutions, even for reservoirs represented by two-dimensional arrays of cells. The situation becomes much worse when one wishes to approximate the reservoir by a three-dimensional array. A great saving in computation or a more detailed solution can be obtained for many reservoirs by using the partial integration of the equations of flow presented in this paper. The integration reduces the three-dimensional equations to two-dimensional relations; and, for studies of two-dimensional flows in vertical cross-sections, the equations are reduced to one-dimensional relations. Most reservoir performance calculations currently are based on one- or two-dimensional flow re1ations.l-3 In some cases flow in the third dimension is approximated by assuming a particular type of vertical saturation distribution, such as gravity segregation.l.2. The relations developed in this paper approach those for segregated flow as the capillary pressures approach zero, and they approach those for uniformly distributed saturations as the capillary pressures are increased. For this analysis, the ratio of the reservoir's thickness to the maximum distance across it must be small. The capillary pressures between the oil and water should also be small compared to the maximum pressure difference in the reservoir. This requirement is met by most reservoirs. It is assumed that the capillary-pressure curves are well defined, whether or not hysteresis effects are included. Also, the reservoir must have sufficient vertical permeability to allow the fluids to segregate. The results presented here provide a firm theoretical foundation to Coats' et aL5 assumption of vertical equilibrium and extend the relations to three-phase flow. Coats' assumption of vertical equilibrium, which he verified by calculations and experiment, is developed here mathematically from basic flow equations. DISCUSSION SATURATION AND PRESSURE DISTRIBUTIONS Appendix A presents a mathematical analysis of fluid flow in reservoirs where the ratio of thickness to maximum distance across the reservoir is small. The results indicate: (1) that the fluids along any line perpendicular to such a reservoir's upper surface are in static capillary equilibrium (vertical equilibrium); (2) that, to a first approximation, the fluid pressures and properties are functions of only areal position in the reservoir and time; and (3) that hydrostatic pressure gradients exist along any line perpendicular to the reservoir's upper surface. The results might be expected after studying several physical considerations. First, no flow is allowed normal to the upper and lower reservoir boundaries, which are relatively close together.

Jan 1, 1969

By Lawrence S. Darken

STAFF: Editor, Gerhord Derge Cornegie Institute of Technology Schenley Pork Pittsburgh 13, Pa. Editorial Assistant, M. A. Redmerski Production Editor, Otto T. Johnson THE METALLURGICAL SOCIETY: J. S. Smart, Jr., President; C. C. Long, Past-President; K. L. Fetters, Vice President; T. D. Jones, Treasurer; R. W. Shearman, Secretary. PUBLICATIONS COMMITTEE OF THE METALLURGICAL SOCIETY: C. L. McCabe, Chairman; H. L. Bishop, K. L. Fetters, J. J. Harwood, W. A. Krivsky, F. C. Longenberg, R. E. Lund, W. 0. Philbrook, L. L. Seigle, R. L. Smith, and F. L. Vogal. Review and selection of manuscripts is under the supervision of the following Publications Committees: Extractive Metallurgy Division: C. L. McCabe, Chairman; R. E. Lund, Vice-chairman; D. H. Baker, Jr., W. A. Krivsky, R. A. Lewis, Paul Qusneau, A. S. Russell, R, E. Shinkoskey, W. W. Stephens, and M. E. Wadsworth. Institute of Metals Division: L. L.Seigle, Chair-man, P. A. Back, J. J. Backer, l.l. Bessen, J. 0. Betterton, Jr., J. 8. Clark, R. S. Davis, A. E. Dwight, R. W. Fountain, R. B. Gordon, C. D. Graham, Jr., R. W. Guard, J. C. Gurland, E. L. Harmon, J. J. Hager, A. A. Hendrickson, M. Harmon, J. N. Hobstatter, H. H. Johnson, Jr., H. 5. Kolish, R. R. Nash, T. N. Rhodin, R. H. Richman, W. Rostokar, P. G. Shawmon, C. W. Spencer, L. Slifkin, J. K. Stanley, C. D. Starr, R. Steinitz, and H. C. Stumpf. Iron and Steel Division: H. L. Bishop, Chairman; 2. E. Boni, F. C. Langenberg, J. B. Wagstaff, and T. V. Wainwright. Published bimonthly by the American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc., 29 West 39th Street, New York 18, N. Y. Telephone: PEnnsylvania 6-9220. Subscription PetroleumEngineers,$30 per year for non-AIME members in United States and North, South, and Central America; 332, foreign; $5 for AlME members. Single copies, $4.00, single copies foreign, $5.00. The AlME is not responsible for any statement mode or opinion expressed in its publications . . . Copyright 1%1 by the American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc. . . . Registered cable address; AIME New York ..Indexed in Engineering Index, Industrial Arts Index, and Chemical Abstracts.. .Second class postage paid at New York, N. Y., and Ann Arbor, Mich. Volume 221, Number 4.

Jan 1, 1962

By B. H. Caudle, L. G. Loncarie

Pilot flooding is one method of evaluating a proposed secondary recovery project. However, the amount and rate of oil recovery from an unconfined pilot area is not usually the same as from an equal area in a large-scale flood. This is true because fluids are free to move across the boundary of a pilot area. The result is that some of the oil produced in a pilot flood may come from outside the designated area and some of the displaced oil may leave the pilot area completely. This paper presents the results of fluid-flow model studies on a five-spot pilot flood. Mobility ratios between 0.1 and to have been studied. The effects of changing the ratio of injection to withdrawal rates are shown. INTRODUCTION A small-scale field test, or pilot flood, is an accepted method for evaluating the applicability of a secondary recovery operation and the economic potential of that operation for a reservoir. The pilot flood is carried on in the same manner, with the same injected materials and at the same pressures as would be used were the secondary recovery program to be expanded to a larger area of the field or to the entire field. If the reservoir fluid and reservoir rock properties are the same in the pilot area as in the rest of the reservoir, the production, injection and other pertinent data associated with the pilot test will represent and measure what should be expected from a full-scale development of this secondary recovery program. There is one major exception which, unfortunately, has been overlooked by many and which has been awaiting quantitative definition. This is the sweep-out pattern the reservoir engineer must use in interpreting the pilot flood and in extrapolating it to the full-scale development. The sweep-out area in a pilot flood is not contained within the five-spot pattern. Further, there is oil flow into and/or out of the five-spot during a pilot test. Thus, production data from pilots must be interpreted with this different flow system and sweep pattern in mind. We have studied the sweep-out pattern that will exist for some conditions of operation of pilot flooding a single five-spot (four injection wells and one producer). In our study, reported here, we have assumed that the reservoir is relatively homogeneous and of uniform thickness in the pilot area. The results of this study en-able the engineer to predict the recovery, injection requirements and project life for a full-scale operation from the pilot flooding data. The effects of various injection to withdrawal-rate ratios and mobility ratios in a relatively gas-free (10 per cent pore volume or less) system are shown. Experimental Method The technique used in this study was the same as that for the X-ray shadowgraph studies of sweep-out pattern efficiencies.' The model of the pilot and surrounding area was made from a uniform packing of round-grain sand consolidated with an epoxy resin. Fig. 1 shows the relation between the model and the pilot area. Only one-eighth of the pilot area had to be represented in the model because we assumed equal injec-

By H. T. Kennedy, J. E. Little

An empirical equation for the prediction of the viscosity of several pure paraffin hydrocarbons and nitrogen is presented. It involves temperature, pressure and six constants of the material, and it applies reliably to both liquids and gases. The equation is similar in form to van der Waal's equation of state. For the paraffin hydrocarbons methane through r-hexane and nitrogen, an average absolute deviation of 1.9 percent was obtained on 1,006 data points described in the literature by 14 authors. When this equation is extended to complex, liquid hydrocarbon mixtures, a correlation was obtained with an average absolute deviation of 9.9 percent. INTRODUCTION Equations describing the flow of gas and liquid through porous media contain the viscosity coefficient of the fluid. If other pertinent variables remain constant, the volume rate of flow is inversely proportional to this coefficient. In dealing with condensate fluids and volatile oils, however, the compositional effects resulting from changing pressure materially affect the viscosity. The effect of compositional changes also may be significant in certain secondary recovery or pressure maintenance processes, notably miscible displacement or gas injection. Early attempts to describe the performance of reservoirs utilized a volumetric material balance method wherein gas and liquid in the reservoir were identified as produced gas and liquid at the surface. This method of analysis proved adequate for reservoirs at moderate temperature and pressure that contained gas with moderately low amounts of condensable materials. The volumetric material balance procedures for "black oil" reservoirs leave much to be desired when applied to condensate and volatile oil reservoirs because phase behavior and compositional changes are relatively more important in these cases. The alternative is a compositional material balance, which in turn, requires a correlation of properties of the reservoir fluid with composition. This paper supplies this correlation in regard to viscosity, for reservoir crude oils. REVIEW OF LITERATURE The literature contains many empirical equations describing the effects of composition, temperature and pressure on the viscosities of pure liquids and binary liquid mixtures. However, the applicability of a majority of these equations is limited to very low pressures and to a small number of systems. Most of them, when applied to complex hydrocarbon systems, are of little value. The lack of utility of the majority of equations results from the fact that they were developed to show the separate effect of temperature, pressure or composition on viscosity, but not to predict the viscosity as a function of all three variables. And with the few exceptions noted below, they were developed to apply to much simpler systems than hydrocarbon mixtures. Eakin1 developed an equation for the viscosity of pure light hydrocarbons applicable in the gas, liquid and dense fluid regions, and in its most general form is written as µ - µo =A(ebP - e-cpk) The pure component viscosity at atmospheric pressure and temperature T, µo, was calculated using the Sutherland equation: µo = BT3/2/T + S The constants in Eakin's equation permitted the term e-CPk to become quite small at high densities (above 0.215 gm/cc), and the general equation would simplify to

Jan 1, 1969

By W. L. Connell, O&apos

The properties of some heavy liquids which can be used in sink-float separations are discussed with major emphasis being given to the halogenated hydrocarbons. Data are presented on density, viscosity, thermal characteristics and the effects of moisture and temperature on the corrosiveness of the liquids towards various materials of construction. The toxicity of these materials, the hazards involved in handling them, and the procedures for handling them safely are also discussed. True liquids have certain advantages over colloidal suspensions for sink-float separation of minerals which makes their use especially advantageous when close separations, fine particle sizes or water-soluble minerals are to be treated. For best separating results, the medium should have an easily controlled, uniform, stable density. Here, true liquids have the advantages of allowing closer control of density and of not requiring agitation to maintain a uniform den- sity in the equipment. Low viscosities are desired in a separating liquid so that rapid separations of fine material can be made. Many liquids have lower viscosities than the colloidal suspensions at operating gravities of 1.4 to 5.0. For economic reasons and to prevent contamination of the product, the separating medium must be easily and completely removed from the ore. Normally, true liquids must be more completely removed than the cheaper suspensions and thus cause more problems in this area. The fact that the medium should not react with the minerals, air, water or the common materials of construction limits the choice of liquids which can be used, but many are available which are sufficiently stable. A more serious objection to the use of true liquids is that many of them present a toxic hazard to operating personnel and users of the product. Most true liquids are toxic to some extent, but modem knowledge of toxicity allows us to recognize the hazards inherent in handling them and enables us to design around them. Three types of true liquids are available for this use: 1) Halogenated hydrocarbons cover the gravity range from 1.2 to 3.3. They are generally more volatile and less viscous than the other liquids.

Jan 1, 1963

By J. C. Bokros, A. S. Schwartz

The irradiation-induced densification of pyrolytic carbon has been shown to take place by a simple first-order rate process. The values of the densification constant, kd, for isotropic carbons are 1.0 x 10-22, 1.4 X 10-22 and 2.8 X 10-22 (nut)-1 at irradiation temperatures of 520o, 670°, and 1000oC, respectively. The apparent activation energy obtained from the temperature dependence of kd for isotropic carbons is about 0.2 ev. Estimates of the maximum stresses that develop in isotropic carbons owing to shrinkage onto an unyielding support show that stresses in excess of 15,000 psi may be avoided during irradiatian at 600" and 1000°C if the initial coating density is kept above 1.5 and 1.9 g per cu cw, respectively. If a carbon coating on an unyielding support is not completely isotropic, stresses may continue to build up at high neutron exposures after densification is complete because of continued anisotropic distortion. Stresses in excess of 15,000 psi from this source may be avoided during irradiation at 1000°C if' the Bacon anisotropy factor is kept below 1.3. A variety of applications of carbon and graphite in nuclear technology has stimulated numerous studies of the effect of neutron irradiation on these materials One of the most interesting problems associated with the use of carbons and graphites in the high fast neutron fluxes of nuclear reactors arises as a consequence of the neutron-induced dimensional changes that occur during irradiation. Energetic neutrons displace car- bon atoms from their lattice positions; and, depending on the temperature, the interstitials and vacancies produced migrate to form clusters, recombine, or are annihilated at dislocations or crystallite boundaries. The competition of various sinks for the point defects results in structure-sensitive bulk-dimensional changes that vary with temperature in a complicated way. This paper deals with the neutron-induced dimensional changes in turbostratic carbons that are being used as coatings on nuclear fuel particles. Details of the structure of these carbons and the variations of their structure with deposition conditions have been reported.'-3 It has been shown in previous work that the neutron-

Jan 1, 1968

By W. A. Tiller, J. D. Harrison

HOT pressing of powder particles has gained importance recently, since it affords a method in which high densities are rapidly attained. In a recent study on hot pressing of alumina powders, Mangsen, Lam-bertson, and Best1 have shown within the limits of their experiment, the validity the rate equation for densification in hot pressing, originally proposed by Murray, Livey, and Williams.2 i.e., where D = fraction of theoretical density, t = time, P = pressure and 77 is the viscosity, all in appropriate units. This equation was derived from earlier work of Shuttleworth and Mackenzie3 which is based on the closing of spherical pores under the action of surface tension. The integrated form of this equation yields a straight-line relation between log (1 - D) and t. Such conditions were found by Felten4 to be true only after extended periods of pressing. In an endeavor to quantitatively evaluate the exactitude of this equation in the initial sintering stage, i.e., prior to sealing of the pores, spherical anti-

Jan 1, 1962

By R. L. Caldwell, E. E. Glenn, L. J. Norton, A. J. D. Straus, S. V. Holcomb, J. Zemanek

A new and unique logging tool, called the Borehole Televiewer (BHTV), has been developed to inspect boreholes and to evaluate formations. Even though geologists and engineers have had only about 3 years' experience with the BHTV, the thinking of many of them has been radically influenced by the fascinating and revealing "log-picture" recorded with the tool. The BHTV fills a need for a logging tool that can produce a direct and descriptive record of the physical properties of the borehole environment. Although primarily developed to evaluate fractured reservoirs, the BHTV has been used successfully to solve a variety of problems related to formation evaluation and borehole inspection. Geologists and petroleum engineers have been confounded for many years by the problems of locating and evaluating fractures. Interpretation of the usual resistivity, acoustic or radioactivity logs, as well as the analysis of cores, for evaluation of fractured reservoirs is extremely difficult and often not definitive. This is understandable since analysis of cores from fractured formations has reported variously: (a) low porosity, (b) no effective permeability, (c) lack of any matrix oil saturation and (d) oil stains on fracture planes as the only indications of potential production.14 In recent years acoustic amplitude logs have been introduced and used with varying degrees of success to locate fractures.8'9'11"13 Conventional amplitude logs at best give only qualitative answers where quantitative ones are desired. The logs reveal nothing of the orientation of the fractures. In addition to these logs, various types of cameras, television, and rubber impression packers have been used for borehole inspection. (See Appendix.) The BHTV logging tool supplies both the quantitative and the orientation answers about fractures. The borehole can be filled with any homogeneous, gas-free liquid such as fresh water, saturated brine, crude oil or drilling muds. This tool takes an "acoustic picture" of the borehole wall. The resulting log is a representation of the borehole wall as if it were split vertically and laid flat. The log is oriented with respect to magnetic north. Any physical changes in the borehole wall are seen as changes in picture intensity. In this way, fractures, deformation or pits are reflected on the log. Tool Description The fundamental parts of the BHTV are shown in Fig. 1. A piezoelectric transducer probes the borehole wall with bursts of acoustic energy. A flux-gate magnetometer senses the earth's magnetic field and provides the means for determining the orientation of the log. A motor rotates the transducer and mag-

Jan 1, 1970

By W. R. Hibbard

Evidence is presented which confirms previous findings that models of solution strengthening depending solely on lattice parameter changes are incomplete. Direct evidence for the Suzuki interaction of chemical effects was obtained from alloys with constant lattice parameter, for which solution strengthening was nearly independent of temperature from 300° to 20°K. SOLUTION hardening principles have been reviewed recently by Parker and Hazlett.' In addition, the interactions of dislocations and solute atoms were reviewed by Cottrell.' It is not proposed to review this information again here, but to refer only to those details which are pertinent to the developments which have occurred since these papers were published. Literature Survey To set the stage, it has been known for some time that solid solutions are stronger than the pure parent metals, and that the strength increases with increasing amounts of alloying element. One of the most extensive earlier investigations was that of Lacy and Gensamer,3 who reported that the solid solution strengthening of iron is a power function of the composition, that the relative strengthening is a function of the solubility limit, and that the rate of strain hardening is a function of the amount of solution hardening. Thus, the slope of the plastic portion of the stress-strain curve increases with increasing yield strength. An approach to the development of principles resulted from work by Gulyeav,4 who reported that the strengthening effect of solid solution alloys is periodic in character when plotted as a function of the atomic number of the solute. A more quantitative approach was to relate the amount of solution hardening to the lattice parameter of a solid solution. This was done quite early by Norbury,5 and later by Brick, Martin, and Angier,6 Frye and Hume-Rothery,7 and French and Hibbard. This relationship is only approximate in character. The next development was to relate the amount of solution hardening to lattice stress, as proposed by Frye and co-workers.9 They calculated what they called ionic overlap from the lattice parameter changes represented as a change in volume, using Bridgman's hydrostatic compression equation. The resulting correlation was somewhat improved as compared to the simple correlation with lattice parameter. The next step was carried out by Dorn, Pietrow-sky, and Tietz,10 who suggested an effect of valence differences in addition to the effect of lattice parameter. Their proposed parameter shows flow stress as a single valued function of the concentration and a relationship involving these two atomic variables. In addition, they contributed new data on the temperature dependence of solution hardening which indicated that it was a strong function of temperature for aluminum alloys. Allen, Schofield, and Tate11 carried the valency effect even further by reporting data indicating that with a given solvent element the stress-strain curve is a function of electron density, entirely neglecting the size factor, which varied by a factor of two. This evidence led to a quantum mechanical calculation by Cottrell, Hunter, and Nabarro,12 based on the formation of a dipole around an edge disloca-

Jan 1, 1959

By William B. Hughes

The rubber-sleeve core barrel was developed to improve core recovery from unconsolidated sands, where it is most difficult to obtain cores with conventional barrels. The use of a rubber-sleeve core retainer, together with other departures from clsual design, has required a considerable amount of testing to prove its op-erability. Tests run in shallow experimental holes and in drilling wells in the U. S. and Vemzuela have, to a large extent, proved the operation of the barrel. Internal mechanism troubles, such as sandbinding of the sleeve, have been largely overcome. Cores have been recovered from completely unconsolidated sands where conventional coring has almost been abandoned because of poor recovery. In addition to retaining the core until brought to the surface, the barrel gives a "packaged-ar-cut" core, which is coilverzient for handling and transportatiorz. In the initial work, drag blade cutters, roller cutters, and tungsten carbide insert cutters were usrd for cutting unconsolidated sands. Further bit head development is presently being conducted using diamond heads in unconsolidated sands where shaler, hard sands, and limestones are encountered in adjacent formations. Thir work should render the barrel capable of cratting and recovering most types of formations, possibly including broken and frac- tured fornlations. This development is being carried on in cooperation with a diamond bit manufacturer. INTRODUCTIO N For many years the oil industry has needed greater recovery of cores from unconsolidated formations. Conventional equipment has been used to core unconsolidated sands with little success. Specifically, a core barrel was needed which would recover unconsolidated sands in a condition that would give useful reservoir information. DEVELOPMENT OF 'THE RUBBER-SLEEVE CORE BARREL Basic Requirements of Unconsolidated Sand Corino The basic need was defined as a core barrel that would obtain a continuous unconsolidated core with sand grains in place as deposited in the formation. A preliminary survey of coring equipment and search of the literature pointed out the weaknesses of conventional core barrels. Laboratory tests using unconsolidated sand in a metal tube simulated actual sand movement into the core barrel during conventional coring. In conventional barrels the core sometimes crumbles and bridges, or fails under compressive column action, becomes oversize, and wedges against the walls of the inner barrel. The core barrel requirements established by the surveys and preliminary tests are as follows. 1. The core should be held to- gether as it is cut so it cannot crumble and bridge against the walls of the coring tool, care being taken not to permit damage from fluid circulation. 2. The core should be continuously supported as it is cut so it will not have to support itself in compression. 3. The core should be packaged in the barrel to retain an undisturbed condition during the trip out of the well. The packaging should be such that the core can be removed from the barrel and shipped to the core analysis laboratory without physical disturbance or alteration of fluid content by exposure to the atmosphere. Operation of the Rubber-Sleeve Core Barrel The rubber-sleeve core barrel (Fig. 1) meets the basic requirements for the recovery of unconsolidated sands.

By K. J. Gill, P. Chiotti

Thermal, metallographic, and vapor pressure data were obtained to establish the phase diagram for the thorium-zinc system. Four compounds corresponding to the stoichiometric formulas Th2Zn, ThZn2, ThZn4, and Th2Zn17 were observed. The melting points of these compounds under constrained vapor conditions were found to be 1055°, 1105°, 1095°, and 1015°C respectively. Four eutectics exist in this system with the following eutectic temperatures and thorium contents in wt pct: 1040°C, 89 Th; 945°C, 79 Th; 1045°C, 55 Th; and 995°C, 35 Th. The standard free energy, enthalpy, and entropy of formation for the compounds were determined from zinc vapor pressure data. ALTHOUGH the thorium-zinc system has been of technical importance in the commercial production of thorium and more recently of interest to some proposed pyrometallurgical separations processes for reactor fuels or blanket materials no detailed investigation of this system has been made in the past. Some previous work has been reviewed by Hanssen.1 The existence of four compounds, Th2Zn17, ThZn4, ThZn2, and Th2Zn has been established and their crystal structures have been studied by X-ray diffraction techniques.2-4 Smirnov et al.,5 determined the solubility of thorium in zinc and investigated the two-phase region between Th2Zn17 and zinc. They calculated some of the thermodynamic properties for these alloys from emf measurements on the cells Th/ThCl4(fused)/Cl2, C and Th2Zn17(s)+ Zn (l)/ThCl4(fused)/Cl2, C. The possibility of reaction between the anode materials and fused thorium tetrachloride to produce a lower valent thorium salt would have to be resolved in order to evaluate the results obtained. The purpose of the present investigation is to establish the phase diagram for the thorium-zinc system and to determine the standard free energy, enthalpy, and entropy of formation for the compounds formed. MATERIALS AND EXPERIMENTAL PROCEDURES The metals employed in the preparation of alloys were Bunker Hill slab zinc, 99.99 pct pure and Ames Lalboratory thorium. The major impurities in the thorium in parts per million were oxygen—1250, carbon—350, iron—100, nitrogen-75, and silicon—70. The metals in the form of several small massive pieces, total weight about 30 g, were cleaned with acid, washed with water and acetone, and dried just prior to their use for alloy preparation. Tantalum containers were found to be suitable for all the alloys studied and were used throughout this investigation. The metals were sealed inside of small 1-in.-diam tantalum crucibles by welding on preformed tantalum covers. A small thermocouple well made from 1/8-in.-diam tantalum tubing was welded in the bottom of each crucible. These crucibles were enclosed in

Jan 1, 1962

By John Boardman

THE latest metal-mine accident report available for the United States is that of the Bureau of Mines for the calendar year 1919. Quoting from Table 20, p. 53, of that report, we find that there were 468 men killed, 7 permanently totally disabled, 321 permanently partially disabled, 7848 injured seriously (more than 14 days disability), and 23,330 of 1 to 14 days disability. We have no records to show what the average days lost per case of accident is, but the records for the Anaconda Copper Mining Co. show that, leaving out the fatalities and total permanent disabilities, and counting those in which the lost time was one or more days, the actual days lost due to accidents, for the Butte mines and shops for five years, 1917-1921, were as follows: Accident Statistics, Butte Mines and Shops of A. C. M. Co. Rate Shifts Days Lost Year Accidents Total Shifts 10,000 Shifts Days Lost Per Acci-dent 1917 2,661 3,169,720 8.395 26,734 10.05 1918 2,765 3,545,149 7.799 39,199 14.17 1919 1,381 1,853,143 7.452 22,797 16.50 1920 1,376 1,879,410 7.321 20,164 14.65 1921 376 776,461 4.842 8,287 22.03 Total... 8,559 11,223,883 7.625 117,981 13.80 In order to place an economic value. on this loss, we will assume that all the 468 fatalities and the 7 total permanently disabled in the United States were com-pensated for at the rate which applies in the State of Montana, that is, $5000 each, and that the 8169 serious accidents in the United States were compensated for at an average of $70 per case, thus bringing the estimated compensation paid by metal-mining companies in the United States to the enormous total of $2,946,830 for the year 1919. The figure of $70 per case was obtained by dividing the total amount paid by metal-mining companies under Plan No. 1 of the Montana Compensation Law, for the first five years of its operation, by the total number of serious accidents for those years.

Jan 9, 1922

By Hubert E. Risser

Although, for about a half-century the percentage of coal production provided through strip mining has steadily increased, recent trends indicate that a peak in percentage (not tonnage) is being approached, principally because of the decline in economic adrantage enjoyed by strip mining compared to underground mining. Factors contributing to the decline are the decrease in the margin of advantage in manpower requirements held by strip mining; an increase in depth and volume of overhurden, requiring larger equipment and capital investment; increasing lack of reserve land blocks large enough to support extensive strip mining operations; more stringent legislation for reclamation of stripped land, with increasingly higher costs of such reclamation; and the increasing costs of land surface rights for strip mining. Already there has been a peak and suhsequent decline in relative importance of strip mining insome major Eastern coal-producing states; trends indicate that a peaking for the whole Eastern region is on the way. Although, in the West the pressures are less severe, they will, nevertheless, reduce to an increasing degree the advantage that strip mining has possessed. For about half a century, strip mining has been providing an ever-increasing share of total coal output in the United States, and in the past 30 years this share has grown from less than 8% to 33.7%, as shown in Fig. 1. Fig. 1 also shows that strip mining is gaining faster in the West than in the East. From 1961 to 1967, output from strip mines grew 63.6 million toqs, or 52.2%. Certainly there is nothing in such performance to indicate any peaking in the level of strip coal-mine production. But the fact is that, if not in actual tonnage, strip mining appears to be reaching its peak in relative importance, at least east of the Mississippi River. And the area east of the Mississippi provides 90.0% of the strip and 94.9% of the total coal production of the nation. The relative economic advantage which spurred strip mining's growth for a third of a century has been diminishing markedly in recent years. Fig. 2 shows evidence of this decline. From 1947 until 1961, strip tonnage output remained fairly stable, at the end of the period showing only a 12.5% decline. Meanwhile, underground coal production fell 44.5%. As the result of the greater decline in underground coal, strip coal in 1961 furnished 30.3% of the total coal produced, compared to only 22.1% in 1947. In the succeeding six years, however, underground coal output increased by 76.5 million tons, while strip output increased only 63.6 million. Further evidence of the strengthening of underground coal's relative position — or if you will, the weakening of strip coal's position — can be found in the major coal stripping states: Illinois, West Kentucky, Ohio, Pennsylvania, Indiana, and West Virginia, which in 1966 provided 80% of the nation's strip coal. Fig. 3 shows what has been happening in three states lying in the Appalachian field and in the total output of these three states. In the figure, the column height represents the output of coal mined by all methods. The number at the base of each column is the percentage mined by stripping. In Pennsylvania and Ohio, the percentage of strip mining increased between 1956 and 1961, but by 1966 had declined from the 1961 level. In West Virginia, a decline occurred during the first five years but was followed by a rise. In January 1968, Coal Age published an article listing the locations and capacities of new large mines in the planning and construction stages that would be operating by 1968-1971. The plans for West Virginia and Pennsylvania indicated all the new mines would be underground. Except to the extent they might replace existing under-

Jan 1, 1970

By AIME AIME

TWO days of solid discussion, with barely time out for meals, characterized the Tulsa meeting of the Petroleum Division. It was preeminently an earnest gathering devoted to technical matters. Sessions were held in the Crystal room of the Mayo Hotel with luncheon served each day in the back of the same room so that talk of methods, while slightly less formal, extended right through the lunch hour. Thursday evening the Committee did provide a little relaxation in an informal dinner at the Tulsa Club where, after a brief musical program and an amusing skit by the local Herman the Great, brief addresses in non-technical vein were made by President Farish and Vice-president Rice of the Humble Company, Henry L. Doherty of Cities Service, Secretary. Bain of the Institute, and others. The presence of leading executives of a number of the oil companies at the dinner and the sessions, and the cordial approval they expressed of the work of the Division were especially gratifying. The total registration was 215 with 100 at the dinner and 70-to 80 lunching together each day.

Jan 1, 1930

By Ernst A. Hauser

IN a paper published three years ago,' the term "silicic chemistry" was used for the first time to emphasize the increasing importance of the chemistry of silicon in science and technology. The development through which the colloid chemistry of siliceous matter has gone since then is in itself ample proof that the coining of this new term for this branch of colloid science was not presumptuous. Until quite recently, however, silicic chemistry concerned itself only with the composition and colloidal properties of natural and synthetic siliceous matter, but had not paid much attention to the genesis of this matter, particularly to that of the clay minerals. What is even more disturbing, particularly from an educational point of view, is the fact that neither mineralogy, geology, nor metallurgy has fully realized the important role colloidal phenomena must have played in the genesis of our planet and the formation of minerals generally speaking. Considering the importance of colloid chemistry today in the fields just mentioned, it is not surprising that the theories most agreed upon by geologists and mineralogists for the origin of clay minerals are not acceptable from a strictly colloid chemical point of view for the genesis of these most important and most abundant components of the earth. Of all the theories pertaining to the origin of clay minerals, those still most accepted by geologists and mineralogists are the "residual clay" and the "transported clay" theories.15 The former is based primarily on the assumption that the formation of clay minerals is the result of surface weathering of fresh rocks, or is due to the action of solutions. Taking the action of water on orthoclase as an example, the most recent ideas have been summarized by H. Jenny13 as follows:

Jan 1, 1952

By V. J. Parks, Leonard Obert, A. J. Durelli

The state of stress in the region where core discing initiates has been investigated through the use of three-dimensional photoelastic models and the results of this study have been compared with those of a previous investigation of rock models. This comparison showed that discing initiates at a point of maximum shear stress, but that the magnitude of the shear stress, as determined photoelastically, is much larger than the shear strength of the rock as deter-mined from conventional triaxial testing. Moreover the shear stress required to produce discing is not constant, but depends on the applied stress field. Possible explanations for these effects are included in this article. In both exploration core drilling and overcore drilling to determine the stress in rock, occasional sections of the core obtained are broken into a series of discs.I* This discing phenomenon has been investigated in the laboratory to ascertain the state of stress required to produce it. The objective of the study was to obtain information that would make it possible to approximate the state of stress in subsurface rock from which disced cores are obtained. Referred to as the discing test, this laboratory study was conducted to determine the applied axial and radial loads required to produce discing in cylinders of rock from several sources. The dimensions of these cylinders are given in Fig. 1. Discing was produced by first applying an axial load to the cylinder and then diamond drilling the core along its axis. The radial load was then incrementally increased until discing initiated. The discs fractured or ruptured* on surfaces approximately normal to the axis of the core (planes A, B, C, D, E, Fig. 2). In many instances, the bottommost disc fractured before the drill had advanced past the points F and F', cre- ating a mush room-shaped fracture surface FEF'. Alternatively, it was also found that the same shaped fracture surface could be created by first drilling in an unloaded core to some point, say F and F', and then triaxially loading the core until fracture occurred on the plane FEF'. Jaeger and cook4 produced similar fracture surfaces in specimens subjected only to a radial biaxial load. From these laboratory studies and observations made in the field, it can be inferred that fracture or rupture initiates in the proximity of the lowest point in the kerf area, (at F and F', Fig. 2) and that the fracture or rupture surface progresses inward from this point. The experiments described above, however, do not provide any information as to the state of stress at the point at which fracture or rupture initiates. In the investigation discussed in the following sections, a three-dimensional photoelastic analysis was conducted to determine the stress distribution in the proximity of the kerf area of a triaxially loaded plastic (epoxy) cylinder containing a short section of core.

Jan 1, 1969

By W. C. Peters, M. W. Pullen, C. A. Bays

During the past three and a half years considerable improvement in the techniques of solution extraction of salt has been made by the use of wells which are cross-connected by hydraulic fracture at the base of the salt. Fracture is initiated by the application of hydraulic pressure. Underreaming and perforating techniques are used to control initiation. The fracture is then extended by continuous pumping until a pressure communication is obtained. Pressure communication is followed by washing-through to obtain a low-pressure connection. Well construction using non-shrinking cements that will bond with the salt and with associated strata is essential to the process. The connecting procedure described permits solution to attack the salt deposit from its base upward, thereby permitting greater recovery, fewer well repairs, better saturation of brine, and overall economy of development and operation. The fracture method of cross-connection requires special pumping of the fluid and is limited by present experience to initial well spacings up to about 1200 feet. The method has been used in bedded salts and is applicable for wells in salt domes. Since spring of 1956, new developnents in salt extraction wells have followed procedures substantially different from those in prior use. Although multiple well systems, connected either by the natural consequence of the solution process or by undercutting under protective pads, have been used previously, the past three and a half years have brought about new designs and new operation procedures based on cross-connection of the wells using hydraulic fracture. To date these techniques have been applied largely in the bedded salt deposits of Michigan, Ontario, Ohio, West Virginia, and New York. To the writers' knowledge they have not been used in salt dome wells. The methods have not yet been in use for a sufficient period to permit any statistical comparison with the older methods. It is evident from experience to date that the methods result in higher recoveries, lower capital and operating costs, better saturation of produced brine, reduced well maintenance and repair, and in considerably fewer production units to insure

Jan 1, 1961

By K. T. Aust

The occurrence of annealing twins in high-purity aluminum resulted in the formation of grain boundaries having orientation relationships which correspond to a high density of coincidence sites. The results provide support for the coincidence site model and indicate that large-angle coincidence boundaries have lower free energies than large-angle noncoincidence boundaries. Observations are presented concerning the coherent structure of twin interfaces in aluminum and the importance of inter-facial energy in preferred orientation. RECENT experiments1 have shown that when an annealing twin is formed during grain boundary migration in zone-refined lead, a large-angle random boundary is replaced at the growth front by a large-angle coincidence site boundary. The coincidence site orientation relationships obtained by twinning were of the type considered by Kronberg and Wilson,2 Frank,3 and Dunn.4 On the basis of the theory of annealing twins advanced by Fullman and Fisher,5 these observations indicate that the energy of a coincidence site boundary is less than the energy of a random boundary by an amount which exceeds the energy of the coherent twin boundary. This energy difference between the coincidence and random boundaries must be at least about 5 pct since the ratio of twin boundary energy to grain boundary energy in zone-refined lead is 0.05 * .014.6 Fullman7 has found that the twin boundary energy in aluminum is about 21 i 5 pct that of a large-angle grain boundary. A twin boundary energy as large as this would be expected to exclude the formation of many coincidence site grain boundaries, especially those which have a relatively low density of coin- cidence sites. Therefore, if the coincidence site model is a useful interpretation of certain large-angle boundaries, then it would be predicted that only coincidence boundaries which separate adjacent crystals with a relatively high density of coincidence sites may be obtained as a result of twinning in aluminum. The present experiments provided a means of testing this prediction since annealing twins occurred during the growth of recrystallized grains into striated, melt-grown single crystals of zone-refined aluminum. EXPERJMENTAL PROCEDURE A striated single crystal of zone-refined aluminum, about 1 cm sq and 37 cm in length, was obtained during zone melting of aluminum of 99.996 wt pct starting purity in a graphite boat under helium atmosphere.8 A molten zone of 2 to 3 cm in length, which was maintained by induction heating. was passed along the length of the bar for eleven passes at a rate of 0.9 mm per min. An additional final pass was given at a rate of 0.2 mm per min. The center portion of the zone-melted bar was characterized by an electrical resistivity ratio between room temperature and 4.2° K of 8000 to 9000. Single crystals of 1 to 2 cm in length were removed from the center section of the zone-refined bar and electrolytic ally polished in a 2:l solution of methyl alcohol and concentrated nitric acid. The specimens were then chemically polished in Alcoa R-5 solution. X-ray analysis of the single crystals indicated the presence of striations or lineage substructure having misorientations as high as 2 deg. New, recrystallized grains were introduced into each striated crystal by the technique of artificial nucleation and growth, previously described.9 During the growth of the recrystallized grains at 300' to 600°C in argon, it was sometimes found that a

Jan 1, 1962