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By F. Seitz

STAFF: Editor, Gerhard Derge Carnegie Institute of Technology Schenley Park Pittsburgh 13, Pa. Editorial Assistant, M. A. Redmerski Managing Editor, James J. Burke THE METALLURGICAL SOCIETY: John Chipman, President; W. R. Hibbard, Jr., Post-President; C. C. Long, Vice-President; T. D. Jones, Treasurer; R. W. Shearman, Secretary. PUBLICATIONS COMMITTEE OF THE METALLURGICAL SOCIETY: R. Maddin, Chairman; Dennis Carney, J. C. Fulton, J. H. Hollomon, T. B. King, C. C. Long, W. 0. Philbrook, J. D. Sullivan, David Swan, and F.L. Vogel. Review and selection of manuscripts is under the supervisian of the following Publications Committees: Extractive Metallurgy D ivis ion: T. 0. King, Chairman; S. J. Dick inson, R. P. Hermsdorf, R. Schuhmann, Jr., and H. H. Kel logg. Institute of Metals Division: F. L. Vogel, Choirmon; R. L. Smith, Vice Chairman; R.W. Balluffi, J. H. Bachtold, A Servi, C.D.Graham, Jr., C. G. Goetzel, F. E. Joumot, Jr., G. E. Pellissier, Paul Gordon, Jock Washburn, Harold Margol in, A. U. Seybolt, I. R. Kromer, R. A. Meussner, R. W. Guard, M. Harmon, J. N. Hobstetter, Dean Starr, P. Shewmon, R. Gordon, J. 0. Betterton, and E. Morgan. Iron and Steel Division: W. 0. Philbrook, Chairman; F. C. Langenberg, C. W. Sherman, J. Wagstaff, and E. J. Whittenberger. Published bimonthly by the American lnstitute of Mining, Metallurgical, and Petroleum Engineers, Inc., 29 West 39th Street, New York 18, N. Y. Telephone: PEnnsylvania 6-9220. Subscription $20 per year for non-AIME members in United States and North, South, and Central America; $25, foreign; $5 for AlME members. Single copies, $4.00, single copies foreign, $5.00. The AlME is not responsible for any statement made or opinion expressed in its publications . . . Copyright 1959 by the Americon Institute of Mining, Metallurgical, and Petroleum Engineers, Inc. . . . Registered cable address, AlME New York ... Indexed in Engineering Index, Industrial Arts Index, and Chemical Abstracts . . .Second class postage paid at New York, N. Y. , ond Ann Arbor, Mich. Volume 215, Number 3

Jan 1, 1960

By Maxwell Gensamer

Jan 1, 1960

By J. P. Neumann, L. Raymond

At temperatures near 1000°C, only the (112) (111) slip systems are operatire in tungsten. Therefore, the substructure introduced into the billet upon rleforming a single crystal by rolling at 1000 "C can be controlled by proper selection 01. processing ral'iubles. Using a reduction of 10 pct pel- pass, the (001)[110] and the (110)[001] crystals will deform by duplex slip rip to a 50 pet reduction in thickuess. These rolled single-crystal sheels are characlerized by anisotropic hardening, retention of ductility with warm working, lattice bending which is related to the conlacl (angle, and macroscopic dimensional changecs in the length bid not the width of the billet. When several slip systems become operative, a greater degree of work hardening is itztvoducetl into the crystal. This rolling- condition is characlerized by isotropic hardening, loss of ductilily with warm working, complex lattice distortions, and macro-scopic dimensional changes in both the length rind Width of the billel. IN tungsten, the {1 10}(111) slip systems are operative below room temperature,' while above 700°C only the {112{ (111) slip systems are observed.2,3 In the transition region, i.e., room temperature. both systems appear. It is the purpose of this investigation to show that tungsten single crystals deformed by rolling at a temperature where only one slip system is operative generate dislocation substructure which depends on the crystal orientation. For a specific crystal orientation. the resulting dislocation substructure can be further influenced by modifying the rolling procedure. Crystals oriented for multiple slip display less substructural sensi- tivity to modifications in processing techniques than do single crystals oriented for duplex slip. Under simple slip modes of deformation, very little work hardening is introduced into a rolled single-crystal sheet. Mechanical properties such as room-temperature strength. ductility, and hardness are used to confirm the existence of the different work-hardened conditions generated within the crystal by modified warm-rolling techniques. EXPERIMENTAL PROCEDURE Material. Single-crystal billets of four different crystal orientations. grown by the Arc-Verneuil technique. were ground to a size of 0.25 by 0.375 by 3 in. In terms of their rolling plane and rolling direction, the billets had the following orientations: (1101 [001 ] (110) [110] (001) [110] (001) [100] The actual orientation of all crystals was within 5 deg of the ideal orientations. The typical impurity content of the crystals is given in Table I. Polishing and Etching. Polishing was done elec-trolytically in a 20 g per liter aqueous solution of NaOH at approximately 10 v. It was established by the Laue back-reflection X-ray technique that the surface damage due to grinding and cutting operations with a diamond wheel did not exceed 0.001 in. Therefore after each cutting or grinding operation at least 0.002 in. was removed electrolytically from the surface in order to eliminate surface effects. By lowering the voltage to 3 v, subgrain boundaries and individual dislocations are identified in agreement with Berlec 4 where the etch-pit traces on a cubic plane form a square. The etching time was about 5 sec at room temperature. Rolling. Rolling was carried out on a Loma 2-high mill (Model 600). The peripheral velocity of the 6-in.-diameter rolls was 500 in. per min, with the surface temperature of the rolls about 400° to 450° C The billets were heated before each pass for 30 min in argon to 1000 C. Oxidation of the crystals during rolling in air resulted in a thin layer of greenish-yellow WO 3 This oxide was removed after each pass by immersing the crystals for a few minutes in a boiling NaOH solution. Prior to the initial rolling pass, a surface layer of 0.001 in. was removed by polishing. The crystals were then annealed in vacuum (10-4 torr) at 2400 C for 30 min. All crystals were rolled in the same direction; i.e., the same end was always introduced into the rolls. The rolling program was conducted in

Jan 1, 1965

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 A. W. Asman

The problem of balanced design in a belt conveyor has been under constant study. Increased use of this method of transport in recent years has stimulated investigations. Conveyor belt, power transmission and other machinery should be adequate to perform the required service. All components of the belt conveyor should work as an efficient unit moving its load continuously between terminals. As part of a long term research project on belt conveyors, Hewitt-Robins established in 1954 a 2-year grant at Pennsylvania State University. Under terms of the grant, certain fundamental phenomena were to be studied. This work evolved a new concept in belt conveyor power determination based on the principle of belt tension. The Penn State contract furnished the foundation for later more detailed studies. From these most recent investigations, more specific factors were defined. In the final analysis, all of the data collected has been worthwhile in belt conveyor design. Units now operate over long distances at speeds of over 800 fpm. Long high lifts are commonplace. Where vertical or inclined shafts were the rule, belt conveyors receive first consideration. Although belt conveyors have moved forward rapidly, the future will see a tremendous gain in their use. The ideal test belt conveyor would be several thousand feet in length and have a maximum tension of at least 70,000 lb., Also, this conveyor should be horizontai and have a variable feed rate of more than one material. Data from such a field belt conveyor combined with laboratory information would permit accurate analysis. Since this type of conveyor was not available, many field locations were visited: An alternate would have been to erect a closed circuit system in the laboratory. Either method had limitations and the first was selected as having the best possibilities. Manufacturers of conveyor belting and machinery basically have been using the same horsepower formula. As more information became available from field installations, factors in the basic formula were modified. Practically all conveyors are designed today by adding together the horsepowers required to move the empty belt, move the load horizontally, and elevate the load. In selecting size of drive motor, the first two elements are relatively unimportant if the last is large. However, it is the combination of

Jan 1, 1961

By L. W. Berger, and R. I. Jaffee, D. N. Williams

The effects of hydrogen on the properties of binary Ti-A1 alloys containing 2.5, 5, and 7 pct aluminum and ternary alloys of the same compositions with added interstitial elements oxygen, nihrogen, and carbon were stzdied. Aluminum increases the apparent hydrogen solubility of the a-phase, resulting in a marked increase in resistance to impact embrittlement. In the Ti-5Al and Ti-7Al alloys, for example, the addition of 180 and 305 ppm hydrogen, respectively, did not cause embrittlement, while unalloyed titanium was embrittled by as little as 75 ppm. The role of aluminum in increasing hydrogen solubility of the a-phase probably accounts for the excellent hydrogen tolerance of a-ß alloys containing considerable amounts of aluminum. There is some evidence that aluminum retards the rate of hydride precipitation. If so, these alloys may be susceptible to slow-strain embrittlement. UNALLOYED a-titanium is extremely sensitive to small amounts of added hydrogen in that there is a marked decrease in notch properties. For example, as little as 100 ppm hydrogen is sufficient to lower the room-temperature notch-impact strength from over 100 to less than 20 in.-lb.' This loss of impact Strength has been associated with the Presence of hydride phase in the microstructure. Hydrogen in the amounts encountered in commercial practice

Jan 1, 1959

By L. W. Berger, R. I. Jaffee, D. N. Williams

The effects of hydrogen on the properties of binary Ti-A1 alloys containing 2.5, 5, and 7 pct aluminum and ternary alloys of the same compositions with added interstitial elements oxygen, nihrogen, and carbon were studied. Aluminum increases the apparent hydrogen solubility of the a-phase, resulting in a marked increase in resistance to impact embrittlement. In the Ti-5Al and Ti-7Al alloys, for example, the addition of 180 and 305 ppm hydrogen, respectively, did not cause embrittlement, while unalloyed titanium was embrittled by as little as 75 ppm. The role of aluminum in increasing hydrogen solubility of the a-phase probably accounts for the excellent hydrogen tolerance of a-ß alloys containing considerable amounts of aluminum. There is some evidence that aluminum retards the rate of hydride precipitation. If so, these alloys may be susceptible to slow-strain embrittlement. UNALLOYED a-titanium is extremely sensitive to small amounts of added hydrogen in that there is a marked decrease in notch properties. For example, as little as 100 ppm hydrogen is sufficient to lower the room-temperature notch-impact strength from over 100 to less than 20 in.-lb.' This loss of impact Strength has been associated with the Presence of hydride phase in the microstructure. Hydrogen in the amounts encountered in commercial practice

Jan 1, 1959

By R. M. Waterstrat

X-ray diffraction and metallographic examination of binary Mn-rich alloys with Ti revealed the presence of intermediate phases in this system. A binary R phase has been identified and also a phase having an a-Mn type structure. The X-ray pattern of the phase TiMn3 is presented and a tentative phase diagram for the Mn-rich portion of this binary system has been constndcted. MANGANESE-rich alloys with titanium have been subjected to thermal analysis at temperatures down to 1100°C by Hellawell and Hume-Rothery.1 Their results indicate the existence of an intermediate phase TiMn3 in this binary system. This phase appears to coexist with the Laves phase TiMn2, and with terminal solid solutions based on the allotropes of manganese, at least down to 1100°C. The above investigators did not attempt to determine the crystal structure of this phase, however. Since, by analogy to the binary systems Mn-V and Mn-Cr3 one might expect to find a phase in this region of the diagram, it seemed desirable to obtain X-ray diffraction patterns of alloys in the concentration range in question, in order to ascertain whether the sigma phase or related structures occur. EXPERIMENTAL PROCEDURES Alloys were prepared by arc-melting electrolytic manganese and iodide titanium in a water-cooled copper crucible under a helium atmosphere. Excess manganese was added to each melt in order to allow for losses incurred during melting. The alloys were then wrapped in molybdenum foil and sealed in evacuated quartz tubes for annealing at various temperatures, as shown in Table I, followed by quenching in cold water. Although the inside of the tubes showed evidence for some loss of manganese from the specimen during annealing, there was no evidence of any reaction between the specimen and either the molybdenum foil or the quartz tube at these temperatures. It was later found that the manganese loss was considerably reduced by annealing these alloys in sealed quartz tubes containing one atmosphere of purified argon. As an added precaution the surface of each specimen was ground off before crushing the alloys to -270 mesh powder, using a hardened steel mortar and pestle. X-ray powder patterns were obtained using either FeKa or CrKa radiation in an asymmetrical focusing camera, which gave excellent dispersion of the closely spaced lines. Pictures were also obtained using a Debye camera of 5-cm radius which provided data in the angular region not covered by the focusing camera. The alloy specimens were polished and examined metallographically, using an etchant consisting of 60 pct glycerine, 20 pct nitric acid, and 20 pct hydrofluoric acid. The 10-g buttons were in each case broken in half and found to be well-melted and free of any gross segregation. One half of certain alloy buttons was submitted to chemical analysis in the "as-cast" condition. No appreciable change in composition seemed to occur during annealing . RESULTS The X-ray pattern of alloy Ti1.17Mn0.83 was found to agree well with that of the ternary R phase which was first found in the Mo-Cr-Co system,' and re-

Jan 1, 1962

By J. R. Long, A. H. Roberson, T. R. Graham, R. S. Dean

EXPERIMENTAL work on the properties of high-purity alloys of the copper-manganese-zinc system has necessarily required extensive metallographic work to determine the equilibrium conditions in this system. Previous work on these alloys is fragmentary and, unfortunately, based on alloys made with impure grades of manganese, thus introducing significant amounts of iron, silicon, aluminum and carbon. Since these elements are known to affect equilibrium conditions, it became desirable to re-examine these alloys made from the pure metals. The alpha solid solution field was of particular interest and, therefore, was chosen for the initial work, which was outlined to determine the composition limits of this field. PREVIOUS WORK Heusler1 conducted an extensive survey of the liquid-solid regions of this system and also made an estimate of the solid-phase boundaries at 340°C. The pertinent part of his diagram is given in Fig. I, but it is of limited usefulness, since it applied to a single temperature only and is based on impure alloys under admittedly nonequilibrium conditions. Bauer and Hansen,2 likewise working with impure alloys, have determined the phase boundaries for alphabeta brasses containing small amounts of manganese and indicate an increase in the extent of the alpha field with increasing manganese. This is not in accordance with Heusler or with data obtained on pure alloys.3 They also described a third constituent precipitating in the alpha plus beta field below 350° to 400°C. but did not identify this constituent. Guillet4 and Heike and Ledibur5 have also noted this precipitate Each of these investigators recognized that impurities present in the manganese could and did have an effect on the structure and properties of their alloys. Corson6 in particular pointed out the hardening effects of silicon, aluminum, and carbon in copper-manganese alloys and Heusler reported that his alloys containing more than 25 per cent manganese were extremely brittle. In all probability this brittleness was due to the impurities present. This early work, therefore, should be taken as a general guide for preliminary studies only, and high-purity alloys may be expected to produce different results. The work of the Bureau of Mines laboratories with electrolytic manganese has been briefly summarized by Dean7 but includes only a short section on this system. Later work3 outlined a limited portion of the alpha field in the neighborhood of 65 per cent copper, 10 per cent manganese, and 25 per cent zinc. The present work was under-

Jan 1, 1945

By Robert Stefanko

With passage of the Clean Streams Act of the Commonwealth of Pennsylvania and its impact on the coal industry, considerable research has been conducted to explore various approaches to the problem, including deep-well disposal. Available drillhole data from gas and oil wells were used to develop cross -sectional maps for various portions of the state and potential disposal zones were evaluated. Bethlehem Mines Corp., faced with a severe water problem at its Marianna operation in Washington County, cooperated with the Dept. of Mining at The Pennsylvania State University in establishing a 1500-ft well into the Salt Sands for the purpose of determining the feasibility of mine water disposal. The thickness, porosity, and permeability of the formation at the well site proved to be below what had been anticipated from drillhole data. Further, subsequent hydraulic fracturing did not improve the flow characteristics of the well; pumping pressures remained in the range of 1800-2000 psig for disposing of water at the rate of 150 gpm. The legal problems of disposal at the site were very formidable. When the Salt Sands proved to be less than satisfactory, permission could not be obtained to dispose in other promising formations. The paper details many of the problems associated with the experimental well and makes an assessment of the potential for deep-well disposal of mine water. The concept of disposing of liquid industrial wastes by deep-well injection is not a new one. Brines associated with crude oil long have been disposed of in this manner, with the additional benefit of aiding secondary oil recovery. More recently, with the expansion of nuclear energy, the lethal, highly radioactive wastes which are by-products of the fission process have created severe disposal problems. During the past ten years, a variety of industries have resorted to subsurface disposal, some of the details of which are given e1sewhere.l,2 The list reveals wide variations in injection rate, pumping pressure, cost, and waste disposition. Included are successful installations in Western Pennsylvania. Enactment of more restrictive clean-water legislation in Pennsylvania recently had a great impact on the coal industry. Among its provisions was the reclassifica-tion of most mine water as industrial waste whose dis-posal is prohibited in any stream of the Commonwealth. This had the effect of accelerating research in a variety of areas, although treatment methods still retained primary interest. When a feasibility study of deep-well disposal was proposed to the Pennsylvania Dept. of Mines and Mineral Industries, the Coal Research Board (CRB) approved it. This paper summarizes the efforts on this project. Acid mine water is a chemically complex liquid. having no definite quantitative relationship among its constituents. However, it is the iron disulfide (FeS2) associated with practically all coal seams that produces the objectionable products present in acid mine water when combined with air and water. The principal contaminants are sulfuric acid (H2SO,) and ferric hydroxide (Fe(OH)2. Ferric hydroxide is a rust-colored gelatinous precipitate that coats stream bottoms and destroys aquatic life. However, other ions and bacteria are present in acid mine water in varying amounts.

Jan 1, 1971

By J. B. Fletcher

The Miami mine first started operations in 1910. For convenience, the history of the orebody can be divided into the following categories (Fig. 1): 1) 1910 to 1925: 24.4 million tons of high grade ore, mined by top slicing, sublevel caving, etc. 2) 1926 to 1954: 102 million tons of low grade ore, mined by block caving.

Jan 1, 1961

By J. Geertsma, F. de Klerk

During the hydraulic fracturing treatment of an oil or gas well the liquid pressure in the borehole is increased until tensile stress in the surrounding rock exceeds tensile strength. Once a tensile fracture is initiated, it is penetrated by liquid from the borehole and fracture propagation under continuous hydraulic action takes place. The fracturing liquid carries a propping agent to ensure a highly permeable flow channel after pressure release. Field results range from failure to obtain increased production to outstanding success. In all cases, however, it unfortunately remains uncertain whether the values chosen for the operational parameters, such as injection rate, pumping time and fluid viscosity, were in fact the ideal ones. Though experience provides a lead, a more satisfactory way to predict results would seem to be to subject the fracture propagation process to a theoretical analysis that (1) makes the maximum use of the relevant physical information and (2) so simplifies the resulting calculations that the field engineer gets practical data that he can handle comfortably. We are attempting here to do this in connection with the prediction of fracture width and areal extent before pressure release. What remains of the fracture afterwards depends on the distribution of the propping agent between the fracture walls, and that is a separate story. Idealization of the Problem To keep the problem tractable, a number of simplify- ing assumptions have had to be made: 1. The formation is homogeneous and isotropic as regards those of its properties that influence the fracture-propagation process. 2. The deformations of the formation during fracture propagation can be derived from linear elastic stress-strain relations. 3. The fracturing fluid behaves like a purely viscous liquid; i.e., any peculiar flow behavior due to the addition of gelling agents or other additives is neglected. Moreover, the effect of the propping agent distribution on the distribution of fluid viscosity in the fracture is not taken into account. 4. Fluid flow in the fracture is everywhere laminar. 5. Simple geometric fracture-extension patterns are assumed — either radially symmetrical propagation from a point source (Fig. 1A) or rectilinear propagation originating from a line source (Fig. 1B). In the first case the periphery of the fracture is circular, in the second case it is rectangular. 6. A rectilinear propagation mode can be accomplished only by injection over a large perforated interval, thus forming a line source. Such a rectilinear fracture must therefore be located in the vertical plane. A circular propagation mode might be expected from injection through a narrow band of perforations. This forms a point source. Because gravity effects are excluded from our considerations, the fracture propagation plane may in this case assume any angle with respect to the wellbore as far as the

Jan 1, 1970

By H. T. Kennedy, S. M. Avasthi

An equation developed for gaseous hydrocarbon mixtures predicts molal volumes with an average absolute deviation of 0.73 percent when applied to 264 natural gas and condensate systems including 2,043 PVT points. Another equation developed for liquid hydrocarbon mixtures predicts molal volumes with an average absolute deviation of 1.12 percent when applied to 346 crude oil systems including 1,759 PVT points. Both equations require composition of the mixture to be expressed as mole fraction of methane through heptanes-plus, hydrogen sulfide, nitrogen and carbon dioxide, together with the characteristics of the heptanes-plus fraction in addition to the temperature and pressure. The equations cover wide ranges of the variables involved, and their accuracy is considerably better than that of other available methods. The equations were differentiated to allow calculation of the coefficients of isothermal compressibility and isobaric thermal expansion. (In this paper the coefficient of isothermal com-pressibility and the coefficient of isobaric thermal expansion will be expressed as compressibility and thermal expansion coefficient, respectively.) Equations to calculate these quantities are presented. INTRODUCTION Calculations of reservoir performance for petroleum reservoirs require accurate knowledge of the volumetric behavior of hydrocarbon mixtures, both liquid and gaseous. Compressibilities are required in transient fluid flow problems, and thermal expansion coefficients are important in thermal methods of production. An accurate laboratory investigation of the PVT behavior of each reservoir fluid encountered would be costly and time consuming. For this reason various correlations for predicting fluid properties have been developed and recorded in recent literature. Correlations have been presented in the form of graphs, tables and equations. Since an increasing number of studies are being conducted with the aid of electronic computers, recent efforts have been directed toward development of correla-tions suitable for computer programming. Application of computers permits the use of more complex correlations which otherwise are not feasible. Moreover, methods for predicting reservoir performance, particularly those based on the compositional material balance, depend upon the capability of accurately expressing the molal volumes and other fluid properties as functions of pressure, temperature and composition. The coefficient of isothermal compressibility c is defined by

Jan 1, 1969

By L. R. Raymond

With the trend toward deeper and consequently hotter holes, measurements of drilling mud properties at atmospheric temperatures are becoming increasingly inadequate.' Both the prediction and control of down-hole mud properties depend in part upon our knowledge of temperatures in the wellbore. Consequently, a better understanding of factors that affect temperatures during circulation and trips could improve drilling operations. It was toward the goal of obtaining this understanding that this study was directed. Other investigators2 have studied the response of fluid temperature in the borehole during trips. However, all of these studies have used an assumed formation temperature profile at the conclusion of circulation and have provided no means to calculate this profile directly. In this study, the formation profile during circulation was calculated. Other investiga-tors3-5 have also studied bottom-hole temperature during circulation. However, they have developed neither general techniques for calculating the entire temperature profile in the system nor generalized methods for predicting bottom-hole fluid temperatures during circulation. Such techniques and methods have been developed and are discussed briefly in the following pages. Temperature Behavior During Circulation Circulation of fluid during the drilling operation is represented schematically in Fig. 1. The process of circulation has three distinct phases: (1) fluid enters the drill pipe at the surface and passes down the drill pipe; (2) fluid exits the drill pipe through the bit and enters the annulus at the bottom; and (3) fluid passes up the annulus and exits the annulus at the surface. To simulate the thermal behavior of the fluid in the system, each of the phases of circulation must be described mathematically. In Phase 1, the fluid enters the drill pipe at a specified temperature, TDo. As the fluid passes down the pipe, its temperature is determined by the rate of heat convection down the drill pipe, the rate of heat exchange between the drill pipe and the annulus, and time. Phase 2 of the circulating process merely requires that the fluid temperature at the exit of the drill pipe be the same as the fluid temperature at the entrance of the annulus; i.e., TD(L,t) = TA(L,l). Thus in Phase 3, the fluid enters the annulus at TD(L, t). As the fluid flows up the annulus, its temperature is determined by the rate of heat convection up the annulus, the rate of heat exchange between the annulus and the drill pipe, the rate of heat exchange between the formation adjacent to the annulus and the fluid in the annulus, and time. These rates of heat exchange and the time dependency of mud temperature are described by well known heat-flow equation.6 Consequently, as shown in the Appendix, the temperature profiles in the drill pipe, annulus, and formation can be obtained by solving Eqs. 1 through

Jan 1, 1970

By M. R. Tek, L. K. Thomas, D. L. Katz

Threshold displacement pressures are needed to determine how much overpressure can be used in storing natural gas. An experimental technique for determining threshold pressures by displacing water with gas from samples saturated with water is presented. Threshold pressures for eight low permeability samples were measured. Threshold pressure data obtained in this work, plus data on higher permeability samples reported in the literature, are correlated with porosity, permeability, surface tension and formation resistivity factor. Mercury injection pressures also were measured and correlated with air-water threshold pressures. Threshold pressures were found to be independent of time. An aerial photograph of gas emerging from the top of a core shortly alter its threshold pressure has been exceeded shows that the gas bubbles are uniformly distributed across the face of the core. Channeling will occur, however, when an increased gas phase permeability is reached, A porous medium can be re resealed alter its threshold pressure has been reached, provided it has not been desaturated below a fixed saturation. Its new threshold pressure will be lower than when the sample is 100 percent saturated with water. INTRODUCTION The degree of overpressure in excess of the discovery pressure that a gas storage reservoir can withstand is determined by the ability of its caprock to contain gas, providing the pressure does not exceed the structural limit of the reservoir. The retention of gas in a reservoir by a caprock saturated with water is a result of the capillary forces acting at the gas water interface. Without the presence of water in a caprock, gas would leak out of the reservoir at a rate determined by the permeability of the caprock to gas. The ability of a caprock to contain gas is expressed in terms of its threshold displacement pressure, which is defined as the minimum pressure needed to initiate the displacement of a wetting phase by a nonwetting phase from a porous medium 100 percent saturated with the wetting phase. The gas industry must be able to predict how much "overpressure" a gas reservoir can withstand before leakage occurs by gas displacing water from caprock overlying the reservoir. This is of economic importance since the storage capacity of a gas reservoir is proportional to its pressure. The discovery pressure for most reservoirs is found between the upper and lower limits1 shown in Fig. 1. Discovery pressures in excess of their hydraulic pressure gradient are attributed to the compaction of an isolated shale formation by the overburden.2.3 The lower limit of 0.433 psi/ft corresponds to the weight of the overburden, the gradient of the rock itself. Somewhere between

Jan 1, 1969

Jan 1, 1969

By H. B. Charmbury, D. R. Mitchell

Everyone in the coal industry from top management to the preparation engineer is vitally interterested in recovering as much salable coal as possible from the run-of-mine product. Coal losses from a preparation plant occur in the solid refuse material being discharged from the plant and in the bleed-off slurry from the water circuit. The refuse is generally hauled from the plant in solid form by trucks, conveyors, or aerial trams to the refuse or culm banks or it may be crushed and transported by hydraulic methods to refuse ponds or dams. The loss of coal in refuse material and the extent of this problem has been covered in another paver.' The loss of salable coal in the plant bleed-off slurry is one of the water circuit problems in coal preparation plants. Slurries originate at various places in the processing circuits and are usually disposed of by transportation to waste ponds known as slurry ponds. Even though the combustible material discharged as slurry and refuse from the plant is labeled a loss, the loss must only be considered temporary. There is a tendency at the present time to examine refuse and slurry losses and to reprocess these materials to recover valuable coal. Slurries from eight bituminous coal preparation plants in central and western Pennsylvania have been sampled and examined to determine the amount of recoverable coal in each. Examinations of the samples were made to determine the tons per hour of solids and the gallons per minute of water in the slurry; the size, ash, and sulfur analyses of the solids; and the sink-float characteristics of the larger solids. The extreme fines (—325 mesh material) from one of the samples has been examined further to determine the micron size fractions as well as the ash and sulfur content of the micron sizes. Collection of the Samples: Field trips were made to each of the plants where samples were obtained and discussions held with the preparation engineer prior to sampling. The flowsheet of the plant operation was studied and a time-period selected to obtain a representative sample. At least 20 1-gal samples of total plant bleed-off suspensions were collected at each plant in increments over designated periods belived to be typical of the plant flow Three of the samples were obtained from plants in the Pittsburgh area. Each plant supplied information on the capacity, operating time, type of cleaning equipment used, water and material balances, and auxiliary equipment. From the time required to collect given amounts of slurry and from the amount of solids in the slurry, total solids discharges from the plant were calculated and compared with the plant flow. Ash and sulfur analyses of the total solids were also checked, at some plants, with company figures. In all cases where checks could be made there was reasonable agreement between company figures and those reported here. Analysis of the Slurries: Representative fractions of properly agitated samples were examined in the laboratory to determine the specific gravities of the slurries. The solids and water were separated by filtration to check the weight of each so that the percent of solids in the pulp could be determined. From the resulting data, presented in Table I, it may be seen that the percent solids in the slurries ranges from 2.8 to 39.0 and the amount of solids from 2.61 to 45.61 tph. Size Analysis of Solids: Representative fractions of the slurries were permitted to settle and the clear water was removed by siphoning. The solids were then wet-screened at 28, 35, 48, 65, 100, 150, 200 and 325 mesh. Results of the size analyses are presented in Table 11. These results indicate the extreme variation of sizes and in most cases the degree of fineness of the solids. The amount of —325 mesh ranges from 22.5 to 84.5 pct and the amount of+200 mesh from 8.3 to 69.1 pct.

Jan 1, 1961

By C. S. Samis, D. P. Seraphim

In the presence of oxygen, galena is oxidized in an aqueous medium containing ammonium acetate in accordance with the following reaction: PbS + 1/2 0, + 2 NH~Ac -» PbAc, + So + 2 NH: + H2O. This reaction was studied in an autoclave under oxygen pressure by polarographic measurement of the concentration of lead ion in solution. Oxidation rate is parabolic. The reaction products are lead acetote and elemental sulfur, the latter forming a film on the galena crystal. Reaction kinetics appear to be determined by the diffusion of lead from the galena phase to the solution interface through the film of sulfur. RECENT applications of pressure leaching on a commercial scale have emphasized the metallurgical importance of the oxidation of sulfide minerals in aqueous media by oxygen under pressure. Research experience has shown that sulfates, thio-nates, and metal oxides are the products of humid oxidation of sulfide minerals in basic solutions. The metal oxides may be solubilized in the presence of a complexing ion.' Certain oxide minerals are also amenable to treatment by this type of oxidation.' Several kinetic studies have been made of reactions of this type. Stenhouse' found that pyrite (FeS?) oxidized in a sodium hydroxide solution to produce a soluble sulfate and an insoluble layer of iron oxide and that the kinetics of the reaction were controlled by oxygen diffusion through the oxide layer. Andersen' studied the oxidation of galena (PbS) in a sodium hydroxide solution under oxygen pressure. He found the lead and sulfur to be simultaneously oxidized to produce plum bite ions and sulfate ions, and that the reaction rate was proportional to the surface area of the galena. The kinetics appeared to be determined by the reaction of oxygen and water with the galena surface. In each of the above reactions the metal and sulfur components of the mineral were oxidized simultaneously and at equal rates. In the present study the alkaline medium has been replaced by an approximately neutral solution of ammonium acetate in which lead sulfate is soluble. Under the conditions no sulfate was produced and no sulfur could be detected in the solution. The metal component of the mineral was solubilized and the liberated sulfur remained as a film of elemental sulfur on the surface of the galena crystal. A kinetic study of this reaction was undertaken to establish the kinetic mechanism and to determine the rate controlling step. Specific reaction rates were determined by oxidizing crystals of galena of measured surface areas in an autoclave maintained at the desired temperature and oxygen pressure. The rate of reaction was followed by measuring the concentration of lead in the ammonium acetate solution with a cathode ray polarograph, employing stationary platinum electrodes incorporated in the autoclave. Experimental Materials and Equipment Crystals of galena obtained from Violamac Mines, Retallack, B. C., were selected for oxidation because

Jan 1, 1957

By J. E. Campbell, A. W. Wesner, M. Pobereskin

This paper summarizes the results of an investigation sponsored by The Coates Steel Products Company. The objective was to determine the relative effects of certain chemical and physical properties on the wear resistance of grinding balls when grinding cement. In making this study, a number of types of balls were used in both dry and wet grinding in commercial ball mills. The radioactive-tracer technique was used in separating the test balls from the rest of the mill charge and in sorting the different types of halls that were all tested at the same time for each of the grinding operations. PROCESSING OF GRINDING BALLS In order to determine whether the properties of grinding balls, namely, composition, microstructure and hardness, can be related to the rate of wear, the halls used in this study were selected to represent various combinations of these properties. It was recognized that the mechanism of wear was not the same in the wet mill as in the dry mill. Therefore, the types of balls tested in each of the two environments were not necessarily the same. However, all of the types of balls evaluated in the dry mill were tested simultaneously for one time period, while those evaluated in the wet mill were tested simultaneously for three different time periods. All of the test balls were separated from the charge when the mill was dumped. All of the balls were of 0.940-inch diameter when charged, and all but the regular production balls were finish ground to this size to eliminate the decarburized surface layers. The steels and processing methods used, as well as the micro-structures and hardness levels of the balls, are described as follows: Regular production forged SAE 1095 steel balls were used in both the wet and dry mills. They were forged to a nominal diameter of 0.940 inch and quenched in oil from the forging temperature. Each retained a partially decarburized surface layer from the forging bar stock; the maximum depth of this layer was about 0.030 inch and the decarburization was negligible where the ball was sheared from the bar. The hardness at the surface was 40 to 46 Rock-well C in the partially decarburized area and 57 to 62 Rockwell C in the areas not decarburized. The hardened zone extended to a depth of about one-third of the radius. Below the decarburized layer, the hardened zone consisted primarily of hard as-quenched martensite with varying amounts of retained austenite. This structure changed to fine pearlite at a depth of about one-third of the radius. In order to eliminate the effect of the decarburized layer, a set of production balls of SAE 1095 steel was forged to about a 1-inch diameter, quenched in oil from the forging temperature, and ground on ball-bearing grinding equipment to a 0.940-inch diameter to remove the decarburized layer. The balls' hardened zones were similar to those in the previous set. The hardness of the finished surfaces was 52 to 60 Rockwell C. A slight amount of decarburization apparently remained after the removal of about 0.030 inch from the surface. Balls of this type were tested in the dry mill only. Another set of forged SAE 1095 steel balls of 1-inch diameter was heated to 1500 F and quenched

Jan 1, 1961

By Y. Baskin

Solid-solubility relationships in the Pseudobinary systems UAS-UP, UAs-US. UAS-UC, aid UAs-UN were investigated. The first two systems exhibit complete mutual solubility, whereas the component compounds in the other two systenzs are immiscible. The above information, together with solid-solubility data joy six additional pseudobinary systems , were analyzed for compliance wilh the Hurrze-Rothery rules for rnetallic systems. The relative size difference of the component nonmetal atoms was found to be the dopainant jactor determining the extent of solid solubility between the NaC1-type uranium compounds. The anionic and covalent radii of the nonmetal atoms appear to be inadequate for these systems, but compuled radii based on rare earth compounds yield consistent results for the uranium compounds. THE actinide elements, like metallic elements of the transition and rare earth series, readily form binary compounds with nonmetallic elements of groups IV, V, and VI of the periodic table. Of particular importance are the NaC1-type equiatomic compounds with carbon, nitrogen, sulfur, phosphorus, and arsenic. The uranium members of this family of compounds have high melting points, are essentially stoichiometric, and exhibit various amounts of mutual solubility. Thus, they are of interest for investigating the factors governing the extent of solid solubility. Previous investigators have determined the solid-solubility limits in the pseudobinary systems between the compounds UC, UN, US, and UP. Anselin et a1 .' reported complete miscibility in the system UC-UN. Baskin and shalek 2 and Allbutt et a1.3 reported that UP and US exhibit complete mutual solubility. Shalek and white4 reported partial miscibility in the system US-UC. At 1800°C the maximum solubility of UC in US is 40 mol pct, but that of US in UC is 4 rnol pct. shalek5 found limited solubility in the system US-UN; the maximum solubility of UN in US is 11 rnol pct at 1800°C, while that of US in UN is only 0.3 mol pct. White and askin 6 found very limited miscibility in the system UP-UC at 1800°C. Approximately 7 mol pct UC is soluble in UP, but there is no solubility of UP in the monocarbide. Phase relations in the pseudo-binary system UN-UP were investigated by askin.' Approximately 0.7 mol pct UN is soluble in UP at 1800°C, while UP is immiscible in UN. The present study was carried out to explore the extent of terminal solubility in the systems UAs-UC, UAs-UN, UAs-US, and UAs-UP. This information, combined with existing data, provided a sufficient basis on which to determine the factors governing solid solubility in pseudobinary systems containing NaC1-type uranium conpounds. I) EXPERIMENTAL 1) Materials. The compounds UC and UN were obtained from the Kerr-McGee Corp. and United Nuclear Co., respectively. The US, UP, and UAs were synthesized by reacting finely divided uranium with H2 S, pH3, or AsH3 gas at low temperature (300° to 500°C), followed by homogenization in a vacuum at moderately high temperatures (1400° to 1700°c).8-10 The materials were essentially stoichiometric, with the exception of UC, which exhibited a C/U ratio of 1.05. Oxygen was the major contaminant in these compounds, ranging from 0.05 wt pct in US to 0.30 wt pct in UC, and it was generally combined with uranium to form UO2. The UO2 content in these materials was usually of the order of 1 wt pct, and did not exceed 2 wt pct. Furthermore, no evidence was found for a high-temperature reaction between uranium dioxide and any of the compounds. Chemical analyses of equilibrated compositions in the systems UAs-UP and UAs-US showed that the non-metal atom to uranium ratios averaged about 1.01, and that the oxygen contents ranged from 0.06 to 0.22 pct. However, the small deviations from stoichiome-try or the presence of minor oxygen impurities do not invalidate the conclusions to be drawn from this study. 2) Experimental Procedures. The component compounds in powdered from were blended in the desired proportions for 5 hr in the ball mill that consisted of stainless-steel balls in a plastic container. Chemical analyses indicated very little metallic pickup from the blending operation and virtually no increase in oxygen content. The pellets were pressed in a 0.270-in.-diam steel die under 40,000 psi pressure. One wt pct of stearic acid dissolved in CCl 4 served both as a binder and as a die lubricant. Chemical analyses revealed that the stearic acid left no carbon residue in the sintered samples. The pellets were sintered in vacuum in an unsealed tantalum crucible. The temperature, measured with a calibrated optical pyrometer, was maintained at 1800" + 30°C for 3 hr. This was sufficient time for attaining equilibrium as no change occurred in either the lattice parameters or the sharpness of the X-ray patterns when samples were annealed for longer periods of time. The pellets were cooled with the furnace. Debye-Scherrer powder patterns were taken at room temperature with a 114.59-mm-diam Norelco powder camera and CuKor radiation (CuGI = 1.5405A). Unit cell dimensions were determined from a Nelson-Riley extrapolation to the high-angle reflections. The values for were precise to k 0.001A. 11) RESULTS X-ray and met allographic investigation revealed that complete mutual solid solubility exists in the pseudobinary systems UAs-UP and UAs-US. The lattice parameter vs composition plots, Fig. 1, show a

Jan 1, 1968