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By J. Gurland

A method of measuring the degree of contact between grains of 1 phase in multiphase alloys is derived. It is shown that the number and the areas of contacts between grains can be determined by metallographic analysis. Relations between the area of contact, the dihedral angle, and the mean free path of spherical grains are developed. It is often desirable to interpret the mechanical behavior of alloys in terms of structural features observed under the microscope. A quantitative description of microstructures of multi-phase alloys requires consideration of geometrical and topological factors such as the amount, size, and shape of grains and the continuity of the constituent phases. The number and dimensions of grains may be metallographically determined by applying the methods described by Smith and Guttman1 and by Fullman2 in their papers on the measurement of particle size and internal boundaries in opaque bodies. The present work intends to show that the same methods can be used to evaluate some of the parameters of phase continuity; namely, contiguity, number of contacts, and areas of contact of grains of 1 phase. Application of these concepts may be found in such problems as the calculation of electrical conductivity of 2-phase alloys, or the evaluation of the length of fracture path through grains of a brittle phase more or less dispersed in a matrix. I. DEFINITION The following definitions and derivations are based on 2-phase alloys, of which the units of the microstructure are grains. Contiguity is defined as the average fraction of surface area shared by 1 grain of a phase with all neighboring grains of the same phase. In a 2-phase alloy of constituents A and B, the contiguity of phase B is given by: where Cb is the contiguity of phase B aBß is the average area of contact between a grain of phase B and adjacent grains of phase B, aAB is the average area of contact between a grain of phase B and adjacent grains of phase A. The contiguity is a measure of the average degree of contact between grains of phase B in the 2-phase mixture. The ratio varies from 0 to 1 as the distribution of phase B changes from a completely dispersed to a fully agglomerated structure. Smith and Guttman1 have shown that the relative areas of 2 kinds of interfaces in a volume are directly proportional to the number of interfaces of each type intersected by a random line. The lines can be drawn on metallographically prepared surfaces as long as these are random sections through the sample. The contiguity ratio of phase B then becomes: Cb = 2NBB/NAB + 2N BB [2] where: NBB is the number of interfaces between grains of phase B intersected per unit length of random line. Nab is the number of interfaces between grains of phase B and grains of phase A intersected per unit length of random line. The factor 2 arises in Eq. [2] because each interface B-B is associated with 2 grains of B-phase, whereas the interface A-B involves only 1 grain of B-phase. The calculations of contiguity do not require any assumption as to volume fraction, particle size, or particle shape. Fullman2 gives an expression for the determination of the mean free path between particles. The mean free path PB between grains of phase A, i.e., through grains or agglomerates of phase B, may be found from the relationship: PB =2fB/NAB [3] where fB is the volume fraction of phase B. The calculation of the mean free path is independent of grain shape and grain size distribution. The calculation of the number of contacts and of contact area requires assumptions of grain shape, grain size, and contact shape. In the case of uni-

Jan 1, 1959

By O. M. McRae

The Courtland-Gleeson area is in Cochise County about 15 miles east of Tombstone in southeastern Arizona. Rocks exposed in the area range in age from Pre-cambrian to Quaternary. The Precambrian is repre-sented by the Pinal schist. Paleozoic rocks include the Cambrian Bolsa quartzite and Abrigo limestone, Mississippian Escabrosa limestone, and the Permo-Carboniferous Naco Group limestones. Rocks believed to be of Triassic and/or Jurassic age include the Copper Belle monzonite porphyry, Turquoise granite, and Gleeson quartz monzonite. The Cretaceous is represented by andesitic volcanics and various sedimentary rocks. Tertiary rocks include the intrusive and extrusive Sugarloaf quartz latite porphyry and numerous dikes of various rock types. Quaternary conglomerates cover the northern and eastern part of the area. The geologic structure is extremely complex. All rocks as old as early Tertiary have been involved in either tilting, normal faulting, high angle reverse faulting, imbricate thrusting or folding and overfold-ing. Major deformation was initiated during the first half of the Tertiary. Northeast-southwest compres-sional forces caused thrust plates containing lower Paleozoic rocks to override Cretaceous rocks. Subsequently, two large slide blocks of lower Paleozoic rocks, acting under the influence of gravity, moved eastward. The imbricate structure and the gravity slide blocks were then broken by late Tertiary normal faults. INTRODUCTION The Courtland-Gleeson area, or Turquoise Mining District, has long been recognized as an area of extreme structural complexity. Gilluly 2 referred to the entire district as a "gigantic thrust breccia". In 1962, Bear Creek Mining Company completed a two year program of detailed geologic mapping supported by exploration drilling. The purpose of this paper is to present some of the results of this investigation and to provide a structural interpretation based on these results. The geologic map that accompanies this report is generalized and shows only the major and significant features. The area was initially mapped on aerial photographs on a scale of 1 in. equals approximately 500 ft. These data were transferred to a planimetric base using a vertical sketch master. LOCATION The Courtland-Gleeson area is in central Cochise County, about fifteen miles east of Tombstone, and about twenty-two miles northeast of Bisbee in southeastern Arizona (Fig. 1). The area is readily accessible over graded gravel roads from both Tombstone and Elfrida. GENERAL GEOLOGY Rocks exposed in the area range in age from Pre-cambrian to Quaternary. wilson3 and Gilluly2 have published very detailed descriptions of the principal rock units exposed in the area. Only a summary description is provided in Table I. A great number of previously unmapped narrow Tertiary dikes and small irregular masses of hornblende andesite porphyry, lamprophyre, and aplite intrude the Gleeson quartz monzonite in the western part of the map area. The scale of the map prohibits showing them. The aplite dikes are related to, and bear the same structural relationships as, the Sugarloaf quartz latite dikes found in this area. For that reason, and because both the hornblende andesite porphyry and the lamprophyre are post-mineral and post-thrusting, their omission from the map is not considered significant. Because so many of the contacts in the district are fault contacts, because bedding faults appear to be prevalent but are difficult to recognize and map, and because igneous intrusions are so common throughout the sedimentary section, it is virtually impossible to measure an exact total thickness of any of the sedimentary rock units. Nevertheless, neither the field mapping program nor the diamond drilling provided any basis for suspecting that the thicknesses of the sedimentary units are significantly greater or less than what might be inferred from surrounding districts.

Jan 1, 1967

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 R. J. Stokes

S. Floreen (international Nickel Co.)— One fairly simple way to differentiate between em brittle me nt due to surface microcracks or due to a dislocation barrier effect might be to load a brittle rock salt crystal in tension to some stress just below the fracture stress and then immerse the loaded crystal in water. If a surface film is retarding plastic flow then one should observe some plastic deformation of the rock salt as

Jan 1, 1962

By Walter G. Perkins

T SEEMS almost sheer presumption to attempt' to discuss Russia in its present chaotic political and economic condition, and were it not that at least two certain absolute factors are continuously at work, it would be impossible to' even approach the subject with any degree of intelligence. These are the inborn love of peace of the people and the national character of the cooperative movement. The love of peace inborn in the soul of every Russian, the desire to be left alone and to- live his life among his home village surroundings, is probably one of the two greatest factors that will make the continuance of the present conditions of civil war impossible. One army or the other may sweep up and down the country. but the Russian peasant will: remain in his own village if not literally darken out. This love of peace is evidenced by the fact that there is no country where personal safety is greater than in Russia in normal times. I have traveled in many isolated parts, carrying considerable sums of money and persolial equipment that; in itself, would be a fortune to any peasant, and have never even encountered a condition in which the most wildly imaginative person looking for adventure, 01: trouble, could muster up even a suspicion of fear. This statement applies also to Southern Siberia and Northern Turkestan, which are inhabitated by the nomadic tribes of Khirghese origin.

Jan 1, 1920

By R. D. Pehlke, J. V. Gluck

AS a portion of a general study of liquid-metal thermodynamics, high-temperature galvanic cells were used to study the effect of added dilute solutes on the activity of zinc in dilute solution with molten bismuth in the range 450° to 650°C. 1,2 The cells were of the type The experimental procedures have been described previously.1 In the course of studies conducted in the bismuth-rich corner of the systems Bi-Zn-Au and Bi-Zn-Cu, marked discontinuities were observed in the electromotive force-temperature relations for a number of the experimental compositions. Above the discontinuity temperatures, the relations, which were linear, exhibited slopes similar to the binary alloy of the same mole fraction zinc, as shown in Figs. I and 2. Below the discontinuity temperatures, the slopes were markedly different, but the relations remained linear. In general, as the amount of the third eletnent was increased, the slope of the lower portion of the relations tended to become less positive. The slopes of electromotive force-temperature relations reflect the entropy of mixing of zinc and, therefore, the occurrence of a discontinuity marks the transition between two different equilibrium situations involving the solution of zinc. A number of other investigators3-5 have used such observations to determine liquidus boundaries in binary alloys. Since the upper portions of the ternary electromotive force-temperature relations of this study had the same slopes as the binary alloys, the discontinuities are interpreted as marking the transition between the single-phase liquid region and the underlying two- and three-phase regions. Reference to the Zn-Bi equilibrium diagram6 confirms that the binary alloys were single-phase liquids at the experimental temperatures. Fig. I shows the electromotive force-temperature relations for the alloys containing Bi-Zn-Au and Fig. 2 shows similar relations for the Bi-Zn-Cu alloys. In the lower portion of each figure, the temperature of the discontinuity is plotted vs the mole fraction of the added solute at the various levels of zinc concentra- tion. Cross-plots from these curves at constant temperature permitted the construction of the partial liquidus surface isotherms shown in Figs. 3 and 4.

Jan 1, 1967

By R. G. Bentsen, D. A. T. Donohue

The cyclic steam injection process has become the most widely applied and most successful thermal recovery technique in use today.1-4 Normally, steam stimulation is repeated several times during the life of a project. The problem is to select the optimum number and size of steam treatments so that the profits realized over the entire life of the project are maximum. Obviously, operating costs rise directly with the frequency and amount of steam injection. Operating efficiency, on the other hand, can be adversely affected if the amount and frequency of stimulation are insufficient. Thus arises a multistage decision problem; that is, a decision must be made at each sub-period (day, for example), as to whether steam should be injected, and, if so, how much. It is desirable that these decisions be made in such a way as to secure maximum net profit before taxes. This can be achieved by dynamic programming. To use dynamic programming, we must be able to predict not only the production rate-time curve resulting from a given stimulation, but also how changes in stimulation policy will affect this curve. In this study, the effect of steam injection on well performance is estimated on the basis of a simple model that takes into account both steady-state and transient flow. Oil production rate is calculated for both types of flow, and the larger of the two values is used. This allows the calculation to change to radial steady-state flow at such time as this mechanism becomes more effective than the transient mechanism. We propose to show how dynamic programming can be used to optimize the steam soak process with respect to net profit. For this, a mathematical representation of the steam soak technique is necessary. A further objective, therefore, is the formulation of a mathematical model capable of realistically simulating the physical process. Oil Production Response Model The advantage of using a mathematical model is its generality and ease of manipulation. However, the model must be an accurate representation of the physical process, for a solution derived from a model can be no better than the model itself. The question now arises as to how well the model should be expected to simulate reality. In general, the simplest model should be tried first, for additional accuracy is apt to require additional cost and time. Also, the search for a high degree of accuracy may yield only greater complexity and difficulty without yielding significantly better results. With this in mind, we kept our model as simple as possible, yet generally representative of the actual physical process. The number of state variables is limited to three, and stochastic variations in the parameters are ignored. As a consequence, use of this model should be restricted to cases in which the underlying assumptions are not severely violated. In

Jan 1, 1970

By S. H. Ward, R. A. Barker

THE Juniper Prospect is in Carleton County, N. B., at approximately 46" 31' north latitude, 67" 20' west longitude. During the summer of 1955 an area in west-central New Brunswick was selected for aerial electromagnetic prospecting with American Metal Co.'s helicopter-mounted equipment. Generalized, small-scale government geologic maps had suggested that this area was located along the western border of the northeast-trending granitic backbone of northwestern New Brunswick and might be underlain by the Ordovician-Silurian sediments and volcanics that are the host rocks for the recently discovered sul-fide deposits of the Bathurst-Newcastle district. The helicopter electromagnetic equipment located an anomalous conductive area, coincident with a small aeromagnetic closure, about five miles west of the town of Juniper. Subsequently 30 mining claims (total area about 6600 x 8000 ft) were staked and company personnel conducted geological, geophysical, and geochemical investigations on the property. The claims and immediately contiguous areas were mapped geologically, and an area of about 2000 x 4000 ft was soil-sampled and also surveyed by ground electromagnetic and gravity methods. Finally six diamond drillholes, totaling 3500 ft in length, were drilled to test the anomalous conditions discovered by the several exploration techniques used. The discovery of base metal sulfides during drilling was a technical success for the exploration methods, but the quantity of sulfides was too small to be profitably exploited.

Jan 1, 1959

By R. W. Stahl

Employees and dollars are necessary to all enterprises and any force, such as fire, which destroys either, can bring very serious consequences, including business failure. Since everyone acknowledges the necessity of conserving human life, we will devote most of our paper to the economic factors involved. A coal-mine fire is considerably more difficult to combat than a fire in a surface building because of the combustible surroundings in the mine, the explosive gases emitted from the coal, the suspension of explosive dust when mine timbers burn and the unsupported roof falls, the limited space in which approach to the fire can be made, and the limited avenues of escape. A survey of coal-mine-fire protection indicated that a rather low value was being placed on property and equipment. This prompted comparison with other industries. The comments made in this comparison are not intended as an indictment of the coal industry, since we do have mines that are well protected against fire, but the comments on conditions at the mines visited are factual and may help others to improve similar conditions. SURVEY PROCEDURES Plants of the steel, aluminum, rubber, chemical, and petroleum industries were surveyed, and all facets of the fire-protection scheme were covered. The industrial plant invariably had four times as much water readily available for instant use than the mine. In many mines where water is available, no equipment for applying it is provided, such as hose, nozzles, and adapters, so that time is lost in collecting this equipment. (See Table I.) EXTINGUISHERS Many more and generally larger portable extinpishers are available at the plant as compared to the mine. The extinguishers are generally placed nearer to sources of danger. In addition, respiratory protective equipment is always available at strategic points in plants but only in a few mines. (See Figs. 1 and Table 11) INSPECTING AND TESTING EQUIPMENT Plant water facilities are checked weekly and flushed at 6-month intervals, and hose is pressure-tested at least yearly; some mines check water yearly, but hose is not tested unless used. Fire extinguishers are inspected weekly in plants and completely overhauled yearly; one mine had monthly checks and overhauls only after use. FIRE BRIGADES AND TRAINING Every plant had designated fire-fighters and some complete full-time brigades; at one mine a chief mechanic was designated as being in charge of fires, and other depended entirely upon officials who might not be familiar with the equipment. COST OF FIRES AND PERCENTAGE OF CAPITAL INVESTMENT IN FIRE PROTECTION The direct cost of recent mine fires ranged from $128,000 to $240,000; indirect costs, such as lost tonnage, idled equipment, lost orders, and the like might run the cost to over $500,000. (See Figs. 2 and 3).

Jan 1, 1961

By W. J. Kroll

Jan 1, 1960

By M. F. Trice

PYROPHYLLITE is a hydrous aluminum silicate (A12Si4010(OH)2)1 that occurs in both the foliated and the massive forms. The foliated variety resembles talc in that it has a greasy feel, a pearly luster, perfect basal cleavage, and usually is white, although in some deposits apple green, gray, brown, russet, and nearly black specimens may be found. The massive deposits of pyrophyllite yield pearl gray to light tan aggregates, some of which are so friable that they may be crushed with the hands into a fine gritty powder. Frequently specimens of the massive variety are studded with crystals of radial structure. The mineral has a specific gravity of about 2.7 and a hardness of 1 on Mobs' scale.1 The chemical composition of commercial pyrophyllite reflects the mineralogy of the deposits, which, according to Stuckey,2 contain pyro-phyllite and quartz, together with chloritoid, sericite, and a few other minerals of negligible importance. The latter, he says, "are noticed in but small quantities to the extent they might occur as accessory constitu-ents of an igneous rock or as products of regional metamorphism or weathering. . . . Quartz is abundant everywhere except in the very best grades of pyrophyllite." Analyses of specimens from several deposits are listed in Table 1, showing that the silica content varies from 57 to 73 percent and the alumina from 22 to 33 percent. Oxides of iron and the alkaline metals are collectively present, with one exception, to an extent of about 1 to 1.5 per cent.

Jan 1, 1940

By C. F. Weinaug, R. W. Farley, J. F. Wolfe

A rapid, accurate method for predicting the dew points of gas condensate systems and their subsequent normal and retrograde phase behavior with pressure decline has been developed. The method predicts dewpoint pressure, volume percent liquid, condensate content of produced gas, and the liquid and gas compositions at pressures below the dewpoint pressure. Use of a modified form of the BWR equation of state, which was established by regression calculations on experimental data from several gas condensates, provides depletion behavior predictions that are significantly improved over predictions using K-values based on convergence pressures and Standing's correlation for density. INTRODUCTION Prediction of complex hydrocarbon-mixture thermodynamics is fundamental to reservoir and gas process engineering. In particular, accurate descriptions of phase behavior are needed to plan production operations for gas-condensate reservoirs. Although analysis of reservoir behavior during producing and cycling operations can be made for simple reservoir models, extensions of these studies to more complex reservoir systems are still difficult, both with regard to numerical techniques and the phase behavior of the fluids. This report presents a mathematical method for handling the complex phase relationships encountered in retrograde condensates; it represents an advance in reservoir behavior technology in that it will aid the development of closed-form mathematical representations of total production systems. A typical phase diagram for a complex hydrocarbon mixture is shown in Fig. 1. When the reservoir temperature T, is higher than the critical temperature Tc, and lower than the critical-condensation temperature Tct' the mixture is a gas condensate. Decreasing the pressure on a condensate while maintaining nearly constant temperature will result in two phases forming at the dew point. Further decrease in pressure will cause additional liquids to be formed. This phenomenon is called retrograde condensation. As pressure continues to decrease, normal phase behavior regions are encountered (liquid vaporizes as the pressure decreases) until the low-pressure dew point is encountered. When a gas-condensate reservoir is produced, gas is withdrawn and the volume of fluids in the reservoir remains nearly constant as the pressure declines. Heavier components tend to accumulate in the liquid phase as a result of retrograde condensation, while lighter components tend to concentrate in the vapor phase. Thus, as the gas is produced the composition of the gas and the condensate

Jan 1, 1970

By R. G. Vardiman, M. R. Achter

Observations of dislocation structure in niobium are presented using two techniques. Triangular pits developed by electroetching are confined to orientations in the stereographic triangle between the (111) pole and planes of the (1ll) zone and require the presence of carbon. Some unusual electroetching phenomena at other orientations are noted. A chemical etch of dislocations decorated by the addition of carbon to 50 ppm reveals the complete dislocation line structure in a surface layer up to 30 p deep, with a resolution of less than 1 p. This effect is independent of surface orientation. The structure of subboundary nets may be resolved for misorientations up to about 1'. Dislocation structures found in strain anneal grown crystals, such as helices, prismatic loops, and high-density areas, are observed. The measurement of dislocation density is discussed and values obtained in different ways are compared. IN the course of some work on the response of refractory metals to thermal-mechanical treatments, it was desired to examine the defect structure of relatively low dislocation density crystals of niobium in bulk form. Surface and bulk methods for the observation of dislocations have been reviewed by ~melinckx,' and include etch pitting, decoration, and various X-ray techniques. The dislocation line structure has been developed by decoration in a few metals, although observations were limited to certain orientations, or by the coarseness and nonselectivity of the precipitate. The most commonly used technique is etch pitting. In niobium, etch pits have been developed chemically'0," in material of high impurity content and electrolyti-cally'' in relatively pure material. In this paper, etch pits developed electrolytically, and the dislocation line structure of a surface layer developed by decoration and chemical etching, are examined, and observations are presented from both techniques. EXPERIMENTAL METHODS Our starting material was electron-beam-melted niobium, swaged to 4 or -in.-diam rod. Chemical analysis is given in Table I. Single crystals were grown by a strain anneal technique using 1 to 2.5 pct of strain and growth temperatures of 1700" to 2300"~.'~ Some crystals grown by zone melting were also examined. The desired surface orientation was exposed either by spark machining or by sectioning with a cut-off wheel and prepared for etching by electro-polishing.

Jan 1, 1969

By A. M. Gaudin

Jan 1, 1962

Pulverized Fuel Combustion The apparatus shown in the illustration is a complete equipment f r supplying coal to boiler and metallurgical furnaces, cement and lime kilns, dryers, and to all furnaces requiring a temperature and quality of fame under prompt and easy control. It is claimed that the Aero Pulverizer makes practicable the highest efficiency obtainable from burning coal. It makes coal burn like a gas, a flame, the physical and chemical character of which is regulable- a flame that may be elongated or shortened, thus placing the zone of highest temperature where needed- a flame that may be made oxidizing, reducing, or neutral, as occasion may require. The coal is burned as pulverized, and there is no storage of the powder with its attendant hazard. Artificial drying before pulverizing is not necessary if the coal supply be sheltered from rain and snow. Where the Aero is used, it is wholly a furnace question whether a dryer should be installed; it is not at all a pulverizing or storage question. Labor is reduced to a minimum. Slack coal at low cost yields its last B.T.U.

Jan 11, 1915

By R. P. Harvey, J. E. Walstrom, A. A. Brown

In view of the large number of wells directionally drilled from offshore platforms and urban drillsites, greater interest is being focused on the directional survey and on the uncertainty inherent in calculating the position of the bottom of the hole, or other benchmarks in the wellbore. Of the two methods presented here for evaluating this uncertainty, the first is analytical and uses the principles of probability and statistics. The second method uses Monte Carlo simulation to generate a pattern of the scatter of possible bottom-hole locations. Both methods are based on a model for which the usual assumption is made that the curvilinear axis of the wellbore is adequately represented by a large number, M, of linear segments joined end to end from the top to the bottom of the hole and closely following the course of the hole. The errors due to this approximation are assumed to be negligible and are not studied here. One form of the model is to consider that for a given hole there exists a perfect set of data describing it, of the above form. Each linear segment has an angle of inclination with the vertical 7, in radians, an azimuthal angle from true north xi in radians, and a length Si, in feet. The subscript variable, i, extends from 1 to M. Each of the M linear segments representing the axis of the wellbore has three components in the X, Y, and Z directions. These components are calculated from the equations: The bottom-hole coordinates as determined from the reference set of data for the wellbore are given by the following for i = 1 to M: X=SX, Y = Sy, Z=SZ; . (2) A directional survey instrument, lowered into the wellbore to the M segments, or stations, measures the values of the 7; and the 3,. In general, because of errors from various sources, the resulting angular measurements will not be precisely equal to the 7" and xi. Random variables l, and Ai are therefore considered with associated probability density functions fi(li) and gi(Ai), respectively, which represent the distributions of potential survey measurements for this hole. Since it is assumed that the values Si are accurately measured they are treated deterministically. The random variables corresponding to the surveyed bottom-hole coordinates are given, for i = 1 to M, by:

Jan 1, 1970

By Olav Mellgren

Part I. The interaction between potassium ethyl xanthate and lead salts has been studied thermo-chemically. It is shown that ethyl xanthate reacts with lead carbonate, basic carbonate, thiosulfate and sulfate according to principles of simple chemistry, whereas reactions with lead sulfite, metasulfite, basic thiosulfate and hydroxide at high pH are associated with secondary reactions. A new compound "xanthogen thiosulfate" is postulated. Part 11. Adsorption of ethyl xanthate on galena has been studied quantitatively and thennochemi-cally. It is shown that an ion-exchange mechanism governs the adsorption process and that the heat of adsorption of xanthate on galena is equivalent to the heat of reaction of ethyl xanthate with bulk lead salts. It is concluded that the entropy content of the surface "compound" on galena is different from that of a corresponding bulk lead salt. Alkali depression is in part shown to be due to the instability of the xanthate-galena system at high pH and to the formation of basic lead salts. Sulfate and carbonate ions are shown to have a stabilizing effect on the xanthate-galena system. PARTI. THERMOCHEMISTRY OF ETHYL XANTHATE AND OF ITS REACTION WITH LEAD SALTS In the past little attention has been paid to the chemistry of lead xanthate. It is known that xan-thates form slightly soluble compounds with lead and that suspensions of lead xanthates in alkaline solution decompose rather readily.' The solubility of lead ethyl xanthate is of the order of 2.6 x 10-6 moles per 1. At increasing pH the xanthate concentration of a saturated solution contains more xanthate. Thus at pH 11 this xanthate content is about 100-fold larger than at pH 7.1 Xanthates are known to be consumed when added to a suspension of slightly soluble lead salts such as lead sulfate and lead carbonate. It is unknown to what extent this xanthate consumption is due to a simple chemical reaction because, frequently, observations are made which reveal secondary reaction products in such reactions. Thermochemical study of the reaction between xanthate and lead salts offers a means to clarify the significance of these reactions as the enthalpy changes can be accurately predicted from heat of formation of lead salts in pure solution reactions. In the present work the heats of formation of lead ethyl xanthate from potassium ethyl xanthate and lead salts are determined and some thermochemical aspects of xanthate in solution are studied. The results of these investigations are presented in Part I. In Part II the heat of adsorption of ethyl xanthate on galena surfaces is presented. All enthalpy changes were measured directly in a microcalorimeter. Calorimeter: The calorimeter used for measuring enthalpy changes was similar to that used by Redinha and Kitchener2 which was based on a description by Derbyshire and Marshall.3 Other useful references4,5 are listed. A sketch of the calorimeter

Jan 1, 1967

By S. G. Gibbs, A. B. Neely

Jan 1, 1967

By E. J. Roberts

Hydrometallurgical operations and many processes in the chemical industry require the separation of dissolved material from solids. One of the decisions which has to be made in designing a plant for such an operation is how this separation shall be accomplished. It is the purpose of this paper to set forth the general principles involved in such separations in order that the optimum flowsheet and equipment may be selected. Countercurrent Decantation with thickeners, or C.C.D. as it is generally known, is, of course, only one way of separating dissolved material from undis-solved. Other unit operations such as Countercurrent Filtration (C.C.F.) and Countercurrent Classification (C.C.C.) are widely used. The same principles may also be applied to centrifugally assisted decantation, as with nozzle or solid bowl type centrifugals, and to separations using screens, either gravity or centrifugal type. Another form of countercurrent washing applicable to granular materials is practiced in continuous ion exchange operations. All of these operations depend on two basic principles, or combinations of these principles. In C.C.D. type operations the solids are concentrated into the smallest possible volume of liquor in each step and the resulting pulp then mixed with a more dilute liquor and recon cen trated, the liquors separated from the more dilute stages being advanced to dilute the more concentrated liquor in a previous solids concentrate, as is shown in Fig. I. This will be termed the solids concentration-solution dilution principle, or, for short, solution dilution. countercurrent decantation- type circuits. The second principle used in washing solubles from solids is that of solids concentration-solution displacement. Here the solids are restrained from movement while wash solution is forced through the interstices in a counter-current fashion, as in Fig. 2. In the simplest application of this principle, once the "cake" has been formed, it is not disturbed until the operation is completed. In continuous filters, the cake is merely moved under the successive washes and the displaced filtrates removed as in Fig. 4. Often, however, after one or two displacement washes, a repulping step is introduced, the cake reformed and washed again. This procedure brings the solution dilution principle into play as well as the solution displacement principle. Merely thickening ahead of filtration, which is often operationally advantageous, does not hybridize he circuit. It still can be a pure solution displacement operation from the washing

Jan 1, 1961

By H. J. de Haan, L. Schenk

Scope for Thermal Recovery in Shell's Heavy Oil Fields in Venezuela The main heavy oil reservoirs on the East coast of Lake Maracaibo (Fig. I), known as "Bolivar Coast", initially contained some 20 billion bbl of oil in place with gravities in the range of 10 to 15° API. The current total production rate is about 400,000 B/D. Since the recovery to date is on an average only 12.5 percent of the initial oil in place, these fields offer a vast potential for secondary recovery methods. The reservoirs are characterized by moderate depth (generally 1,000 to 3,000 ft; maximum 5,000 ft), good formation properties such as net oil sand thickness (50 to 300 ft), high porosity (30 to 40 percent) permeability (1 to 3 darcies) and oil saturation (initially about 80 percent) and high oil viscosity (100 to 10,000 cp in situ), all of which are favorable for the application of thermal recovery processes. Since 1957, steam drive, steam "soak" and underground combustion have been tested or are being tested in this area.1-3 This paper deals with a major steam drive test in the Tia Juana field. The test was commenced in Sept., 1961, on the basis of encouraging results of laboratory experiments and pilot field tests, which will be discussed briefly. Early Laboratory Investigation of the Steam Drive Process In 1956 a series of model experiments was carried out in the Koninklijke/Shell Laboratorium, Amster- dam, to investigate the displacement of heavy oil by steam.' The prototype studied was a horizontal, un-consolidated heavy oil reservoir, subjected to a linear steam drive. The model, representing a slab from this reservoir along the main flow direction, consisted of a steel tube filled with oil-saturated sand, provided with layers of rock at the top and bottom to simulate conductive heat losses to cap and base rock. Lateral heat losses, perpendicular to the main flow direction, were minimized by insulating the sides of the model. Heat flow and viscosity and gravity forces were scaled by taking the steam injection rate and sand permeability inversely proportional to the geometric reduction factor of the model, and using materials (oil, steam, cap rock, etc.) identical with those of the prototype. The main feature of the process was a frontal displacement mechanism that was observed within wide ranges of injection pressure and rate, oil viscosity, initial oil saturation and sand permeability. The high stability of this front can be attributed to the high volumetric steam flow rates, combined with the reduction in oil viscosity. High recoveries were obtained due to the low residual oil saturation of about 15 percent in the zone swept by steam. The latter value pertains to the specific test conditions (heavy oil, uncon-solidated sand) and may be lower for light oil, due to the effects of steam distillation. The applicability of this experimental approach is limited, as it does not take into account the fact that

Jan 1, 1970