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By Robert E. Bush, E. S. Mardock

The objective of this paper is to present practical methods of applying radioactivity logs to problems of interest both to those engaged in evaluating fundamental reservoir data as well as to those engaged in subsurface structural work. The basic theories underlying the operation of radioactivity logging methods are briefly discussed along with some of the problems arising in the interpretation of the log. Relative methods of quantitative interpretation are described, with a discussion of relative reference lines and specific examples are given showing the application of these relative quantitative interpretation methods. To show the variation of the methods described, specimen wells penetrating formations widely divergent in point of geologic age were selected to demonstrate the application. A relative reference line is determined for the Neutron Curve and by comparison to known petrophysical data such as porosities from diamond cores, a direct quantitative relationship is developed. The application of this relative calibration curve to logs of unknown wells will permit a reasonably accurate determination of porosity in limestone and dolomite formations. Specific examples are given showing the application of these relative methods of interpretation to logs of the Smackover limestone in Louisiana, the Edwards limestone and dolomites of South Texas, and Permian dolomites of West Texas. Radioactivity logs have been used extensively by the petroleum industry for a number of years and recognition of their value has grown steadily, not only as tools to aid in the solution of specific stratigraphic problems, but also as potential sources of the basic data necessary for the estimation of net pay and reserves. The value of radioactivity logs for stratigraphic work has been pointed out in the literature,1,2,4,5,6 and now has long been recognized by the industry, but the quantitative application of the logs has advanced but little beyond the stage of a strong conviction that radioactivity logging curves will some day provide the information on such important quantities as the porosity and the liquid saturation of the formations. During the past few years the staffs of the Lane-Wells Company and Well Surveys, Incorporated, have devoted a great deal of time, thought, and experimentation to the relationships existing between radioactivity curves and the lithologic conditions encountered, and this paper is, in a manner of' speaking, intended as a progress report of this work and includes suggestions which the authors have found useful in the interpretation of radioactivity logs. The section on theory is not intended as a complete exposition of the physical processes involved, but rather as a brief introduction to the reader of these processes so that he may acquire a better understanding of the behavior of the radioactivity curves under the varied conditions encountered in normal well logging. Three relative methods for using neutron logs for the quantitative estimation of porosity in limestone or dolomite are presented. These methods are based on the comparison of logs and porosity data from wells in Louisiana, South Texas, West Texas, and New Mexico. These areas were selected because not only were there more core data available from these areas but also the majority of these data were from limestone or dolomitic zones. The correlation between core data and logs is simpler for limestones and dolomites than it is for sandstones due to the fact that sandstones are more complex than limestones and differ more widely among themselves as to composition of cementing materials, siltiness, etc. When data applicable to the various types of sandstones are available, the authors hope to present a discussion similar to this paper covering sandstones or possibly a more general discussion covering all types of reservoir rocks. The relative methods for estimating porosity which are presented in this paper fall short of the absolute method sought. However, these methods possess the advantage that they can be applied to almost any neutron log as long as the range of application is held within the limits imposed by the local lithologic conditions which prevailed during calibration, i.e., these methods are for short range application only. THE THEORETICAL BASIS FOR RADIOACTIVITY LOGGING The two redioactivity logging curves commercially available today are the

Jan 1, 1950

By Ben-Zion Weiss, Melvin R. Meyerson

Chromium diffusion coatings on commercial Armco iron lead to carbide precipitation at the grain boundaries in and below the coatings. High compressive stresses are introduced into the coating and, as a result, tensile stresses are introduced into the base material below the coating. In coated samples, fatigue cracks form at the grain boundaries below the coating after only a limited portion of the total lifetime (5 to 10 pct). Residual tensile stresses and a stress concentration caused by precipitated carbides seems to be responsible for early crack nucleation. Stage I of Propagation may be divided into two substages: I-a in which the crack Propagates along grain boundaries, and I-b in which the crack propagates along slip boundaries according to a shear mode. In uncoated samples, the cracks form at slip bands after 40 to 50 pct of the total lifetime. In coated samples the Propagation process takes longer than in uncoated samples because of the moderate rate of crack extension until the crack breaks through the coating. The chromium-diffusion coating causes little if any increase in fatigue life. CHROMIUM diffusion is one of the most popular processes used to apply coatings to iron alloys. This popularity stems from the fact that the diffusion treatment is comparatively easy to carry out, and it improves certain surface properties such as corrosion and wear resistance as well as some other properties. Very little effort has been devoted to the investigation of the effect of chromium-diffusion coatings on mechanical properties and particularly on fatigue properties. Since the chromium coating usually represents a small fraction of the total volume of the base material it is generally assumed that the macro properties are dependent principally on the base material rather than the coating. Insofar as fatigue is concerned, there are indications that the fatigue life of the chromium coating is not less than that of the basic material and the fatigue properties are generally not reduced by it.' But chromium diffusion causes drastic structural and chemical changes in the region of the material surface2-4 which introduce additional residual stresses. Such changes must affect fatigue crack nucleation and may sometimes affect the initial stages of propagation. Furthermore, it is conceivable that the secondary stages of the crack propagation could be influenced by some irreversible structural changes in the core of the material, which stem from the long-time heat treatment at high temperatures required to apply the coating. This paper analyses the structural and compositional changes produced in commercial Armco iron by a chromium-diffusion coating and the effect of the coating on fatigue crack initiation and propagation. EXPERIMENTAL PROCEDURES The investigations were carried out with commercial Armco iron. The chemical composition of the iron, the number of specimens tested, the grain size produced during chromizing and heat treating, and the thickness and microhardness of the chromized layers are shown in Table I. Samples were chromized by a gas diffusion process. The temperature and time of the diffusion coating process were chosen according to a previous grain growth study. It had been found that at a temperature of 970°C and a holding time of between 3 and 9 hr there are practically no changes in grain size. To describe the grain size more accurately the ASTM method5 was supplemented by a statistical analysis of the mean volume diameter as outlined by Fullman6 and The The mean volume diameter was deter- mined from D = p/2m where D is the mean volume diameter, and m is the mean reciprocal value of grain diameters as seen on the micrograph. The shape and the size of the asymmetrical sample, see Fig. 1, were chosen so as to facilitate the study of fatigue crack initiation. Before coating, the samples were machined and the surface of the groove was polished. After chromizing, the two side surfaces were machined and polished so as to retain the coating only on the top surface of the groove. Residual stress in the chromized layer was measured on the top of the grooved section of the specimen after the diffusion process. The inclined incident X-ray beam procedure was used.9'10 The computations were performed with the initial assumption of a zero surface normal stress component. An electron microprobe analyzer was used to obtain the relative amounts of chromium and iron con-

Jan 1, 1970

By W. C. Hayes

The site selected for the United States prototype pumped storage project of Union Electric CO. was Proffit Mountain, five miles from Taum Sauk, the highest point in Missouri. Factors influencing final location were: high local relief; satisfactory rock type and structure; and an economic location in respect to existing transmission systems. The upper reservoir was constructed by excavating rhyolite porphyry from the crest of Proffit Mountain and constructing a rock fill dike encircling the area to form a 4350-acre foot reservoir. A 6564-ft tunnel connects the upper reservoir with the generating and pumping facilities. A concrete gravity dam on the East Fork of the Black River forms the 6350-acre foot lower reservoir. Precambrian rhyolite porphyry forms the crest of Proffit Mountain and the floor of the upper reservoir. The tunnel was excavated in rhyolite prophpy, granite porphyry, dolomite, shales and conglomerate. Abutments and the foundation of the gravity dam are in rhyolite porphyry, and much of the valley floor of the lower reservoir is underlain by dolomite and shale. Core drilling provided data on soundness of rock type, structure, depth of weathered zone and potential water loss in the fractured igneous rocks. After a six-year study of pumped storage and cost comparison with alternate stream generating units, the Taum Sauk pumped storage project was authorized by Union Electric Co. on Dec. 11, 1959.' The site selected is located in the St. Francois Mountains of southeast Missouri approximately 90 miles south of St. Louis (Fig. 1). The lower reservoir was provided by damming the East Fork of the Black River, a small tributary of the Black River with a minimum flow of about 1 sec ft. Construction of the upper reservoir was effected by quarrying the crest of Proffit Mountain - five miles from Taum Sauk Mountain, the highest point in Missouri — to provide material for a rock fill dike surrounding the quarried area. This provided a 55-acre mountain top lake with a water depth of 92 ft (Fig. 2). A vertical shaft and tunnel connect the upper and lower reservoirs through the two reversible pump-turbine motor-generator units operating under 800 ft of hydraulic head (Fig. 3). The output rating of the plant is 350,000 kw with daytime generation of about 2.2 million kw-hr under normal use. Night pumping will replenish water to the upper reservoir in about 91/2 hours3. The automatic operation is remotely controlled from the Osage plant and from the dispatchers office in St. Louis. GENERAL GEOLOGY Mountains of the St. Francois area consist of Precambrian granites, granite porphyries, extrusive fel-sites and basic dikes. Basal conglomerates overlain by Upper Cambrian Bonneterre dolomites and shales onlap the exhumed Precambrian knobs and hills and are exposed in the narrow valleys. Cambrian and Ordovician residuum as much as 200 ft thick is present on the slopes of many hills. Proffit Mountain consists of rhyolite porphyry and granite porphyry. All excavation for the upper reservoir was in rhyolite porphyry, and the same rock is present under the Bonneterre at the plant site and under alluvium at the lower reservoir dam site. The region has been dissected to the stage of early maturity with only small upland flats remaining. Considerable local relief (a requisite for the project) approaches 1000 ft. Streams flowing across the Precambrian ridges have formed restricted narrows, termed shut-ins. A shut-in approximately two miles downstream from the plant site provides an excellent site for the lower reservoir dam. TEST BORINGS Preliminary to final approval of the project, 12 test borings were made to determine subsurface geologic conditions (Fig. 2). Drill hole No. 12 at the lower reservoir dam site showed 20 ft of alluvium over solid rhyolite porphyry. Drill holes No. 1, 2 and 3 were drilled in the tail race area to depths of 66 ft, 75 ft and 95 ft respectively, and all bottomed in Bonneterre. Drill hole No. 4 at the plant site provided NX core to a total depth of 98 ft in Bonneterre. Drill

Jan 1, 1965

By J. Szekely, Robert G. Lee

Calculations are presented for the prediction of the combined radiative-convective heat loss from molten steel held in a ladle, covered by initially molten slag. A mathematical formulation is given and numerical solutions are presented of the resultant partial differential equation. It is shown that a slag layer of about 2 to 3 in. thick would prevent any significant heat loss from the top metal surface for Periods of up to 1 hr. For thinner slag layers (or in the absence of the protective slag) appreciable heat losses would occur; plots given in the paper allow the quantitative evaluation of the fall in the metal temperature due to this heat loss. The ironmaking-steel processing operation involves several intermediate steps where the molten metal is held or transfered in ladles. The quantitative assessment of the heat losses occurring under these conditions is of considerable importance in process design considerations since the temperature of the metal may have to meet rigid specifications in any given part of the processing sequence. While the metal is held in a ladle, heat is lost by two mechanisms: i) by conduction into the ladle walls; ii) by radiation and convection from the top surface. Calculations relating to the conductive heat loss, are readily made and information may be found in the literature both on data pertaining to metallurgical situations and on the techniques that are available for performing additional computations.'-3 The evaluation of the combined convective-radiative heat loss is less straightforward, especially when there exists a protective slag layer covering the metal. In this latter case, as the top slag surface loses heat partial solidification may occur and the latent heat thus given up by the slag may represent an effective barrier to the heat loss from the metal. A semiquantitative assessment of the role played by the slag in preventing heat loss from the metal has been made in a previous paper,4 where it was shown that a slag layer 6 in. thick would act as a near-perfect insulator for periods of up to 2 hr. However, this first paper reported on an essentially preliminary investigation that considered only one slag layer thickness; furthermore, the boundary conditions used for the calculations were somewhat restrictive since no allowance was made for changes in the metal temperature. The purpose of this second paper is to extend the scope of the preliminary investigation previously reported by: i) considering several slag layer thicknesses; ii) allowing for variations in the metal temperature; and finally iii) by performing calculations on the net loss from the metal rather than from the slag surface. FORMULATION Consider a slag phase extending from y = 0 to y = L1, covering a metal phase that occupies the region extending from y = Ll to y = L, as illustrated in Fig. 1. Denote the slag and metal temperatures by TS and Tm and assume that initially both slag and metal are molten, having a uniform temperature Ti. At time = zero the surface represented by the y = 0 plane (top slag surface) is brought into contact with cold air, the temperature of which is given as T Thus for time > zero, heat will be transfered from the slag to the air by natural convection and thermal radiation; as a result of this heat loss the slag temperature will fall and after some time a solid phase is formed and a solidification boundary (more realistically described as a zone) will move progressively from y = 0 toward y = L1. Once the region of temperature gradients, moving ahead of the solidification zone, reach the slag-metal interface (y = L1) there will be a net transfer of heat from the metal through the slag to the cold air, across the y = 0 plane. In the formulation of moving boundary problems, involving phase changes that require computer solution, it is convenient to represent both phases by a single equation, making allowance for the latent heat of solidification by assigning an appropriate temperature dependence to the specific heat content. Thus the energy equation for the whole of the slag may be written as follows:

Jan 1, 1969

By J. M. Karpinski, R. O. Tervo

A method and equipment have been developed for measuring the impact strength of grains of brittle materials. It is shown that brittle materials develop a characteristic particle size distribution when fractured by impact. A simple mathematical model has been found to describe this distribution, and one of the parameters of the model has been designated the r value. The r value is directly proportional to impact energy and, for fixed impact energy, it becomes a useful criterion of grain strength. Data are presented on the variation of the r value as a function of sample history, initial size, energy input and number of impacts. The results are interpreted in terms of the flaw theory of brittle fracture. The view is now widely held that brittle materials comprise a strong matrix, throughout which flaws or points of weakness are scattered at random. Failure always starts at one or more of these imperfections, and planes of fracture are established by the geometry of the flaw distribution. This view has been developed extensively by Weibull 1,2 and experiments of a confirmatory nature have been reported.3,4 Thus the process of fracture or size reduction of brittle materials can be regarded as a process of elimination or creation of flaws, and the concept of strength is intimately connected with the size and history of the specimen tested. One consequence of the point of view described above is that brittle materials will fracture to yield similar size distributions, although the impact energy to produce a given amount of fracture may vary greatly from one material to another. Generally speaking, experimental investigations of brittle fracture in solids have been confined to two extreme experimental situations. On one hand, we have tests on single specimens of well-defined, but artificial, geometry and, on the other, empirical data have been obtained on the feed-product relation in a variety of mills. The first situation necessitates specimen preparation, which in the case of brittle materials is equivalent to a priori size reduction, while the second one suffers from the disadvantage that little knowledge is gained about individual fracture events. Also, the statistical significance of single specimen tests may be questioned. Our approach lies somewhere between these two extremes. We test a large population of sized specimens and yet subject each specimen to a single fracture event. In 1956 G.H. Fetterley of Norton Co., Chippawa, Ont., made the empirical observation that product size distributions obtained from impacting sized grits can be described by the following equation where R is the proportion by weight of the grain that remains on a screen having an opening x on a side, x, is a parameter having the dimensions of length, and r is a number. This equation has since been derived on a theoretical basis by Gaudin and Meloy.5 They identify x, with the initial size of the test piece and r with the number of flaws per unit length. As will be shown below, our experiments indicate that both x, and r are functions of energy and hence they should more properly be called the effective initial size and the effective number of flaws respectively. Also, our empirical data give us no basis for assuming that r represents the effective number of flaws per unit length, rather than per unit volume. METHOD AND MATERIALS The impact test machine has been designed to feed specimens, essentially one at a time, into an evacuated chamber, where they fall freely and are struck with random orientation by one or the other of a pair of flat steel vanes. The vanes are mounted at opposite ends of a steel bar, which rotates at a closely controlled angular velocity about a vertical axis. Fig. 1 shows the flat circular vacuum chamber with the cover removed, and the horizontal steel bar with the steel vanes at the ends. The cylindrical pot in which the grains are collected after impact appears at the left. Fig. 2 shows the equipment assembled for a test. The vacuum chamber occupies the central position with the variable speed drive below the table surface, the vacuum pump at the extreme left

Jan 1, 1964

By T. H. Alden

A correlation has been found in rock-salt structure single crystals between the latent hardening, measured by the direct stress activation of oblique slip systems, and the stress-strain behavior in simple compression. Materials with high latent hardening, like LiF, strain-harden at a low rate (Stage I) even when severely constrained. KCl, in contrast, shows low latent hardening and a tendency to strain-harden at a high rate (Stage 11). This correlation suggests that oblique slip is essential for Stage II hardening of these materials. THE role of secondary slip in the strain hardening of metal single crystals is a topic of lively controversy. On the one hand are theories in which secondary dislocations participate directly in Stage II hardening in the fcc metals, for example through the production of sessile dislocations,1 forest intersections, or jog formation. Much of the experimental evidence on which these theories are based has been reviewed by Clarebrough and Hargreaves.~ On the other hand, a recent theory5 denies that secondary slip has an essential role in Stage II hardening or in the transition from Stage I to Stage 11. In the latter view, Stage I is not terminated by an increase in the activity of secondary systems but by the exhaustion of undeformed material.6 The experiments reported in this paper will not resolve this controversy since the materials being studied are cubic ionic crystals rather than metals. However, the results do show in an unusual way a direct connection between "secondary" (nonortho-gonal or oblique) slip and strain hardening in these materials. Specifically, a correlation has been found between two independently measured properties, first the latent hardening of oblique (110)(1i0) slip systems as measured by direct stress activation of these systems, and second the stress-strain behavior at small strains. From prior work, it was known that in most cubi-cally oriented rock-salt structure crystals, two orthogonal slip systems operate and exclude the other equally stressed pair, oblique to the first pair.7'8 This observation apparently indicates that a significant interference exists between slip on oblique (110) planes and a relatively small interference between orthogonal (110) planes. The present experiments were begun with the intent of obtaining a quantitative measure of this difference by means of a study of latent hardening in these crystals. I) EXPERIMENTAL METHODS The experiments were basically of two types, first the determination of stress-strain curves by compression along a single (100) axis, and second the measurement of latent hardening by compressive prestrain along one cube axis followed by the determination of the yield stress in a second (latent) cube direction. All tests were done at room temperature in an Instron machine by compression between lapped, parallel steel faces. Three specimen shapes were used. For long crystals (nominal dimensions, 1/8 in. square by 1/2 in. long) the ends were lubricated with an oil-graphite mixture. Superior results with short crystals (about 1/8 in. cube) were obtained using 0.003-in. teflon film.' Thin crystals (1/4 in. square by 3/32 in.) were used for latent-hardening measurements and similar results were obtained with either lubricant. Test specimens were cleaved from Harshaw single crystals which had been irradiated to a dose of lo8 roentgen using a cobalt-60 source. The irradiation raises the yield stress and tends to prevent plastic deformation during sample preparation.10 Prior to testing, the irradiation hardening was removed by an anneal at 400°C. Ideal compression specimens have flat, parallel faces. In short specimens particularly, satisfactory results demand a close approximation to this ideal. In the present work, cleaved surfaces were often used directly as compression faces. The degree of success using this method depends on two factors: 1) the smoothness of cleavage faces, and 2) the extent to which the crystal is deformed or crushed by the chisel during the cutting of a long crystal into short pieces. Unfortunately, only one material of those studied, LiF, was completely satisfactory. NaF, NaC1, KC1, and KBr behaved less well so that

Jan 1, 1964

By L. W. Pommier, F. B. Brien

In order to determine the ability of cyclones with heavy liquids to preconcentrate ores, a study of the variables which govern the behavior of the solids in the apparatus has been made. To assess the test results, the cyclone products have been examined by sink and float analysis at various specific gravities and the results examined by the Tromp type curves. This analysis has allowed the development of the SG50 unit — specific gravity of the particles, 50% of which goes to overflow and 50% to underflow — rather than the d50 (size) unit used in classification. The results of tests using the closed circuit laboratory cyclone assembly with dry feed samples show the validity of the equation: Results indicate that 83% of the feed may be rejected containing 0.1% Sn. Recoveries in excess of 80% are obtained at a grade of 1.7% Sn from feed samples assaying 0.4% Sn. As water-wetted particles may comprise the plant feed, separate tests were performed to examine the effect of water in the feed material. Results indicate that the entrained water divides into two fractions, one of which is defined as free water and is rejected to the cyclone overflow, the other fraction forms an adhering envelope of water on the ore particles, altering their effective size and density. The presence of the envelope of water on the particles increases the ease with which the heavy liquid can be recovered but decreases the concentration efficiency. It is proposed that the detrimental effect of water in the cyclone may be minimized by using a higher feed pressure cx by the use of surfactants. A higher feed pressure, by increasing shearing forces, would reduce the thickness of the water envelope on the particles. The surfactants, by adsorbing on the particles and producing hydrophobic surfaces, would displace the water envelope and allow the heavy liquids to wet the modified surfaces. In both cases a larger proportion of the entrained water would report to the cyclone overflow as free water, thus minimizing the detrimental effect of water on the concentration efficiency. Additional testing is required on the behavior of water in the system; to determine the optimum particle size for the preconcentration step; to determine final particle size for optimum liberation and subsequent treatment of the products in present plants and to determine the efficiency with which the heavy liquids may be recovered from the products. For many years tin mining in Bolivia has been very important to the economy of the country. In recent years the tin content of the ore reserves has been steadily declining. An improvement in concentration efficiency is highly desirable in order to increase productivity from the present low-grade mine ores and to allow retreatment of the many millions of tons of tailings from past operations, some of which equal the present ores in tin content. A number of investigators have been or at present are working on various phases or approaches to the problem. Gravity concentration is used in Boliva today as it has been in the past to recover tin minerals from the mine ores. An objective of the work reported in this paper was to examine the possibility of treating present low-grade ores and sink-float tailings products, at a relatively coarse grind, in order to produce a higher grade feed material to the present gravity concentration plants. The possibility of using heavy liquids in cyclones to treat large tonnages with a minimum of outlay presented itself and is of particular interest since heavy liquids are now available with physical properties which lend themselves to simple recovery methods. Tests were carried out using a closed circuit laboratory cyclone assembly. It was desirable to determine the value of using the SG50 concept and Tromp curves for analyzing the cyclone concentration test results. The effects of entrained water on the behavior of ore particles in the cyclone were examined. THEORY AND TECHNICAL CONSIDERATIONS Three types of heavy liquids are available: aqueous solutions of very soluble salts, salts or mixtures of

Jan 1, 1964

By A. E. Wraith, N. J. Petch, J. D. Embury, E. S. Wright

The two most important parameters controlling the fracture behavior of a solid are its intrinsic properties, e.g.,grain size, and the operative stress system. The latter may be modified in laminates by the presence of weak interfaces. This is studied in notch-impact tests on a mode1 system of mild steel laminates containing a variety of interfaces. The effect of these is evaluated in terms of the ductile/cleavage transition. Two laminate geometries are distinguished, here called "crack-arrester " and "crack-divider". In both, cleavage is inhibited. This arises because of relaxation of a state of triaxial tension. In the crack-avrester laminates, cleavage initiated at a notch is confined to the layer containing the notch. In crack-cliuider laminates, a thick specimen behaves as the Sum of a number of thinner ones. Additional benefit may derive from improved intritnsic propevties of- the lanlinate layers arising from greater deformation in their manufacture. It has long been recognized that the two most important parameters controlling the fracture behavior of solids are their intrinsic properties (e.g., grain size friction stress,3 distribution of second phase particles4) and the operative stress system under which fracture occurs. In solids that show a ductile/cleavage transition, cleavage is favored by the presence of a notch. This is because triaxial tensions, generated by the localized plastic constraint at the notch, are operative when fracture occurs.= Anything that suppresses these triaxial tensions will be unfavorable to cleavage. Such suppression may possibly occur in laminates containing weak interfaces and the purpose of the present paper is to explore this possibility. Two basic laminate geometries, here termed "crack-avrester" and "cvack-divider", are examined. They are illustrated in Fig. 1. With the crack-arrester laminates, there is the possibility that, when the fracture crack approaches the interface, this, if weak, may delaminate due to the tensile stress acting parallel to the plane of the crack.= If this happens, energy will be used in delamination, the crack will be completely blunted, and the triaxial tension associated with the crack will be relaxed. To fracture the second portion of the laminate, crack reinitiation will be necessary and, because of the relaxation of the triaxial tension, this reinitiation will occur under conditions of nearly uniaxial tension, which are unfavorable to cleavage. Thus there is the possibility of cleavage suppression in the second and subsequent subunits of a crack-arrester laminate. With the crack-divider geometry, there is again the possibility of delamination at the interfaces. This will divide the crack into a series of cracks propagating through the individual laminate subunits. If these are sufficiently thin, the triaxial tension will be relaxed towards a state of biaxial tension in each of them. Thus, with the crack-divider laminates, there is again the possibility of cleavage inhibition. In the present work, these possibilities are explored using a notched impact test on mild steel laminates bonded with soft solder, silver solder or copper. Even if delamination does not occur, it is still possible that cleavage may be inhibited in laminates. With the crack-arrester geometry, the cleavage crack in the first layer may be blunted and arrested by plastic deformation in the laminate bond, if this is ductile. Partial relaxation of the stress transmitted ahead of the crack into the second layer will then result and this will reduce the significance of this stress in the fracture of the second layer. With the crack-divider geometry, there cannot be much effect in the absence of delamination unless a large amount of energy is absorbed in rupturing the ductile material. EXPERIMENTAL DETAILS The composition of the mild steel (wt pet) was: 0.04 C, 0.29 Mn, 0.01 Si, 0.006 P, 0.008 S. "As-received" plate was annealed for 2 hr at 900°C and slowly cooled to give a grain size of 0.04 mm. The laminates were made by brazing or soldering together mild steel plates 8 by 3 in. by various thicknesses. These were obtained from the annealed plate by machining, so that the intrinsic material properties were .kept constant. Laminates containing two to six steel layers were studied using standard Charpy V-notch specimens cut from the bonded plates. Standard homogeneous specimens from the annealed plate and subsize ones from the laminate components

Jan 1, 1968

By T. A. Pollard, C. R. Sandberg, E. B. Elfrink

This paper presents an evaluation of compressibility factor data and a discussion of their application to the estimation of gas reserves. A correlation is presented which provides compressibility factors for use in both two-phase and single-phase hydrocarbon systems. Accuracies comparable to those obtained previously for single-phase systems only can be expected. A simple means of predicting the presence or absence of a liquid phase in a condensate system of known composition is illustrated. The correlation is based on 1,030 compressibility determinations from 21 hydrocarbon samples taken from eight oil fields. Of the data used, 75 per cent were from California, 15 per cent were from the Mid-Continent area, and 10 per cent were from South America. The average numerical deviation of the experimental data from this compressibility chart is 1.22 per cent. Charts and tables are included and discussed which illustrate the errors involved through the misuse or nonuse of compressibility factors in estimates of gas-in-place. INTRODUCTION The compressibility factor is a coefficient which expresses the deviation of a gas of given composition from the Perfect Gas Laws. A factor such as this is necessary in any calculation involving volumes of gaseous mixtures, and finds extensive application in the estimation of natural gas and condensate reserves. It is used in the decline curve, the volumetric, and the material balance methods of gas reserves estimation. The behavior of gases at high pressures has been investigated extensively in recent years and considerable data have been assembled on the compressibility characteristics of a number of gases. Notable among the investigators of high pressure gas relationships are Kvalnes and Caddya, Kay" Sage and Laceys, and Brown, Standing" and Katz4. Other contributors are Smith and Watson, Roland and Kaveler', and Stevens and Vance". The data on compressibility factors assembled by these investigators have been presented and correlated in numerous ways; particularly noteworthy is the method first presented by Kay5 which relates compressibility factor "Z" to pseudo-reduced temperature and Pseudo-reduced pressure. Other investigators have used this empirical relationship successfully and numerous charts covering a large number of gases have been constructed on this basis. It is the purpose of this paper to evaluate compressibility factor data and to illustrate the importance of their proper use in the estimation of gas-in-place for both gas and condensate reservoirs. EVALUATION OF COMPRESSIBILITY FACTOR DATA The compressibility chart presented by Standing, Katz, Brown and Holcomb in 1941 is probably the most recent and reliable chart for natural gases. The reliability of the Katz chart has been investigated by the writers for a fairly large number of gases (single-phase) in the pressure range from 500 to 10,000 psia and temperature range from 80 to 400°F. A summary of this comparison is presented in Table I. The numerical average deviation of the chart compressibility factors from the experimental compressibility factors is 1.05 per cent, and the algebraic deviation is -0.28 per cent. The Katz correlation appears to be quite accurate for single-phase hydrocarbon systems. It was based on single-phase systems and does not necessarily provide a means of accurately predicting the behavior of two-phase systems which might be encountered in condensate work. Data published recently by Sage and Oldsl' have enlarged the knowledge of phase behavior in condensate systems by covering extensively the Compressibilities of systems in the two-phase as well as single-phase regions for a wide range of temperatures, pressures and gas-oil ratios. An evaluation of these data indicates that conditions can arise, especially in condensate systems having fairly low gas-oil ratios, in which two phases occur and the usual gaseous compressibility factors do not accurately apply. The measured PVT data of Sage and Olds covering two-phase systems have been correlated with additional such data from the Mid-Continent area and South America; these are presented in Fig. 1. This chart is the result of 1,030 compressibility* determinations from 21 hydrocarbon samples taken from eight oil and condensate fields. Of the data used, 74.75 per cent were from California, 15.45 per cent were from the Mid-Continent area, and 9.80 per cent were from South America. The chart construction is based on the original

Jan 1, 1949

By W. G. Pfann

The simultaneous segregation of two solutes during the directional solidification of an ingot is treated mathematically on the basis of simplifying assumptions. Expressions are derived for the difference in concentration of two solutes, and for the location and concentration gradient of a pn barrier formed in a semiconductor by the segregation of a donor and an acceptor. THE problem of normal segregation of a single solute during the freezing of an alloy has been treated mathematically by a number of investigators. Gulliver' showed that coring increases the quantity of eutectic above that to be expected at equilibrium, for a system having limited solid solubility and, on the basis of simplifying assumptions, calculated the fraction of eutectic to be expected. Scheuer2 expressed composition of solid solution in terms of a distribution coefficient and the fraction solidified and compared experiment with calculation for the systems A1-Cu, Al-Zn, Cu-Sn, Cu-Zn. Hayes and Chipman,3 in a detailed study of segregation in a low carbon, rimming steel ingot, calculated distribution coefficients for a number of solutes in iron, compared calculated and experimental segregation curves, and discussed the effects of process variables such as rate of solidification and stirring. In the present paper a mathematical analysis is made of the simultaneous segregation of two solutes during the orderly freezing of a solid solution system, with particular emphasis on the difference in solute concentrations. Although the analysis is quite general and can be applied to the segregation of minor elements in alloys, it is directed in particular at the solidification of a semiconductor containing a donor and an acceptor. Normal segregation has unique aspects in a semiconductor, because of the ways in which donors and acceptors affect the electrical properties. The difference between two solute concentrations becomes of importance, as does also the gradient of the difference where the difference goes through zero, this being the concentration gradient of excess carriers at a pn barrier. A primary object of this paper is to extend the mathematical treatment of segregation to include these newer aspects which are of particular significance for semiconductors. One property of interest is the electrical conduc- tivity, which arises from the presence of donors 'or acceptors in solid solution. The conductivity may be either n-type or p-type depending on whether donors or acceptors, respectively, are in atomic excess. For both germanium and silicon, elements of Group V of the Periodic System, such as P, As, and Sb, are donors and elements of Group 111, as B, Al, In, and Ga, are acceptors.4-6 If a donor or acceptor is present alone in solid solution, the conductivity is proportional to its concentration." If both a donor and an acceptor are present, then the conductivity is proportional to the difference in their atomic concentrations. If the donor and acceptor segregate at different rates then a pn barrier in certain circumstances may form at some point in the ingot. Accordingly, equations are derived and illustrated which express the effect of segregation on: 1—the concentration of a single solute with a discussion of the assumptions; 2—the difference between two solute concentrations and means for minimizing its variation in an ingot; and 3—the location and concentration gradient of a pn barrier. The analysis is applicable to processes in which the entire charge is melted and then progressively frozen from one end. The method in which an ingot is solidified in a crucible7 and that in which a solidifying rod is pulled from the melt8 both fall into this category. Segregation of One Solute If a cylinder of molten alloy is caused to freeze slowly from one end, a normal segregation of solutes will usually occur, producing a lengthwise concentration gradient in the ingot. Depending on whether a solute raises or lowers the melting point of the solvent, it will become concentrated in the first or last regions, respectively, to freeze. If it is assumed that freezing is such that there is no diffusion of solute in the solid, complete diffusion in the liquid, and that k, the distribution coefficient, defined as the ratio of solute concentration in the just-freezing solid to that in the liquid, is constant, then the

Jan 1, 1953

By H. C. Chang, N. J. Grant, A. R. Chaudhuri

During the creep of coarse-grained polycrystalline magnesium at elevated temperatures, a nonbasal type of slip was found to play an important role in the deformation processes. The nonbasal slip traces were examined metallographically in eight specimens (13 grains) and the observed glide plane located stereographically for each grain. The tests were run at 500&apos; and 700°F at stresses of 148 to 786 psi. Based on these measurements and theoretical calculations, the crystallographic elements for nonbasal slip were determined. WHEN a metal deforms by slip, the conventional appearance of the slip bands on the surface of a specimen is that of straight lines. Such is the behavior of the face-centered-cubic metals, as for example, aluminum. The particular slip system on which slip occurs in these metals is governed by the criterion of resolved shear stress. Work on the body-centered-cubic metals a-iron,&apos;. &apos; molybdenum, and columbium4 has shown that the process of slip is somewhat more complicated than the simple gliding of one close-packed plane of atoms over another in a close-packed direction and that it results in the formation of wavy and irregular slip traces on the surface. The recent reviews and experiments of Vogel and Brick and Chen and Mad-din3 show that, for the body-centered-cubic metals, the resolved shear stresses along the planes and the degree of close-packing do not necessarily determine the slip system. Theirs and other investigations indicate that a complete understanding of the slip process in the body-centered-cubic metals is not yet possible. However, one behavior displayed by all these metals is that the slip direction is invariably one of the close-packed directions <11l>. The wavy nature of the slip-band traces has been explained on the basis of cooperative slip by planes sharing this same slip direction.1&apos;3l&apos; It is generally acknowledged that, when the hexagonal-close-packed metal magnesium (axial ratio c/a = 1.624) deforms by slip at room temperature, it does so by basal slip in the close-packed direction <1I%>. This type of slip has the conventional appearance of straight lines and is governed by the critical shear-stress law. Schmid and coworkers" showed that basal slip was operative in the temperature range of —185" to 300°C (—300" to 572°F). Work by Servi, Norton, and Grant6 has shown that, during the creep of coarse-grained aluminum at high temperatures, new slip systems come into operation. The existence of a new high temperature slip system at temperatures greater than 225 °C (437°F) for magnesium was suggested also by Schmid. This was later indicated by Bakarian and Mathewson&apos; to be slip along the pyramidal planes (10i1) in the close-packed direction <11%>.* They * Mention will be made in the text of pyramidal planes and prismatic planes. The pyramidal planes referred to are the type I. order 1 of the form {10il); and the prismatic planes of the type 1 of the form (10i0). For the sake of brevity, they are termed in the teat as pyramidal (10il: and prismatic (10i0) planes, respectively. Where reference is made to the pyramidal plane type 1, order 2 of the form {10i2), they are referred to as the pyramidal planes of the type (10i2:. observed that this kind of slip resulted in irregular markings on the specimen surface. According to them, a possible cause for the appearance of the markings was due to "limited accessory slip on the pyramidal {10i2) planes." Burke and Hibbard," on deforming a single crystal of magnesium at room temperature, found evidence of slip on a pyramidal plane {1011). They explained it as being due to the effect of grip restraints. It is pertinent to note at this point that, although basal slip has received a fair amount of attention, only two specimens have been investigated, that of Bakarian and Mathewson and of Burke and Hibbard, to establish the elements of nonbasal slip in magnesium. During the study of the deformation mechanisms

Jan 1, 1956

By N. J. Grant, A. W. Mullendore

Three aluminum alloys of 0.94, 1.92, and 5.10 pct Mg, prepared from very high purity metals, were tested at 500°, 700°, and 900°F in creep rupture. The degree of strengthening through solid-solu-tion alloying and the effects on the deformation characteristics and fracture were examined. The ductility of the alloys as a function of stress and temperature was closely followed. STUDIES of the creep process in pure metals in recent years have done much to expand the understanding of the fundamental deformation and recovery processes that contribute to overall creep behavior. In order that this knowledge may be applied to commercial alloys, it is necessary to know the principles governing the effect of alloying on the mechanisms of creep. A limited amount of work has been performed in this field, but few investigators have attempted to follow the changes in particular creep mechanisms with alloying. Recently, studies of the effects of solid-solution alloying on the plastic properties of aluminum have been conducted by Dorn, Pietrokowsky, and Tietz,1 Sherby, Anderson, and Dorn,2 and Sherby and Dorn.3 This paper presents the results of an investigation of the effect of solid-solution alloying of high purity aluminum with magnesium on the creep-rupture properties, and correlates these observations with changes in the creep mechanisms. This work is thus an extension of the creep-rupture observations of Servi and Grant4,5 and the deformation studies of Chang and Grant.6,7 Experimental Procedure Three alloys of aluminum containing approximately 1, 2, and 5 pct Mg were tested. These alloying additions are all within the solid-solubility limit at the testing temperatures.&apos; The analysis of the materials is presented in Table I. The tests fall into two categories: l—creep-rup-ture tests at 500°, 700°, and 900°F, and 2—structure study tests performed primarily at 700°F. Speci-mens of 0.160 in. diameter with milled flats for metallographic observations" &apos; were utilized for the structure studies. All specimens were annealed in one step to give the desired grain size for the tests. Table II presents the annealing data and final grain sizes. The specimens were polished electrolytically before testing with Jacquet solution (2/3 acetic anhydride, 1/3 perchloric acid) at 25" to 30°C, and 15 to 20 v. Creep-rupture testing was performed under constant load with the apparatus previously described." Results and Discussion Creep-Rupture Properties: The log-log plots of creep-rupture data are presented in Figs. 1 and 2. For these very pure single-phase alloys, the minimum creep rate and the rupture life both exhibit straight-line dependence on stress in this method of plotting as they have for commercial alloys0,10 and for pure aluminum." Curve breaks, based on the use of straight-line segments, at 500°F have been found by metallographic study to correspond to a transition from low to high temperature behavior and so represent zones of equicohesion. Specimens on the high creep-rate side of the break showed normal granular deformation processes whereas those on the low creep-rate side showed rapidly increasing grain-boundary sliding and migration with extensive evidence of intercrystalline cracking at 500°F. Two micrographs of the 0.94 pct Mg alloy, Fig. 3, show the increased participation of the grain boundary in the deformation process at 500°F with decreasing stress. In Fig. 3a is shown the structure of a specimen which exhibits little deformation along the grain boundaries and failed transgranularly; in Fig. 3b is shown the increased deformation along the grain boundaries at a lower stress for a specimen which showed appreciable intercrystalline cracking. The severity of intercrystalline cracking increased with increasing magnesium content at 500°F. Intercrystalline cracking disappeared in most of the specimens at 700°F and persisted only in the 5 pct Mg alloy at high creep rates. At 900°F all of the specimens deformed with extensive grain-boundary participation, including extensive grain-boundary migration. None of the alloys at 900°F showed intercrystalline cracking.

Jan 1, 1955

By C. R. Sandberg, T. A. Pollard, E. B. Elfrink

This paper presents an evaluation of compressibility factor data and a discussion of their application to the estimation of gas reserves. A correlation is presented which provides compressibility factors for use in both two-phase and single-phase hydrocarbon systems. Accuracies comparable to those obtained previously for single-phase systems only can be expected. A simple means of predicting the presence or absence of a liquid phase in a condensate system of known composition is illustrated. The correlation is based on 1,030 compressibility determinations from 21 hydrocarbon samples taken from eight oil fields. Of the data used, 75 per cent were from California, 15 per cent were from the Mid-Continent area, and 10 per cent were from South America. The average numerical deviation of the experimental data from this compressibility chart is 1.22 per cent. Charts and tables are included and discussed which illustrate the errors involved through the misuse or nonuse of compressibility factors in estimates of gas-in-place. INTRODUCTION The compressibility factor is a coefficient which expresses the deviation of a gas of given composition from the Perfect Gas Laws. A factor such as this is necessary in any calculation involving volumes of gaseous mixtures, and finds extensive application in the estimation of natural gas and condensate reserves. It is used in the decline curve, the volumetric, and the material balance methods of gas reserves estimation. The behavior of gases at high pressures has been investigated extensively in recent years and considerable data have been assembled on the compressibility characteristics of a number of gases. Notable among the investigators of high pressure gas relationships are Kvalnes and Caddya, Kay" Sage and Laceys, and Brown, Standing" and Katz4. Other contributors are Smith and Watson, Roland and Kaveler&apos;, and Stevens and Vance". The data on compressibility factors assembled by these investigators have been presented and correlated in numerous ways; particularly noteworthy is the method first presented by Kay5 which relates compressibility factor "Z" to pseudo-reduced temperature and Pseudo-reduced pressure. Other investigators have used this empirical relationship successfully and numerous charts covering a large number of gases have been constructed on this basis. It is the purpose of this paper to evaluate compressibility factor data and to illustrate the importance of their proper use in the estimation of gas-in-place for both gas and condensate reservoirs. EVALUATION OF COMPRESSIBILITY FACTOR DATA The compressibility chart presented by Standing, Katz, Brown and Holcomb in 1941 is probably the most recent and reliable chart for natural gases. The reliability of the Katz chart has been investigated by the writers for a fairly large number of gases (single-phase) in the pressure range from 500 to 10,000 psia and temperature range from 80 to 400°F. A summary of this comparison is presented in Table I. The numerical average deviation of the chart compressibility factors from the experimental compressibility factors is 1.05 per cent, and the algebraic deviation is -0.28 per cent. The Katz correlation appears to be quite accurate for single-phase hydrocarbon systems. It was based on single-phase systems and does not necessarily provide a means of accurately predicting the behavior of two-phase systems which might be encountered in condensate work. Data published recently by Sage and Oldsl&apos; have enlarged the knowledge of phase behavior in condensate systems by covering extensively the Compressibilities of systems in the two-phase as well as single-phase regions for a wide range of temperatures, pressures and gas-oil ratios. An evaluation of these data indicates that conditions can arise, especially in condensate systems having fairly low gas-oil ratios, in which two phases occur and the usual gaseous compressibility factors do not accurately apply. The measured PVT data of Sage and Olds covering two-phase systems have been correlated with additional such data from the Mid-Continent area and South America; these are presented in Fig. 1. This chart is the result of 1,030 compressibility* determinations from 21 hydrocarbon samples taken from eight oil and condensate fields. Of the data used, 74.75 per cent were from California, 15.45 per cent were from the Mid-Continent area, and 9.80 per cent were from South America. The chart construction is based on the original

Jan 1, 1949

By C. A. Doh, R. Q. Fields, M. Lebourg

A formation tester run on logging cable is now available to the oil industry. It offers a method of safely and rapidly testing possible producing formations in uncased holes. These tests can be made up the hole after running the electric log. Reservoir pressure data is continuously recorded at the surface as the fluid sample is extracted. The tester may be assembled with a reservoir of 1-, 2.75-, or 5.5-gal capacity. A retaining pad on the body of the tool is expanded against the wall of the hole at the exact depth desired; this depth is determined by electrical log control. Two bullets are then fired through the center of the retaining pad which create a connection between the formation and a flow line to the sample chamber. When the chamber is filled, a valve is closed and the fluid sample sealed at maximum pressure. The tool is retracted to minimum diameter and brought out of the hole. Electrical circuits permit a complete recording at the surface of the mechanical operations of the tool as well as the formation pressure build-up and the hydrostatic mud pressure. The tool was introduced commercially during the latter part of 1955 in the Gulf Coasts of Louisiana and Texas. Over 1,000 operations have been made to date (Sept. 1, 1956); 50 per cent of which resulted in successful tests. Failures have been due mostly to ineffective sealing in unconsolidated sands. One major company had 41 successful tests out of 80 attempts with 23 ineffective pad seals. Results for this company were very gratifying as to pinpointing gas-oil ratios, indicating productive permeabilities and aiding in determination of fluid content where electrical log and side-wall coring information were inconclusive. Eight typical pressure curves are discussed (including misruns). Six types of fluid recoveries are interpreted. Eight actual field examples of electric logs, showing the problems solved by the formation tester, are illustrated. The present applications of the tool are discussed: 1. Determination of productive fluid—varticularlv differentiating between gas and oil. 2. Determination of reservoir pressure as an aid to: (a) safety in completion technique, (b) reduction in drilling costs, and (c) reservoir analysis. 3. Determination of minimum gas-oil ratios. 4. Location of gas-oil or oil-water contacts. 5. Recovery of samples for examination and analysis: oil (gravity); gas (hydrocarbon content); water (salinity). Additional applications envisioned for the future are also given: (I) subsurface exploration based on accurate pressure, (2) recovery of fluid samples from the undisturbed reservoir for PVT work, and (3) possible quantitative study of permeabilities or productivity index. Running the formation tester requires no special pre-cautionary measures. Because full hydrostatic mud pressure is maintained at all times, well depth is no problem. Thus, the method allows safe, economical testing in wells which heretofore could only be tested by setting casing. INTRODUCTION A new method of safely and rapidly testing possible producing formations in uncased holes is achieving considerable success. The method offers promise of further advances in reservoir study. Called the formation tester, the new instrument is unique in that it operates on logging cable. It thus offers all the advantages of wire-line operations and becomes an important adjunct to present logging and side-wall coring services. The tester is operated against the wall of the hole at any depth desired. Zones to be tested are usually determined by a study of the electrical and the micro-caliper surveys. Reservoir data, as well as the operating cycle of the tool in the hole, are continuously recorded at the surface during the operation. The tester, as it was originally designed, was capable of recovering a 1-gal sample of reservoir fluid per trip in the hole. Tools with reservoirs of 2.75- and 5.5-gal capacity are now available. The 5.5-gal reservoir is equipped with a segregating system, set before going in the hole, so that the last portion of the recovery (usually 1 gal) is automatically separated from the first portion. This makes it possible

Jan 1, 1958

By R. B. Full

DURING the summer of 1949, the United Nations Scientific Conference on the Conservation and Utilization of Resources met at Lake Success. As summed up by one writer, the purpose was: "That everyone will try to learn how to feed more people from an acre of land." That objective is a stimulus to the phosphate rock industry as well as other industries. Phosphate rock was mined first in the Canadian province of Quebec where it was found as an apatite in pockets. In 1863, mining began near the Rideau Canal, first in open trenches and quarries until shafts were sunk. These operations were difficult since hard rock had to be drilled and blasted. Steam was the source of power. The phosphate rock was hand-selected and recovery ranged from 6 to 10 pct, averaging 70 pct to 85 pct bpl (bone phosphate of lime). Costs, f.O.b. Montreal, were $14 a ton, and selling prices averaged $17 a ton. In 1885, about 29,-000 tons were sold on this basis, but by 1892 the output fell to 8000 tons at an average price of $15 a ton at Montreal. South Carolina Deposits Phosphate rock was first discovered in South Carolina in 1837, but a mining company was not formed until 1867. It was immediately successful, and the industry continued to develop and ship an increased tonnage of land and river rock, shipments increasing from approximately 20,000 tons in 1868 to 537,000 tons in 1890, when the shipments began to decrease. In 1892 only 350,000 tons were shipped. In this field there were two types of deposits: land rock and river rock. More land rock tonnage was mined until about 1887 when river rock production began to equal it. The land rock was mined adjacent to and in the river marshes by pick, shovel, and wheelbarrow. Each worker dug daily a space 6 ft wide, 15 ft long and 6 ft deep, which was overburden, and then loaded about 3 cu yd of phosphate rock into wheelbarrows. His helper would wheel the barrows to small steam railroads up to 250 ft distant. Water was kept from the pits by steam pumps connected to railway cars. The phosphate rock was loaded into railroad cars, hauled and dumped into a log washer to which water was added, and run over trommel screens to eliminate the clay and loose sand. Steam shovels for loading were introduced about 1891. River rock was mined by floating dipper dredges and at low tide was loaded into barges by laborers using oyster tongs, the large lumps being hand-loaded. Barges and bateaus were unloaded by wheelbarrows which were wheeled to the same type of land rock washers. The washer product was piled with stacked pine cordwood in alternate layers and fired for drying. Usually this was done under sheds along the river bank. The dried rock then was transferred to ships, usually three or four-masted schooners. Cost of production of both land and river rock, including $1 a ton royalty paid to the state for state-owned property, was approximately $4.25 a ton averaging 60 pct bpl. The selling price was approximately $7 a ton f.O.b. In 1886 the courts handed down a decision permitting anyone to mine, and many additional companies were organized immediately. As a result, the selling price was lowered to a profit margin of 50Ø or less per ton. The South Carolina mines were eventually shut down when a more profitable source of phosphate rock was discovered in Florida. Florida Deposits Phosphate rock was discovered in Florida in 1882, and in 1883 a small quarry was opened near Hawthorne. In 1886 phosphate rock of good grade was discovered on Peace River, and the Arcadia Phosphate Co. was formed. In 1888 the company began shipments amounting to 3000 tons that year. During the latter part of 1888, hard-rock phosphate was discovered near Dunnellon. Exploration extended rapidly, and deposits of hard-rock phosphate were mined over a wide area so that shortly after 1900

Jan 1, 1952

By J. M. Uys, T. B. King

The solubility of water in silicate melts of various compositions was measured. The basicity of the silicate did not appreciably affect the water solu-bulity at low-base content (acid compositions). Near the orthosilicate composition the solubility increased with basicity for silicates in which the cation displayed a weak ion-oxygen attraction and apparently decreased for those in which the cation showed a strong ion-oxygen attraction; metasilicates of the former class dissolved more water than those of the latter. Temperature had little effect on water solubility. The experimental results are interpreted on the basis of two modes of solution, the contribution of one decreasing, and that of the other increas -ing, with increased melt basicity. In the former, solution occurs through interaction with doubly-bonded oxygen atoms and in the latter, through interaction with singly-bonded oxygen atoms, or, in very basic melts, through reaction with free oxygen ions. THE hydrogen content of a steel melt is in a large measure determined by water dissolved in the slag. In some glasses water may be a major cause of "seeds". Water vapor in the furnace atmosphere is the primary source in both instances. A knowledge of the mechanism of water solution in silicate melts should help in assessment of practical methods for its control in steelmaking and glass refining. Walsh et a1.l measured the water content, expressed as hydrogen, of 40 pct lime-20 pct alumina-40 pct silica and 62 pct manganese oxide-38 pct silica melts as a function of the steam partial pressure, in equilibrium with the melt. Tomlinson 2 and, also, Russell3 investigated this relationship for a molten 30 pct soda-70 pct silica glass. In all three investigations, the solubility of water was found to be proportional to the square root of the partial pressure of steam. Moulson and Roberts 4 confirmed this relationship for a silica glass. On the basis of the square root relationship, Tomlinson2 and Russell3 interpreted the solution reaction as "network-breaking", similar to that expected on the addition of metal oxides to silica. Walsh et al.&apos; postulated two possible modes of solution, one the mechanism suggested by Tomlinson and Russell and the other the reaction of the water molecule with an oxygen ion to form hydroxyl ions. These two modes of solution suggest opposite effects of melt basicity on water solubility. However, little appears to be known about the effect of melt basicity on water solubility. Walsh et a1.l found, in the lime-silica system, that the water content increased slightly with increased basicity. As these authors pointed out, this does not appear to be in accord with their further observation that slags containing little or no silica dissolve very little water. Kurkjian and Russell5 measured the effect of basicity on water solubility in alkali silicates in the composition range 15 to 45 mole pct alkali oxide. They found a minimum in the water content at about 25 mole pct alkali. This was interpreted on the basis of two concurrent solution reacZions; one in which solubility was proportional to the activity of doubly-bonded oxygen and, in the other, proportional to the activity of singly-bonded oxygen. The present work was aimed at establishing the effect of basicity on water solubility in silicate melts over as wide a range of compositions as practical. APPARATUS AND EXPERIMENTAL PROCEDURE The silicate melt was equilibrated with a "carrier-gas" of accurately known water content, quenched, and analyzed for water by a vacuum fusion technique. Some pertinent details of the equilibration procedure, analysis technique, preparation, and handling of the silicates are given below. Gas-Silicate Equilibration. The apparatus used to equilibrate the melt with the gas mixture was similar to that used by Walsh et al.&apos; but with some important modifications.6 Purification trains were provided for nitrogen and hydrogen; whenever air or oxygen was used as carrier gas the nitrogen purifiCation train was used with the copper furnace at room temperature. Gas flow rates were measured with capillary flow meters; bleeders filled with a mixture of dibromo and tribromo ethyl benzene (density about 2 g per cc) were used for convenience in controlling flow rates.

Jan 1, 1963

By E. S. Machlin

An extension of the thermodynamic theory has been made for the case of irreversible growth processes occurring by the motion of an interface. The theory is applicable to such diverse phenomena as diffusion, growth in recrystallization, continuous grain growth, growth of carbides, etc., growth of eutectoid products, growth in solidification, recovery, "slipless" flow, etc. THE publication of a recent book1 has served to focus attention on a very powerful means of treating certain irreversible processes. This method which has been formally described as the thermodynamic theory of irreversible processes is applicable to processes which involve an approach to equilibrium and for which the deviations from equilibrium are small. The irreversible processes can be classified into three groups: chemical reactions, transport processes (diffusion, heat and electrical flows), and relaxation phenomena involving a degradation of internal energy to more stable states. The limits of applicability of the theory can be precisely defined1,2 for each type of irreversible process. For example, in a chemical reaction at constant temperature and pressure, the Gibbs free energy released per mol in the process should be less than the thermal energy, RT. Another type of irreversible process, which sometimes involves a combination of the first two of the above-mentioned groups, is treated in this paper. This process is one characterized by the motion of an interface separating two regions having different values of free energy and may be briefly described as a growth process. Prigogine2 and Herring3 have treated special cases of this type of process. Previous conscious applications of the theory in metallurgy have been limited to the field of diffusion, one of the transport processes. Darken,4 Bardeen,5 Prigogine2 and others have made significant contributions in this respect. Some other applications of the theory are described in this paper. The Theory The thermodynamic theory of irreversible processes is based on the work of Onsager,6 DeDonder,7 Prigogine2 and others. A resume of the theory has been given by Prigogine2 and DeGroot.1 A brief description of the theory follows, although for a complete understanding the reader is urged to read the references. It is first assumed that the change in entropy, even for a system removed from equilibrium, is given by dS = [dU + pdV - Si µi, dn, - Sk Pk dxk]T-1 Using this expression, the irreversible entropy production in the system is calculated by subtracting the contribution to the change in entropy of the system by transfer of heat, work, or matter from the surroundings. Thus, for example, the irreversible entropy production of a system at constant temperature and pressure is given by dtS = — — dG (DeDonder7) Now it has been shown by Prigogine,2 DeDonder,7 and DeGroot1 that the rate of irreversible entropy production diS/dt, when calculated in the manner suggested, can be written as a sum of products of conjugate forces XK and fluxes Jk, i.e., d,s/ = Sk Jk Xk [I-1] dt The assumption is next made that a linear relation exists between a given flux and the forces, obtained from Eq. I-1, i.e., Ji = Sk Lik Xk (i = 1, 2, . . . n) [I-2] Generally, there is a degree of freedom in choice of the fluxes and forces. However, for all the choices consistent with Eq. I-1 the Onsager8 relations, based on the principle of microscopic reversibility, namely, Lik = Lki, are valid. The coefficients Lik, depending upon the choice of the conjugate fluxes and forces, may be more or less dependent upon the parameters defining the state of the system. In general, the proper choice of fluxes and forces utilizing Eq. I-1, makes the coefficients Lik independent of time. Also, because many of the three classes of irreversible phenomena have already been treated,1,2 a proper choice can be made by analogy. In any case, the validity of Eq. 1-2, from whatever choice made using Eq. I-1, must be tested by experimentation. The theory, thus, comprises the following steps: 1—The irreversible entropy production is calculated to yield Eq. I-1. 2—The terms in Eq. I-1 are grouped

Jan 1, 1954

By R. F. Sheldon

The discovery of the Carlin deposit was the result of discriminating geologic research and prospecting devoted to the objective of finding a gold deposit that could be mined by open pit methods. By the late 1950s, Newmont Mining Corp. was becoming increasingly concerned about the trend of rapidly rising underground mining costs unless bulk mining methods could be applied. The desirability of finding an open-pittable gold deposit was apparent. The attention of Newmont geologists was directed to Nevada by the publication of two papers: "Paleozoic rocks in North-central Nevada" (1958) and "Alinements of Mining Districts in North-central Nevada" (1960), both authored or co-authored by Ralph J. Roberts of the United States Geological Survey. John Livermore, geologist of Newmont Exploration Ltd., attended a talk given by Roberts in Ely, Nevada in the summer of 1961. These papers and the address by Roberts gave details concerning the Roberts Mountain overthrust, a 483 km (300-mile) long, shallowdipping fault which pushed clastic and volcanic rocks of early and middle Paleozoic age eastward over younger marine formations. Subsequent uplift and doming with consequent erosion had locally removed the upper plate strata exposing windows of lower plate carbonate rocks. Roberts noted that the principal mineral deposits of the region, including gold, were associated with these windows which exhibited a preferred alinement. In the summer and fall of 1961 Newmont&apos;s exploration geologists John Livermore and J. Alan Coope began a systematic examination of gold occurrences associated with these windows, aided by further discussion with geologists of the US Geological Survey. Attention was directed to the Lynn and Carlin windows, particularly to those formations lying immediately above and below the Roberts Mountain fault. It was appreciated at the time that many of the gold occurrences in the region were unusual in that no colours were obtained even when panning high grade samples. A large number of rock samples were collected and analysed using fire assaying procedures, and background values for gold were established. This systematic rock sampling resulted in the identification of a distinct area of anomalous gold values, and a block of claims was staked in late October, 1961. These claims, plus an adjoining optioned 32.4 ha (80 acres) of ground, cover the main area of the present Carlin gold mine. Prior to snowfall that winter, one of the bulldozed assessment pits required to establish a claim&apos;s discovery exposed 24 m (80 ft) of mineralization assaying 0.007 kg/t (0.22 oz per st) gold. In the spring of 1962 a program of trenching, sampling, and geological mapping followed by rotary drilling was underway. Other properties in the area were acquired. The generally undistinguished nature of the dolomitic siltstones and silty dolomitic limestones hosting the micron-sized gold particles, coupled with the lack of visually associated guide minerals, made identification of the gold bearing areas very difficult. The entire drill column had to be assayed to ensure that values were not overlooked, as very often sections that might be assumed to be waste turned out to be high grade. On September 10, 1962 a high grade intersection of 24 m (80 ft) assaying over 0.03 kg/t (1 oz per st) gold was encountered in the third hole drilled. An expanded program of both rotary and diamond drilling led to the further delineation of the ore body. By December 1963, the exploration program had established an initial reserve of 10 Mt (11 million st) grading 0.01 kg/t (0.32 oz per st) gold. A 1.8 kt/d (2,000 stpd) processing plant was constructed and the first gold bullion was poured in May, 1965, just two years and eight months after the discovery hole was drilled. REFERENCES Roberts, R.J., Holz, P.E., Gilluly, J., and Ferguson, H.G., 1958, "Paleozoic Rocks in North-central Nevada," Bulletin American Association of Petroleum Geologists, Vol. 42, No. 12. Roberts, R.J., 1960, "Alinements of Mining Districts in North-central Nevada," Professional Paper 400-B, US Geological Survey, Article 9.

Jan 1, 1985

By S. J. Prison, C. R. Smith

The effect of fluid injection to control water coning in oil and gas wells was investigated. Analytical and model techniques were employed. The factors investigated were the position and length of the completion interval, the point of fluid injection, the viscosity of the injected fluid and the relative thickness of the oil and water sections. The resulting influence of these factors on the net producing water-oil ratio was determined. Several important conclusions can be drawn from the study. In general, it was found that the net producing water-oil ratio can be reduced by fluid injection. The magnitude of this reduction depended on the factors listed above. An important practical consideration is that the injection fluid may be either oil or water. If the injected fluid is less dense than the connate water of the reservoir, the fluid will not be lost. This fact is reassuring when valuable oil is being injected. Efforts to suppress water production were more successful when the injection fluid was more viscous than the reservoir oil, or when a zone of reduced permeability existed in the vicinity of the point of fluid injection. Under test conditions, little benefit was derived through the use of impermeable barriers or cement "pancakes". INTRODUCTION The occurrence of water coning has been known for at least 60 years. In thin oil or gas pay sections, the presence of an oil-water or gas-water contact hinders production and often causes early abandonment of the afflicted well if a completion is even attempted. Even when relatively thick pay sections are found, the encroachment of water when a water drive is present will eventually pose serious water coning problems. This water is often corrosive, expensive to separate from the oil or gas and is costly to dispose of. The theory of water coning has been discussed by a number of authors. 1,2,3,4 Briefly, water coning to the producing interval in a well is due to pressure gradients resulting from the production of fluid from the reservoir. These pressure gradients will cause a water cone to rise toward the bottom of the producing interval if a water-oil or water-gas contact exists. The tendency of the water to cone is offset or partially offset by gravity forces since the water has a higher specific gravity than the oil. A balance then exists between two forces, gravitational forces arising from the difference in specific gravities of the oil and water, and the pressure gradients causing the flow of fluids to the wellbore. If the pressure gradient exceeds the gravitational force, water coning to the wellbore occurs and water production results. Through the years considerable thought has been given to the water coning problem. More than 50 U. S. Patents have been granted to inventors on the subject. A relatively complete literature review of the water coning problem has been made. 5 A number of these patents hold considerable promise for the solution or the partial solution of the water and/or the coning problem. Very little has been written describing field tests of techniques for the suppression of water coning. A notable exception is the paperby West. 6 He reports success in reducing gas coning by a combination of gravel packing and oil injection above the oil-producing interval. He also describes a comparable method to prevent water coning, but provides no field examples. This study experimentally and analytically verifies the benefits of oil injection as a means of partially or completely suppressing the water cone. While the gas coning problem was not treated, it is anticipated that results comparable to those obtained in water suppression could be obtained with reduced oil injection since the viscosity contrast between oil and gas exceeds that between oil and water. For the purpose of this study, the conventional potential flow theory was applied to the water-coning problem. The experimental verification centered on both a radial and a linear model. The model study permitted the investigation of complex flow configurations and the use of fluids of differing densities and viscosities. No analytic expressions are available to permit a solution of the problem as stated (see Fig. 1).

By J. D. Alexander, W. L. Martin, J. N. Dew

This paper presents data obtained using a flood-pot technique to determine the fuel available and the corresponding theoretical air requirements for in situ combustion of crude oils. Since the technique is relatively quick and easy, it is a practical and convenient tool for evaluating reservoirs as fireflood prospects. It is also a research tool which facilitates systematic study of the variables affecting fuel availability and corresponding air requirements. The understanding of these variables is of prime importance to those concerned with the technical and economic development of in situ combustion as an oil-recovery process. The experimental results show conclusively that the fuel available for in situ combustion is not a constant but, rather, varies with crude-oil characteristics, porous-medium type, oil saturation, air flux and time-temperature relationships. Thus, the fuel availability for specified field applications should be determined using actual reservoir crude and core material and the process conditions expected during in situ combustion in the reservoir. INTRODUCTION In situ combustion is a thermal process for recovering crude oil from reservoirs. The thermal energy released during the combustion of a small amount of the oil in place aids in the displacement of the remaining oil. Numerous articles have been published describing the in situ combustion process giving detailed results of laboratory and field experiments.10 In order to engineer an in situ combustion project, a number of important factors must be considered and determined. These factors include: (1) the amount of fuel consumed per unit of reservoir volume swept by the combustion zone, (2) the composition of the fuel consumed, (3) the amount of air required to consume this fuel, (4) the portion of the reservoir swept by the combustion zone, (5) the appropriate air-injection rates and pressures, (6) the amount of oil that will be recovered, (7) the rate of oil production and (8) the operating costs. Nelson and McNiell1 recently have described a procedure which utilizes laboratory combustion-tube data as a basis for the calculation of some of these design factors. Various authors have attempted to describe the in situ combustion process mathematically, and considerable progress has been made. Analytical solutions to the problem of heat transfer from a moving combustion front have been obtained for linear and radial systems."-&apos; All of the published results involve the assumptions that: (1) fuel concentration is constant throughout the reservoir, or that fuel concentration is inversely proportional to the velocity of the front for a given rate of oxygen consumption; and (2) the fuel reacts instantaneously with injected oxygen, while liberating a constant amount of heat per unit weight of fuel at all temperatures. It seems both desirable and reasonable to test the validity of these assumptions experimentally. This paper presents laboratory data which were obtained by means of a "fire flood-pot" method for determining fuel availability and composition, and the corresponding theoretical air requirements for in situ combustion of crude oils under variable conditions. The mechanics of the method are similar to a conventional tube-run experiment.&apos; The important differences involve the size of the reservoir model used and the method for providing the experimental environment. The new method subjects conventionally-sized core samples or unconsolidated sands to a programmed environmental sequence similar to that experienced by a similar volume of rock during the approach and passage of a combustion front in a long tube or in an oil reservoir undergoing in situ combustion. Restored-state samples can also be used. The small samples and relatively simple techniques involved allow an experiment to be set up, run and calculated in about three 8-hour days. This is a considerable improvement over long-combustion-tube techniques which can require several days to run and several more work days to set up and calculate. All the runs presented were run at 40-psig injection pressure. Pressure was not considered as a variable for these experiments, since we previously had found that it had only a small effect on fuel availability up to 600 psig.APPARATUS AND MATERIALS APPARATUS The fire flood-pot apparatus consists of a consolidated