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By A Guinier

RECIPITATION in alloys is undoubtedly one of the most essential phase transformations in metallurgy and, besides, it is a phenomenon of great interest to physicists. It seems then that it can be chosen as a topic for an Annual IMD Lecture. Of course, the subject is a very wide one and I shall discuss here only a very restricted part of it. I should like to show why it is now considered that there is, at the beginning of the process, a stage distinct from the real precipitation, which is the pre-precipitation. We shall be chiefly interested in the atomic structure of the metal in this preprecipi-tation stage. Numerous reviews on this subject have been published recently.', ' The latest was given by H. K. Hardyh t the last meeting of the Institute of Metals in London. One of the most complete articles has been written by the late Dr. Geisler." I should like, at the beginning of this lecture, to pay a tribute to the memory of our friend Arthur Geisler. Some of the ideas which will be developed here are different from those advocated by him. But everybody knows the considerable progress in experiment and in theory which we owe to him and, personally, I deeply feel how fruitful have been the long discussions which we have had during many years. Experimental Basis of the Precipitation Problems Let us recall the essential facts pertaining to the problem of the precipitation. The starting point and the final one are well known. The initial stage is the supersaturated solid solution before quenching. The dissolved atoms replace some of the atoms of the solvent at the points of a definite lattice. It is generally considered that the distribution of the atoms is completely random, and that the lattice distortions are relatively weak. These assumptions are only an approximation. It has now beenproven", that, in some cases, the dissolved atoms have a tendency to segregate to form very small nuclei. These fluctuations of composition are greater than the normal statistical fluctuations in a purely random alloy. We shall see the role played by these nuclei later. The final state is obtained by a very long annealing at such a temperature that an equilibrium is reached in a reasonable time. The alloy is then composed of a matrix which is a saturated solid solution, much poorer than the initial one. Imbedded

Jan 1, 1957

By A. B. Cook, C. J. Walker, G. B. Spencer

Although water will displace oil from a petroleum reservoir to a greater extent than gas will, there are some reservoirs in which gas rather than water should be used for pressure maintenance. This is indicated by the high-percentage oil recovery in the case history reports on the Pickton field1 in East Texas and the Raleigh field2 in Mississippi. In gas cycling, total oil recovery includes vaporized products from the immobile oil in addition to oil produced by displacement. If a large part of the immobile oil is vaporized, total oil recovery may be higher than that obtainable from pressure maintenance by water injection. However, the amount of immobile oil vaporized may range from almost 0 to 100 percent, and no simple and reliable method has been presented in the literature for calculating oil vaporization. Development of such a method was the purpose of this study. Several papers concerning the calculation of oil vaporization have been published,3 6 and each is based on the concept dealing with K values — equilibrium constants for the various components in reservoir oils. (K for a component in a system of vapor and liquid in equilibrium is the mole fraction in the vapor phase divided by the mole fraction in the liquid phase.) This appears to be the most logical approach. Yet, the problem is too great for a perfect solution, even with modem laboratories to analyze oils and high-speed digital computers to perform calculations; the number of components in reservoir oils is too large. Because of their complexity no two reservoir oils are exactly alike. Also, K values change not only with variations in pressure and temperature but also with composition of the reservoir oil. In addition, during gas cycling, the lighter hydrocarbons tend to vaporize first. Thus, the reservoir oil becomes more dense and less volatile as gas cycling continues. Furthermore, the greatest amount of oil vaporization occurs near the injection well. Therefore, a simplified method is required for calculating oil vaporization because a rigorous method is not practical. The present methods of calculating vaporization generally require knowledge of the reservoir oil composition in which the mole fractions of the lighter components through hexanes are given; the remaining oil is described as C, + (heptanes and others of greater molecular weights). Assigning one K value for the C,+ system provides the simplest solution, but this incorrectly assumes that K for C, + does not change as gas cycling continues. This assumption can cause large errors because the K value may become less than a thousandth of the original after a large amount of oil vaporization. Another way to solve the problem is to determine changing K values for C, + according to how much of the C, + has been vaporized. To determine these values a sample of the reservoir oil is injected into a pressure-volume cell, and dry gas is batched in and out of the cell. Appropriate measurements and tests are made to determine K

Jan 1, 1970

By L. E. Lynd

Ilmenite concentrates prepared from beach and dune sands of Florida, India, Australia, and other localities deviate to varying degrees from the theoretical composition of pure ilmenite, and generally contain more TiO2 than the formula FeTi03 would indicate, and some Fe2O3. This variation in composition is due to different amounts of altered ilmenite in the concentrates. (') The alteration has been shown to take place by oxidation and leaching of the iron in ilmenite, to yield residual products consisting of amaphous or very finely crystalline titanium dioxide and ferric oxide. Other studies(2) have stressed that ilmenite may alter first to an amorphous titanium-iron oxide, or to an amorphous mixture of titanium and iron oxides, with later alteration to crystalline titanium dioxide. There has been some speculation as to whether alteration of ilmenite is usually caused by weathering or by hydrothermal pr0cesses.(3,4,5 Three main methods of approach were used to study the mechanism and rate of ilmenite weathering. (1) Etch tests were used to learn the relationship between crystallographic orientation and the rate of chemical attack on ilmenite. (2) Altered ilmenites in New Jersey sands were compared with ilmenite in rocks of the area from which the sands were probably derived. (3) Experiments were carried out to determine at what rate, and by what agents, originally fresh ilmenite could be altered in the laboratory under simulated weathering conditions. ETCH FIGURES ON ILMENITE CRYSTAL PLANES A rather large ilmenite crystal from Sannidal, Norway, about 11/2 x 11/2 x 2 inches, bearing a few natural faces with imperfect surfaces, was prepared for etching by grinding and polishing crystal planes whose Bravais-Miller indices (referred to hexagonal axes) had been determined by X-ray methods to be 00.1, 10.0, and 10.2. Metallographic examination showed that the crystal was homogeneous, and uniform in orientation, except for the presence of twin lamellae which were oriented with their broadest surfaces parallel to the 00.1 planes of the large crystal. Since ilmenite is rather inert to standard etch reagents, strong solutions of hot sulfuric acid and cold hydrofluoric acid were used. Preliminary tests established that better etch figures were obtained using HF than with H2So4 solutions. The etch figures produced on 00.1 and 01.0 planes of ilmenite by etching 3 to 5 minutes in cold concentrated HF solution are shown in Figures 1, 2, and 3. The figures on 00.1 are "etch hillocks", rather than pits, and according to Honess(6), this phenomenon

Jan 1, 1961

By R. N. Edmondson, L. Mair, M. Tenenbaum

It is the policy of The Metallurgical Society to provide, in the TRANSACTIONS OF THE METALLURGICAL SOCIETY OF AIME, a prompt and accurate medium for publication of reports of significant new research in both the scientific and engineering aspects of metallurgy. Papers submitted to the Society are judged by competent reviewers according to established criteria for technical merit, accuracy, originality, and presentation. STAFF: Editor, Dr. Gerhord Derge; Editorial Assistant, M. A. Redmyrski; Staff Coordinator, James J. Burke. THE METALLURGICAL SOCIETY: W. R. Hibbard, Jr., President; J. C. Kinnear, Jr., Past-President; John Chipmon, Vice President; T. D. Jones, Treosurer; R. W. Shearman, Secretary. PUBLICATIONS COMMITTEE OF THE METALLURGICAL SOCIETY: A. w. Thornton, Chairman; Dennis Carney, John Chipman, J. C. Fulton I. H. Hollomon H. H. Kellogg, A. E. Lee, R. Maddin, J. D. Sullivan, and D. Swan. Review and selection of manuscripts is under the supenision of the following Publications Committees: Extractive Metallurgy Division: T. 0. King Chairman; S. J. Dickenson, R. P. Hermsdorf R. Schuhmann. Jr.. and P. T. Stroup. Institute of Metals Division: Robert Maddin, Chairman F. Lincoln Vogel Jr., Vice-chairman, W. A. Baikofen, R. W. Boliuffi J. H. Bechtold M. B. Beyer. R S. Busk, C. G. Gaetzel, Paul Gordon C. D. Groham, Jr., Robert F. Hehe-mann,' R. I. Joffee, F. c. Joumot Jr lrving R. Kramer A. J. Lena Harold Morglin, C. J. McHargue, Russell A: Meussner, J. B. Newkirk H. W. Paxton, G. E. Pellissier, I. S, Servi, Alon U. Seybolt, A. J. Shaler, and Jack Washburn. Iron and Steel Division: J. C. Fulton, Chairman; T. B King, F. C. Langenberg, W. 0.. Philbrook, and T. 0. Winkler. Published bimonthly by the American Institute of Mining Metallurgical and Petroleum Engineers Inc., 29 West 39th Street, New York 18, N. Y. Telephon: pEnnsvlvanio 6-9220. Subscription 522 Per year for non-AIME members in United States and North South and Central America; $25 foreign;, $5 for AIME members. Single copies, 54.00, single copies foreign, $5.00. The AIME is not responsible for any statement made or opinion expressed In its publications . . . Copyright 1958 by the American lnstltute of Mining Metallurgical and Petroleum Engineers Inc. . . . Registered cable address AIME New York , . . lndexed in Engineering Index Industrial Arts Index and Chemical Abstrats . . . Application for second class mail privileges ii pending at New York, N. Y. Volume 212, Number 4.

Jan 1, 1959

Q: It is May 1961 at Bill Wrather's Washington house. Bill, think back to your first job after college. Wrather: Perhaps I ought to go back a little bit further than my first job. I entered the University of Chicago with the idea of studying law. My intention was to take a 4-yr liberal arts course and superimpose a law degree on that. But during my undergraduate work I fell under the influence of R. D. Salsbury. He decided I had some talent as a geologist and influenced me to take a geological course. Nevertheless, I did not give up the idea of law. While in school I took a spell of typhoid fever and almost died. The doctor recommended outdoor exercise, so a geological job seemed logical. W. H. Emmons was a graduate student in the University and he interceded with Dr. Hayes of the USGS. I went on the payroll as assistant packer at $60 a month. I had one of the most glorious summers I ever spent in my life. That fall and the following year I took law courses and became thoroughly convinced that I was cut out for a geologist rather than a lawyer. I finished up my law work in 1908 while waiting for a job with Bill Emmons, who was doing a careful study of Goldfield and Tonopah.

Jan 4, 1964

By W. J. Kroll

Jan 1, 1960

By P. van Meurs, C. van der Poel

From observations of the linear displacement of oil by water from a porous medium as visualized in transparent models, new insight into the mechanism of vircous fingering, as occurring in the case of unfavorable oil-water viscosity ratios, has been obtained. A mathematical description of the observed phenomena leads to formulas. expressing both oil production and pressure drop across the formation as a func-tion of cumulative water injection with the oil-water viscosity ratio as a parameter. Theoretical results are compared with those obtained from scaled laboratory experiments in sand-filled rubes in which water was injected at the one end and production was obtained from the other end. In the second part of the paper the same principles are used to calculate a more realistic production scheme in which production of oil and water is obtained from wells regularly distributed over the field. Results show satisfactory agreement with production data of an actual oil field. Application of the theory is extremely simple as only a limited number of readily available parameters have to be known and results are presented in an analytical form. INTRODUCTION When oil is displaced from a porous medium by water having a viscosity lower than the oil. the oil-water interface is essentially unstable and has the tendency to break up into what are called "fingers" or "streamers". This Viscous fingering has been noted before by Engelberts and Klinkenberg' and has recently been demonstrated in transparent models by van Meurs-. It is highly questionable whether it is at all possible to perform relative permeability measurements In the laboratory reproducing the same distribution of water and oil in the cores as Present in practice. Therefore, we based our descriptive theory on an idealized model which was "tailored" to the fingering mechanism as observed in transparent models under scaled conditions. This approach was the more attractive, as a highly simplified model had already yielded an adequate description of the process. Though we are aware our theoretical approach can be extended in several ways, it is given here in its simplest form to explain the fundamental principles and to avoid complicated formulas. SIMPLEST CASE OF A LINEAR DRIVE Observations and Theoretical Model In Fig. 1 a series of photographs shows how water penetrates into a formation saturated with an oil which is considerably more viscous than the water. The technique for obtaining these photographs, using transparent models, has already been described?. The fingers can be clearly observed and are seen to be mainly parallel to the flow direction. Note that the contours of these fingers are not smooth but show protrusions of water enclosing oil pockets.

By H. T. Kennedy, S. G. Dardaganian, J. L. Clanton

This paper presents equilibrium ratios measured on oil and gas samples taken from the Kelly-Snyder field at the reservoir temperature of 128°F. From these data smoothed curves were constructed for the reservoir fluid up to the bubble-point, 1,874 psia. A material balance calculation, based on the use of equilibrium ratios instead of the usual solubility and shrinkage meayr~rements is made on the field and compared to the con\.entional method. DETERMINATION OF EQUILIBRIUM RATIOS The equilibrium ratios, or K values were obtained by recombining separator samples of oil and gas taken when the reservoir was above its bubble point, and thus represented the reservoir fluid before any change had occurred due to the evolution of gas. The well sampled had a gas-oil ratio of 617 cu ft of high pressure sepalator gas per barrel of separator oil. and a bottom-hole temperature of 128°F. Samples were brought to equilibrium by agitating for 24 hours in a thermostat, maintained at the proper temperature within 0.2ºF, mercury being added when necessary to maintain the pressure constant. Samples of oil and gas were then taken by constant pressure displacement, and analyzed by low temperature frac-tionation. Equilibrium ratios were determined at 128°F and 500, 800, 1,000 and 1,400 psig. At the latter pressure, there were indications that the gas samples were contaminated with small quantities of oil, and only data taken at the first three pressures were included in Fig. I. This figure has been extended to higher and lower pressures by the use of the Fluor charts for 3,000 psi convergence pressure, on which the experimental points fit well. MATERIAL BALANCE EQUATIONS The possible errors involved in conventional material balance equations have been analyzed by Muskat1. Where the errors occur in field measurements, or in obtaining effective averages from variables such as gas-oil ratio and pressure, they will evidently be involved in any attempt to estimate the content of the reservoir. On the other hand, substantial errors may be introduced in conventional material balance calculations by: (1) the neglect of the amount of oil dissolved in gas at high pressures and temperatures in the reservoir, but which condenses under separator conditions; (2) the assumption that the separation of oil and gas in the reservoir may be duplicated by a differential liberation in the

By S. Ramachandran, N. J. Grant, T. B. King

MANY investigations of the rate of the sulfur transfer reaction between carbon-saturated iron and blast furnace type slags have been made." It is evident that the reaction is complex, the rate being affected by the presence of elements dissolved in the metal that are readily oxidized and therefore capable of existing in the slag phase. Thus Goldman, Derge, and Philbrook- have shown that carbon, silicon, manganese, and aluminum, in order of increasing effectiveness, accelerate sulfur transfer from iron containing these elements to blast furnace type slags. Quantitative information is still, however, not available on the relation between what have been termed side reactions, such as silicon transfer and CO evolution, and the sulfur transfer reaction itself. In other words, the stoichiometry of the reaction has not been investigated. In the present investigation, the transfer of all reacting elements and the evolution of CO have been measured simultaneously in order to establish the mechanism of the reaction which occurs in practice. Information of this nature cannot be deduced from equilibrium studies. It should be pointed out that in kinetic studies of this type quantitative conclusions are applicable only to the system studied. This restriction should be borne in mind when attempts are made to compare results from different investigations. Apparatus The apparatus used enables slag and metal samples to be taken at frequent intervals and also provides a continuous record of the amount of gas evolved. A sketch of the apparatus is given in Fig. 1. It may be considered in three sections: 1) furnace section, 2) blank volume section, and 3) pressure measuring section. The furnace section is shown in detail in Fig. 2. It consists of two graphite crucibles, C and D, super-

Jan 1, 1957

By R. W. Drier

THE conductivity of copper wire is of prime importance to the electrical industry and consequently to the copper refiner and wire manufacturer. Annealed copper wire has a higher conductivity than hard-drawn wire, but, on the other hand, its tensile strength is lower. In an attempt to explain the reasons for these changes in property or at least to study the conditions existing in these two types of copper wire, the experiments described here were carried on in the Department of Metallurgy of the Michigan College of Mining and Technology. This is only a partial and preliminary report on some of the work done to date on a research program of which the object is an intensive study of copper. It is offered with the hope that, though it is not an exposition of the most rigorous of conclusions, the general trend of inferences which may be drawn will be of value and interest.

Jan 1, 1929

By H. E. Criner, M. G. Driessen

THE cyclone thickener has two important applications in wet washing plants: (1) water clarification, and (2) fine coal recovery. The thickener consists of a conical chamber into which the fluid is injected through a tangential nozzle at the periphery of the large end. The solids of the slurry are concentrated and removed from the apex of the cone while the "thinner" portion is discharged from a central tube in a flat head at the large end, fig. 1. The advantages of the cyclone thickener are that large volumes of slurry may be treated with small space requirements and that the underflow concentration may be controlled easily and readily to meet varying feed conditions. Control of Washery Water Solids Concentration: The first requirement, in the process of controlling solids concentration, is that the solids be removed from the body of circulating water at the rate at which they are introduced. If this condition is satisfied the concentration will remain at a fixed value and will not increase to uncontrollable levels. The second requirement is that the solids concentration

Jan 1, 1951

By M. G. Driessen, H. E. Criner

THE cyclone thickener has two important applications in wet washing plants: (1) water clarification, and (2) fine coal recovery. The thickener consists of a conical chamber into which the fluid is injected through a tangential nozzle at the periphery of the large end. The solids of the slurry are concentrated and removed from the apex of the cone while the "thinner" portion is discharged from a central tube in a flat head at the large end, fig. 1. The advantages of the cyclone thickener are that large volumes of slurry may be treated with small space requirements and that the underflow concentration may be controlled easily and readily to meet varying feed conditions. Control of Washery Water Solids Concentration: The first requirement, in the process of controlling solids concentration, is that the solids be removed from the body of circulating water at the rate at which they are introduced. If this condition is satisfied the concentration will remain at a fixed value and will not increase to uncontrollable levels. The second requirement is that the solids concentration

Jan 1, 1951

By T. Egleston

The materials containing copper which are refined in the United Statrs, are, for the most part, the natiye noppers of Lake Superior. IJntil quite recently but little pig copper Was made for sale, and that came principally from the pure sulphorous ores of New England and the Sonth, and was generally sdd to reSneries not far from the ore filrnaceu. A stnall aiuoiint found its way into the'niarket which was produced either as the by-product of the treatment of gold and silver ores, or as the result of the treatment of impure copper ores; but both these grades, on account of the impurities they contained, were loolced on with stlspicion, and were not sought for. A11 the grtlGis of pig coppcr are sold by the unit of oopper contents, a great redtiction being made in the price when impurities are present. There are at the present time only three works which treat native copper, the two of the Detroit and Lake Superior copper Company, and the works of C:G. Hussey & Co., in Pittsburgh. There are a few works ivhich smelt sulphuroris ores and refine their pig; bo sides these t1le1-e arc a few siuall works where gig copper is refined uuly. Some of these purcIlase blscir copper, refine scrap, or simply refine such grades of ingot copper as are found in the market, but nlostly that from Lake Superior, for the purpose of getting it into swh shapes that can be handled cpmtriercially to advantage, such as in making large plates or high grades of wire fir electrical purposes. A nomher of such works are situated in the Xaugaturk Vatley aud elsewhcre in New England. The recent discoveryof vnlt~sblc ores in Ariarona makm it probable that within a few year8 the refining of capper In the United States will make great develupments. Up to the time of the discovery of the mines on Lake Superior, only a very small quantity of native copper had ever been foond, not sufficient to justify the erection of worlrs fbr its special treatment. It had, besides, never been found in very large maweq so that the discovery of greabblocks of it presented serious difficulties, not oolp in mining it,-I- but in bringing it into a merchantable condit'ion. It seemed a very simple process to melt these large maws,

Jan 1, 1881

By J. Moore, D. Gault, R. V. Lugn

Impact of small projectiles with velocities between 0.9 and 7.3 km per sec on basalt produce craters chiefly by the ejection of fragments. Weight-size distributions of the ejecta are linear for part of the size range of the fragments. Cumulative weight-size distributions of the ejecta from different craters vary because of erratic formation of large fragments and a large percentage of ejecta below 0.1 mm. In the range of velocities studied, the crater depth is approximately proportional to the 0.75 power of velocity of the projectile. This relationship may represent a transition regime between the fluid impact regime and the undeformed projectile impact regime. The volumes per unit of projectile energy of the craters produced are comparable to those reported for lower speed projectile impact and drill bits. An experimental investigation of projectile impact on rock is being conducted jointly by the Ames Research Center of the National Aeronautics and Space Administration and the U.S. Geological Survey. Projectiles are launched with light-gas guns at the Ballistics Range of the Ames Research Center. The craters and ejecta produced in these experiments are being studied by the U.S. Geological Survey. Steel, aluminum and polyethylene projectiles weighing from 0.25 to 0.015 g were accelerated to velocities of 0.88 km per sec (2,900 fps) to 7.3 km per sec (24,000 fps) with a light-gas gun, using hydrogen as the propellant medium. Projectiles impacted the targets normal to plane rock surfaces in an atmosphere of air with a nominal pressure of 25 to 50 mm of mercury. The metal projectiles were mounted in supporting four-piece nylon sabots, which guided the projectiles down the launching tube. After launch, aerodynamic drag acted to separate the sabots from the projectiles. Impact velocities were determined with time measurements and spark photographs of the projectiles in flight. Ejecta were collected in lucite and aluminum containers placed around the target block. A small hole in the containers permitted projectile entry. Impact of projectiles of the size employed produced craters in the rock targets chiefly by ejection of fragments. The craters are small, roughly conical depressions with crushed and intensely fractured rock at the bottoms of the depressions. The ejecta are composed of pieces of the projectile and rock fragments ranging in size from a few tenths of a micron or less to several centimeters in maximum dimension. In this paper, the structural features of the craters, the weight-size distributions of the recovered ejecta, and crater depth and crater volume relationships are described. DESCRIPTION OF CRATERS Typical craters (Fig. 1) produced by experimental projectile impact in basalt are shallow, wide base

Jan 1, 1963

By Frank Rieber

THE study of earthquakes long ago developed the fact that by studying the travel times of the various groups of waves from the same earthquake, as received on seismographs at varying distances, major discontinuities in the earth's crust could be reasonably well defined. Using this original discovery, and adapting the mathematical methods originally devised in seismology for determining the depth below the surface at which such discontinuities occur, other investigators were able to develop a new branch of seismology which promises to be extremely useful in extending the boundaries of our information on local conditions below the earth's surface. As an outstanding example of the applications of this work, we have the so-called "seismograph" exploration of the Gulf Coastal region, which has resulted in the discovery of a large number of salt domes, from many of which oil fields may be developed. The original seismological investigations, from which different major discontinuities in the earth's crust were deduced, as well as these later successful experiments in locating salt-dome structures, involve relatively simple problems. In each case we are dealing with surface materials in which elastic waves will be propagated with a fairly definite velocity. Under this material we have something quite different, in which the elastic waves will be propagated with a much higher velocity. The transition from one medium to the other is likewise relatively abrupt. For example, in the Gulf Coastal region the sedimentary formations have a velocity of 6000 or 7000 ft. per sec., while the velocity of elastic waves in the cap rock of a salt dome may exceed 15,000 ft. per sec. Under such conditions, delineation of the formation is a relatively simple matter, and, furthermore, there is very little opportunity for ambiguous results.

Jan 1, 1928

By R. M. Waterstrat

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

Jan 1, 1962

By D. S. Pye, J. P. Gallus

Successful hydraulic pressure treatment of oil and gas wells that have long producing intervals, multiple pay zones, fluid thief zones, or natural or induced fractures has long been a serious problem plaguing the petroleum industry. High fluid-injection rates, straddle packers, ball sealers, and either liquid or solid additives to the treating fluids are being used to cope with this difficult and costly problem.l-6 The use of ball sealers and straddle packers is limited, in practice, to wells that have been completed with perforated cemented casings or liners. Well stimulation with ball sealers and straddle packers is usually successful as long as the cement remains competent. The other techniques of diverting are used with all types of completions. However, there are two significant disadvantages of the high rate method: excessive horsepower requirements, and the need of large treating-fluid volume. Consequently, most well stimulation techniques that involve diverting depend upon ball sealers or granular materials. Liquid diverting agents, and some of the solid ones in use today, frequently will cause formation damage. On the other hand, the most popular particulate diverting agents often are so soluble in the treating fluid that they become largely ineffective; their particle size is severely reduced as they dissolve while being transported through thousands of feet of pipe to the formation face down hole. In our attempts to deal with the shortcomings of these diverting agents, we experimented with a large variety of potentially suitable deformable materials the solubility of which could be controlled. Following are the criteria for the diverting agent sought: 1. The material must be effective in reducing fluid loss to thief zones, including existing fractures and very high permeability layers in the formation to be pressure treated. 2. The material must have enough strength to bridge under the treating pressure. 3. The material must be insoluble or slowly soluble in the treating fluids so that the particles retain sufficient size to be effective after they reach the formation face. 4. The material must be completely soluble in the produced oil or condensate liquid so that it can be removed readily; it must not cause formation damage. A number of products consisting of various polymers blended with waxes and other solid hydrocarbons were examined. All these materials satisfied the criteria for a diverting agent and also exhibited some degree of plastic deformability. On the basis of initial tests of strength and hardness, several blends of wax and polymer were selected for extensive testing in the laboratory and the field. These compounds have congealing temperatures ranging from 140 to 190F; they are insoluble in water and soluble in oil. They conformed, therefore, to the criteria specified for a theoretically superior diverting agent. Laboratory and field tests were conducted using these wax-polymer materials to demonstrate that the use of a deformable diverting agent can significantly improve fluid diverting performance. Data in this

Jan 1, 1970

By P. J. Closmann

Steam zone growth as a function of time has been calculated for the case of constant rate steam injection into a preheated reservoir. To simplify the calculation a linear temperature profile has been assumed in the cap and base rock at the start of steam injection. The results indicate that at early times augmentation of steam zone growth due to preheating should be greatest. At longer times the steam zone development becomes close to that calculated with no preheating. INTRODUCTION With the increasing application of thermal recovery processes to recover viscous oil, cyclic steam injection has become important in many large-scale projects. In this process, the cycle of steam injection followed by oil production is repeated a number of times. At the beginning of the second and later cycles, steam is injected into a reservoir that has already been heated but that has lost part of its heat both in produced fluids and by conductive heat loss away from the injection zone. In such a case, the temperature level of the injection zone and the temperature distribution of the surrounding rock will affect the growth of the steam zone developed during the subsequent steam injection. Knowledge of the size of steam zone developed is important in determining the amount of oil displaced and the extent of heating in the reservoir. It is also useful to be able to compute the size of the steam zone for cases where thief zones take most of the injected steam. This paper presents a fairly straightforward method of estimating the steam zone developed in a preheated formation, based on certain simplifying assumptions. Some cases of steam injection into a reservoir at its original temperature have already been considered elsewhere.1-3 Because it is difficult or impossible to obtain an accurate representation of the temperature distribution in the reservoir some time after initial heating has taken place, in this work, a linear temperature profile in the cap and base rock is assumed (Figs. 1A and 1B). The linear profile has the advantage of yielding heat flow equations that

Jan 1, 1969

By A. J. Terrones

THE classical papers on contact metasomatic deposits by Lindgren on the Clifton-Morenci district,' by Barrell on Marysville, Mont.,' and by Gold-schmitt on the Oslo district, Norway,' laid the foundation for understanding of the importance of separating the metamorphic process from the subsequent metasomatic stage. Knopf' made a big step forward by recognizing that sulfide ore minerals are invariably younger than silicates and by further stressing the importance of structural control" in ore finding. Some years later Harrison Schmitt" fought the idea that contact metasomatic deposits are erratic, irregular, bunchy, economically marginal, and of small size, concluding that these descriptions have little factual basis. He emphasized the importance of detail mapping and careful geological study as fundamental requirements for a better understanding of these deposits. This article presents a comparative description of the structural features at the Magistral, Antamina, Morococha, Vilca, Ferrobamba, Katanga (Quibio), Tintaya, and Huarca contact deposits (Fig. 1). Further, it will describe how these structural features controlled the emplacement of the intrusives, their shape, distribution of metamorphic and metasomatic halos, and sulfide deposition in post-skarn structural channelways. Finally, the modifications introduced by a superimposed hydrothermal stage recognized at some localities will be discussed. Primary exploration and careful sampling of recognized structural targets were instrumental in outlining the copper ore potential at the Antamina and Tintaya districts, thus proving the benefits and reward of careful geological examinations in this type of deposit. The Magistral District: This district lies in the Province of Pallasca, Department of Ancash, in northern Peru, at 8o 16' S and 77" 47' W. High to medium grade copper orebodies in garnetite, bordering a quartz monzonite stock, are exposed at the bottom of a glaciated valley in the western slope of the Andes at 4250 m (14,000 ft)* elevation.

Jan 1, 1959

By Samuel M. Shallcross

The principal function of the Bell limestone mine, of the American Lime & Stone Co., at Bellefonte, Pa., is to supply raw material to the company's modern rotary kiln plant at Bellefonte. Because mining costs are naturally higher than many open quarries with more favorably lying strata, it cannot compete, except to a limited extent, in the markets for road material and fluxing stone. In the broad sense, mining does have an advantage over the average open quarry when the end products are designed for and controlled by process and final inspection for the exacting demands of the industrial and chemical markets. Approximately 80 per cent of the output of the Bell mine is sold in the industrial and chemical markets. And as higher standards are set each year for construction and agricultural work, the remainder of the mine output goes to these two classes. Mining produces more fines than open quarries, and these fines are difficult to market; on the other hand, owing to absence of contaminating clay and impure rock, a greater percentage of the output of a mine is marketable. Because of the great production of fines, rotary kilns for lime burning are necessary when the stone must be mined. In 1921 the American Lime & Stone Co. operated 19 quarries and 72 lime shaft kilns spread over an area of 40 miles between Bellefonte and Altoona, Pa. At that time the lime-production capacity of the 72 kilns amounted to approximately 700 tons per day. After 15 years the company operates three rotary kilns and six shaft kilns, with a combined output of approximately 500 tons of lime per day, concentrated in its single Bellefonte plant (Fig. 1). Its only stone-producing plants are now the limestone mine at Bellefonte and a construction-stone open quarry at Union Furnace, near Tyrone, Pennsylvania. Since the middle of 1922, the management of the American Lime R. Stone Co. has been under the direction and ownership of the Warner Company, of Philadelphia. To the Warner Company's experience, gained through successful operation of lime plants in eastern Pennsylvania for many years, and the successful solution of material-handling problems

Jan 1, 1937