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By W. WANJUKOW, H. O. Hofman

(New York Meeting, February, 1313.) I. INTRODUCTION. IN the metallurgical treatment of most metallic sulphides it is usually necessary to carry on a roasting-operation. In some cases the raw ore will have to be roasted.; in others the intermediary product, matte, produced in smelting the ore; again, both ore and matte may have to be subjected to oxidation at elevated temperatures. Most metallic sulphides, when given an oxidizing-roast, pass through the state of sulphate before they are converted into oxides. All metallic sulphates are completely decomposed by heat, with the exception of those of lead and bismuth, but the temperatures at which decompositions take place vary with the metals. Some metallic sulphates are converted directly into oxides, others first form basic salts. Alkali-earth sulphates show a behavior similar to that of metallic sulphates, while alkali sulphates do not part with their sulphur trioxide even at elevated roasting-temperatures. The older data on the decomposition of metallic sulphates by beat are only approximations. Thus Kerl 1 gives the order in which metallic sulphates are decomposed with increasing temperatures as (Ag2, Fe, Cu, Zn, Ni, CO, Mn, Pb) SO4. More recent statements give definite temperatures and modify the formerly accepted order of decomposition. But the temperatures given by various observers do not agree. The reasons for this are to be found mainly in the method and manner of carrying out experiments. Four methods have been used: 1. Heating in an evacuated tube; 2, heating in a tube closed at one end, without air-cur-

Sep 1, 1912

By A. Moskowitz, L. S. Redmerski

The corrosion resistance of stainless steels can be strongly affected by surface treatments. Changes in corrosion resistance can relate to surface composition, integrity and stability of the passive film, and to surface profile (roughness). Operations producing oxidation at the surface, such as annealing, heat treating, and welding, can result in a chromium-rich scale and a chromium-depleted metal surface. In order to restore full corrosion resistance, chemical or mechanical clean-up techniques must remove not only the oxide, but also a very thin layer of metal. Laboratory and field test studies show that these factors are particularly significant in less highly alloyed steels. Annealing stainless in a reducing atmosphere (bright annealing) avoids chromium depletion, but as-bright-annealed material does not display optimum corrosion resistance in certain environments. Electro passiva-tion can be applied to improve pitting resistance without significantly changing bright surface appearance. Potentiometric studies show that electropassivated material also displays significantly greater resistance to breakdown of passivity in acid solutions. The application of special surface finishes for appearance purposes can affect corrosion resistance. Roughness is a key factor. Samples of related appearance but with different surface profiles can show significant differences in corrosion resistance. Thus nonreflec-tive stainless with a relatively smooth surface produced by a special rolling process is much superior to material chemically etched to a similar low reflectivity. THE corrosion resistance of a stainless steel is affected by other factors in addition to its bulk composition and metallurgical structure. These other factors include those relating to the specific chemical and physical condition of the steel's surface. This paper will consider certain aspects of surface condition in relation to corrosion resistance. In particular, studies will be described on the effects of oxidation encountered in heat treating or welding operations, of passivation after bright annealing, and of different surface finishes. EFFECTS DUE TO OXIDATION When stainless steels are exposed to high temperature in an oxidizing environment, as in annealing or welding, the oxides formed are relatively rich in chromium. As a consequence of oxidation, the metallic layer directly beneath the scale may be low in chromium to some very thin but finite depth.1"8 Such a change in chromium content could lower the corrosion resistance at the surface, whether or not the oxide layer is removed. Studies were performed relating to the effect of oxidation and chromium depletion produced during annealing and welding on the corrosion resistance of stainless steels. The nominal compositions of steels used in this study and others are given in Table I. A) Annealing Studies on 17 pet Cr Steels. 1) Effects of Pickling Treatments. Studies were performed to investigate the corrosion resistance of air annealed type 430 stainless as a function of the amount of electrolytic pickling after annealing. The material used in this study had been air annealed and electrolytically pickled in the mill. All scale had been removed, and yet the material showed unusually poor corrosion resistance. Laboratory electrolytic pickling studies were performed to determine whether additional metal removal from the surface would improve corrosion resistance. Electrolytic pickling was performed in a sulfuric acid bath using various conditions of bath acidity, temperature, time, and current density. The samples were then rated for corrosion resistance in a ferric chloride spot test. For this spot test, a solution was prepared by dissolving 10 g of FeCl3 . 6H2O, 5 g of NaCl, and 2.5 ml of concentrated HC1 in 200 ml of water. An area on a specimen was cleaned and a drop of test solution was placed on the prepared area. After 5 min, the drop was rinsed off and the area wiped dry. The spot was then rated between 1 and 5 by visual comparison with standard spots. The numerical rating of the standard spots can be described as follows: 1—No clouding of surface; 2—very slight clouding of surface; 3—slight clouding of surface; 4—moderate clouding of surface; 5—strong clouding of surface. A rating of 1 or 2 was considered to have passed the test, a rating of 4 or 5 represented failure, and a rating of 3 was considered borderline. The severity of etching in this test has been related to the actual chromium content at the surface.4 Etching (clouding) occurs on type 430 stainless (rating of 4 to 5) when the surface chromium content is 14 pct or less. The effects of current density and retention time when electrolytically repickling this material in 6 pct sulfuric acid are shown in Fig. 1. Increasing the cur-rent density or retention time improved corrosion resistance as measured by the spot test. Similarly, increasing acid concentration of the bath or bath tem-perature was found to improve corrosion resistance. The conditions making for improved spot ratings resulted in increased metal removal, regardless of specific pickling conditions used, Fig. 2.

Jan 1, 1970

By Y. C. Liu

Both the habit plane of martensite and the orientation relationship between the matrix and martensite platelets of different habit planes have been investigated in binary titanium alloys with molybdenum, chromium, and iron. The effect of the mode of deformation on the martensite habit plane was studied. A micrograph of an exposed mar-tensite platelet is presented. IN the study of martensitic transformation in Ti-Mn alloys,' two martensite habit planes—{334), and {344)8—were reported. The {334), habit was also observed in unalloyed titanium upon transformation,' although there is disagreement with respect to the exact indices. The other habit plane, {344),, has not been reported in martensitic transformation in any other alloys. The present investigation was made to determine whether other binary titanium alloys with P-stabil-izing elements would exhibit a crystallography of transformation similar to that of Ti-Mn alloys. Furthermore, since martensite platelets can be induced by deformation under certain conditions, it was of interest to investigate whether the mode of deformation, compressive or tensile, would influence the formation of martensite platelets on a specific plane in an alloy system which possesses two martensite habit planes. Experimental Procedure The material used for the preparation of the binary alloys of iodide titanium with molybdenum, chromium, and iron had the following purities: 99.99 pct iodide titanium, 99.9 pct molybdenum, 99.423 pct chromium, and 99.9 pct iron. The compositions of alloys listed in this paper are in nominal weight percentage. All specimens used were prepared and treated according to the procedure described in reference 1, unless stated. For the subzero temperature treat,ment the following experimental schedule was followed. After specimens had undergone the grain-growth treatment, they were quenched into an ice-water bath and were then metallographically examined. In specimens of higher alloy content, no martensitic transformation was observed. In those in which mar-tensitic transformation did occur, only specimens in which the martensite platelets existed as fine needles in localized regions were used. All specimens were reannealed 17 hr at 1200°C, quenched into ice water. and the capsule was broken. They were held in the ice water for from 5 to 10 sec, then transferred to a liquid-argon bath. This stepped quenching procedure was found to be more efficient than direct quenching into liquid argon. In the latter case, as soon as the hot specimen was immersed in the liquid argon, a protective, insulating layer of argon gas formed, and the specimen continued to glow vividly in the bath for some time. In the study of the habit behavior of martensite produced by deformation, specimens were deformed at room temperature either by compression, tension, or rolling. Martensite habit planes were determined by the two-surface analysis procedure described in reference 1. A stereographic net of 153/4 in. diam was used throughout the investigation. The method for determining the orlentation relationship between martensite and the matrix follows that used by Greninger and Troiano.' A diamond-polishing table with its auxiliaries was used in order

Jan 1, 1957

By Zdzislaw Specht

THIS paper discusses elementary laws pertaining to seismic reflection methods and presents a general and simple criterion for determining the direction of dipping of a reflection horizon from observational data of distance and time. The important development of practical geophysics and the successful results obtained in America, Germany, and other countries, caused introduction of geophysical methods of prospecting in Poland. Of all methods, seismic prospecting has proved most successful in the area of the Carpathian foreland, where new oil reserves are to be expected. Because of the great depth of the sedimentary column in that area, rang-ing sometimes over 2000 meters, it was obvious that only the seismic reflection method could give reliable information regarding the structural features of these strata at such a depth. During the experimental surveys it appeared that the complicated geological conditions of that area do not always allow prediction of the depth and the angle of dipping of reflecting horizons, and for that reason information about the inclination of a given horizon has great importance in the determination of subsurface structure. Therefore the problem arises of obtaining from seismic reflection data reliable information as to the direction of dipping of reflecting strata, without any previous knowledge of the average velocity and depth of geologic horizons under consideration.

Jan 1, 1940

By W. F. Wheeler

IN the study of the coals of Illinois now being carried on by the State Geological Survey, an attempt is being made to determine the most satisfactory basis of comparison between different coals. The following discussion is based upon work done for the survey in the laboratories of the State University and under the general direction of Prof. S. W. Parr. " Pure coal " has been defined by Mr. A. Bement1 as ash- and moisture-free coal, and the use of this " pure coal " as a basis for comparing different bituminous coals has lately been much discussed among engineers in the middle West. By some the B.t.u. of the pure coal is being used to check calorimetric results, and to calculate the calorific value of different coal-samples from the same seam, for which purposes it is necessary to assume-first, that the composition and calorific value of pure coal from different parts of the same coal-seam are uniform, and, second, that these values remain constant after the coal is mined, both of which assumptions there are reasons to believe are inconsistent with the facts. Certain variables are included in pure coal, as ordinarily defined, and disregard of them may lead to serious error. In any event, where delicate shades of difference are involved, no sure interpretation of results can be made, unless these variables be eliminated. As a basis of comparison between coals, ash- and moisture-free coal is much to be preferred to " dry coal," and still more is it to be preferred to " moist coal," as ordinarily reported in analyses. There are, however, two constituents other than ash and moisture which are similar in effect to them, and which

Jan 1, 1908

By I. H. Van Horn

IN the development of the incandescent electric lamp one aim of the investigators has been to establish the fundamentals of lamp design, so that the performance of any new lamp may be accurately predicted. The study of the temperature relations in lamps has done much toward establishing these fundamentals. Fig. 1 gives the typical FIG. 1.-ARRANGEMENT OF PARTS IN MAZDA B AND MAZDA C LAMPS. arrangement of the lamp parts in both the Mazda B (vacuum) and Mazda C (gas-filled) lamps. The outstanding differences are the filament form and the bulb shape. The ideal lamp is one in which the filament operates at a uniform temperature throughout its length. In practice, it is necessary to disturb this uniformity by the introduction of supports and terminals. The amount of cooling at the supports and terminals affects the over-all efficiency of the filament as a light producer. The life of the lamp is ordinarily proportional to the maximum and not to the average filament temperature. The Holborn-Kurlbaum type of optical pyrometer has

Jan 9, 1919

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

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

Jan 1, 1969

By Carroll Forbes

INTRODUCTION MANY different shapes of drill bits are in use with hammer drills, but little definite information is available whereby to judge which one of these shapes is the best. The following investigation was undertaken in order to determine what effect, if any, the shape of the cutting edge has on the cutting speed and wearing qualities of drill bits. The bits tested were those in common use, namely, the 4-point or cross bit, the 6-point bit, the Z bit and the "Carr" bit. The rock in which the tests were made was the red granite from southeast Missouri. It is a coarse crystalline granite containing an unusually large amount of quartz and is extremely hard, and on account of its uniform texture is admirably adapted to this work. While tests in other rocks might show somewhat different results, nevertheless it is the opinion of the authors that the relative cutting quality inherent in the shape of the bits would be the same in all rocks. Other qualities, such as mudding freely, freedom from fitchering, etc., might make one bit more desirable than another in softer rocks. DESCRIPTION OF BITS TESTED The 4-point bits were the usual shaped bits commonly made on the Leyner sharpener with 14° taper on the wings and a 90° angle between cutting edges. Some tests were run at 85 lb. pressure with a 4-point bit made with a 5° taper on the wings. This was made by using the Carr bit die. The 6-point bits were the usual shaped hits made on, the Leyner sharpener. The Carr bits were made with a 5° taper and an angle of 100° between cutting edges.

Jan 8, 1917

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

Possible applications of cyclone thickeners for: (1) clarification of the washery water and, (2) recovery of fine coal from the plant bleed. The paper shows: (1) that it is possible to remove all particles including the very finest, from the circulating water, thus obtaining a closed water system and, (2) that reduction of the ash content of the solids of the plant bleed is feasible by means of cyclone thickeners. Performance data for different size cyclones is given in the form of graphs.

Jan 1, 1950

By M. Cross

INTRODUCTION The results of the Japanese dissective investigations have [l-4] transformed our understanding of how the blast furnace operates. These studies revealed an internal structure of the furnace burden with five main zones, as illustrated in Figure 1. In the granular zone the charged material retains its structure whereas in the cohesive zone the iron ore particles are at advanced stages of reduction and form a semi-molten mass with a relatively high flow resistance. In the active coke zone molten iron and slag flow through a matrix of loosely packed coke. The raceway is a relatively small void space generated by displacement of coke due to the hot blast momentum, whilst the hearth is packed with coke, slag and molten iron. [ ] It is now well appreciated that furnace control is largely achieved and maintained by using the burden charge distribution to determine the gas glow distribution within the furnace and, hence, the shape and extent of the cohesive zone. In fact, Wakayama et a1 [5] of Nippon Steel Corporation state that optimum furnace operation is synonomous with the formation of a desirable cohesive zone shape, which in turn is almost solely determined by the burden charge distribution and its mechanical properties [6]. Much of the development work on operating furnaces since the dissective investigations has been oriented towards the identification of external furnace measures which reliably predict the shape of the cohesive zone. Currently the most popular measures are top gas temperature, velocity and CO/CO, ratio profiles [5]. More recently pressure distributions as evaluated from a series of wall measurements down the height of the furnace are also being utilised [7] to identify the position and shape of the cohesive zone. A great deal of emphasis has been placed upon achieving a consistent quality in the burden charge materials, establishing a suitable set of operating conditions and only making changes when forced to, ie., the operation for some reason moves outside a desired operating range or the production requirements change. Operational control schemes based upon this philosophy (eg., Kawasaki's GO-STOP system [8]) have been remarkably successful at achieving both high production rates and relatively low fuel costs. Mathematical models have long been used as tools to assist in the analysis of the blast furnace process. Although, the models have been useful in post-operative analysis and for identifying trends, etc., they have not proved reliable for detailed design criteria or as the basis for effective control schemes. Such mathematical models have moved from simple statistical correlation, through overall and stagewise heat-and-mass balance calcu-

Jan 1, 1984

By P. Nicholls

THOUGH the burning of fuels extends far back into antiquity, and though fuel beds are the most common and widely distributed example of chemical actions and engineering practice, there has been little attempt to group fuel beds by types or to define the principles associated with them. This paper does not profess to cover completely the subject of fuel beds. It suggests some of the over-all principles of the two more com-mon types. No new investigational data are included, but the deduc-tions are largely based on a recent publication of the U.S. Bureau of Mines1. DEFINITION OF TYPES There are three primary types of fuel beds: (1) Underfeed, in which the fuel and the air move in the same direction; (2) overfeed, in which the fuel and the air move in opposite directions; (3) crossfeed, in .which the fuel and the air move at right angles to each other. The principle that fixes the type is the relation between directions of the flow of fuel and of air. Fig. 1 shows the three types diagrammatically. All other types are compounded of these three in a simple or more or less complex manner. It does not follow that these three type designations are limited to the methods used in representing them in Fig. 1; they may be turned in any direction, and as long as the relative directions of the fuel and air are the same the type is not changed. For example, A as shown resembles a pot-type stoker, but the air and fuel can move downward as in the so-called smokeless heating boiler furnace. Also, C can be placed hori-zontal, as in chain-grate stokers. For this reason, the terms used to designate the three types are not all that could be desired; more logical ones could be coined, but those used probably are satisfactory until the discussion of fuel-bed types becomes more common.

Jan 1, 1935

By R. R. Joseph, K. A. Gschneidner

The solid solubility of magnesium in the close-packed modifications of lanthanum, cerium, praseodymium, neodymium, gadolinium, dysprosium, and lutetium was determined from approximately 250°C to the eutectoid temperature by the X-ray parametric technique. The maximum solubility at the eutectoid temperature was found to be 9.4 at. pet in La, 8.2 in Ce, 9.2 in Pr, 8.2 in Nd, 14.1 in Gd, 13.5 in Dy, and 11.5 in Lu. The solubility when compared at a homologous temperature was found to increase in a smooth manner with decreasing size factor from lanthanum to lutetium. It was found that the apparent atomic radius of magnesium when dissolved in the lanthanide solvent was constant and could be accounted for by consideration of several models dealing with departures from Vegard's law. The eutectoid temperatures for the lanthanide-rich La-Mg, Ce-Mg, and Nd-Mg systems were found to be 544", 505°, and 551°c, respectively. A study of the solid solubility of magnesium in the lanthanide metals was initiated because the valency and electron egativity difference are essentially constant and favorable for solid-solution formation, and thus one could examine the effect of size on terminal solid solutions. The size factors based on metal radii range from 14.6 pet for lanthanum to 7.5 pet for lutetium. Since the electronegativity difference is small, 0.06 unit or less, application of the Hume-~othery' and Darken and Gurry2 criteria for solid-solution formation indicates that the solubility of magnesium would be expected to be small for lanthanum (between 5 and 10 at. pet) and to increase as we proceed along the lanthanide series. A search of the literature revealed no data on the solubility of magnesium in the lanthanide metals except for the solubility of magnesium in cerium at 450oCA typical phase diagram for the lanthanide-rich end of the lanthanide-magnesium phase diagram is shown in Fig. 1. EXPERIMENTAL PROCEDURES Preparation of Alloys. The lanthanide metals used in the preparation of alloys for this investigation were prepared from the corresponding fluoride by metallothermic reduction techniques previously described by Daane.4 The chemical analyses of the metals used are listed in Table I.

Jan 1, 1965

By William B. Plank

IN this paper are presented the results of a complete statistical survey of the enrolment, courses and degrees, and the employment situation of recent graduates in all of the 46 institutions in the United States, including Alaska, and four of the six schools in Canada that grant degrees in mineral technology. The data were collected by the writer by means of a questionnaire in December, 1933, to which all the institutions, except one, replied. Included also are data of a similar study made by the writer in May, 1933, for the S. P. E. E. summer session of mining and metallurgical teachers at the University of Wisconsin and published in the Journal of Engineering Education for December. 1933. Some of the data of a paper of the writer's entitled, "The Trend of Mineral Engineering Student Enrolment in the United States," read at the A. I. M. E. meeting on Feb. 16. 1931, are given for comparison. Acknowledgment is made to all the administrative officers of the institutions who took the time from their busy lives to supply the in- formation asked for. Their fine cooperation has alone made possible these two surveys with a completeness of detail never before attempted

Jan 1, 1934

By GUY B. HUNNER

THOSE magnetite ore bodies comprising the Clifton Mines are situated in the south central part of St. Lawrence County, New York, on the western slope of the Adirondack Mountains. The topography is made up of gently rolling hills densely wooded with second-growth maple, birch, and hemlock. Drainage is north and west to the St. Lawrence River.

Jan 1, 1943

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

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

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

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

Jan 1, 1970

By D. H. Gurinsky, D. G. Schweitzer

The empirical equilibrium constantsd the heat of reaction for the reduction have been determined from 300° to 500°C. The mechanisms of the oxidation of uranium and magnesium from dilute bismuth solutions have been investigated. The kinetics of some of the reactions were affected by air adsorbed on the uranium oxides. THE Liquid Metal Fuel Reactor studied at Brook-haven National Laboratory uses a solution of uranium in bismuth as the fuel. Corrosion and stability problems require that the fuel solution contain corrosion inhibitors and deoxidants. Of the additives tested, magnesium has been found to be the best deoxidant and zirconium the best corrosion inhibitor in bismuth. Some experiments1 indicate that magnesium may play a secondary role in increasing the effectiveness of zirconium in inhibiting corrosion. The work reported here was intended to determine the relative concentrations of Mg and U required to prevent oxidation of the uranium fuel in the event of an air leak. In addition, an attempt was made to identify some of the mechanisms of the oxidation and reduction reactions occurring in the liquid bismuth solutions. EXPERIMENTAL Apparatus and Procedure—The equipment shown in Fig. 1 was designed so that the reaction kinetics could be studied as functions of temperature, melt composition, pressure, and flow rate. At the start of a run, the 10-liter bell jar (F) is removed by opening the bottom Dresser fitting (L), and the bismuth and additives are placed in a pyrex crystallizing dish (I). The bell jar is replaced, the system is evacuated to 10-5 to 10-6 mm Hg and then the heater (J) is turned on. When the selected temperature is reached, the oxidizing gas is admitted to the system to the desired pressure as read on the manometer (D). Gas is introduced through the slide tube (Q) which has a pyrex frit (R) sealed to its bottom. Stirring is accomplished by immersing the end of the tube in the melt. To maintain a constant pressure under flow the input and evacuation rates must be equalized. To obtain this condition stopcock (C) is closed and flowmeters (B) are matched. The reaction is "stopped" by closing the inlet flowmeter and quickly evacuating the system. To obtain a liquid metal sample, the system is evacuated with the sampler positioned near the surface of the liquid. The sampler, Fig. 2, is then immersed until its thermocouple reading matches thermocouple (G) Fig. 1. The system is then pressurized with helium which forces the solution through the frit. Twenty to 30 min elapsed between the time the system was evacuated and sampled. During evacuation and pressurization of the system, the temperature variations did not exceed ± 5°C. While bubbling occurred the temperature remained constant to within 1/2 oC. The volume of the equipment was determined by adding a known volume of air at atmospheric pressure to the evacuated system and noting the resulting pressure.

Jan 1, 1962

By K. T. Aust

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

Jan 1, 1962

By W. A. Burns

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

Jan 1, 1970

By E. B. Johnson

Cleveland-Cliffs lron Co., which operates Marquette lron Mining Co.'s Republic mine, conducted a test whereby 35,000 tons of self-fluxed pellets were produced in the grate-kiln system from specular hematite flotation concentrates. A brief description of the pelletizing plant is presented along with pertinent operating details. Date is included which compare operating conditions and the chemical and physical properties of the green and fired pellets for the self-fluxing pelletizing test with the normal acid pelletizing operation. The success of self-fluxed sinter in enhancing the operation of the blast furnace during the past few years has reasonably led to the assumption that the use of self-fluxed pellets might result in even greater furnace efficiencies. A great share of development work in agglomeration has been directed towards techniques related to the production of self-fluxed pellets, but only a limited tonnage of self-fluxed pellets had been produced on a commercial scale until this past year when The Cleveland-Cliffs Iron Co. produced 35,000 tons of such pellets by the grate kiln system at the Republic mine during the period May 21-June 5, 1962. REPUBLIC'S GRATE-KILN PLANT The grate-kiln pelletizing process consists of four stages, namely: feed or balling circuit, traveling grate, rotary kiln and annular cooler (Fig. 1). The balling section is conventional and utilizes four 9x30-ft balling drums in closed circuit with 5x14-ft vibrating screens having 3/8-in. rod decks. The traveling grate is 12 ft wide by 126 ft long and has 14 windboxes — six in the drying section and eight in the preheat section. The rotary kiln is 15 ft ID shell and 114 ft long. The annular cooler is 40 ft in diameter and has 12 windboxes. The cooler is divided into two zones by a moveable curtain wall. The high temperature air from the first zone is used as secondary combustion air in the kiln. Normally the only heat supplied is through the burning of No. 6 oil in the single kiln burner. Hot gases pass counter to the pellet flow through the system. The exit gases from the kiln pass down draft through the preheat section through cyclones and are drawn through the drying bed prior to exiting via the stack. The temperatures are normally held within the following ranges: Kiln 2400-2445 °F Preheat 1850-1950°F Drying 480-520°F Exit gas 200°F Pellets 120°F The design capacity of the Republic mine grate-kiln system was 2500 Itpd. Sustained production in excess of 35% over design capacity has been achieved. No screening of the cooler product is practiced. PELLETIZING TEST CONDITIONS When a decision was made to proceed with a test at the Republic mine pelletizing plant to produce 35,000 tons of self-fluxed pellets, several potential failure factors had to be carefully considered. Research work on a batch and pilot plant scale indicated that the grate-kiln system at Republic would require some major changes in order to obtain optimum conditions. In many cases compromises were agreed upon as major equipment changes and revisions were not feasible. The pelletizing conditions which laboratory development tests revealed were required in order to insure successful production of self-fluxed pellets were: 1) Good mixing of limestone and concentrate and proper moisture control; 2) Higher gas flow rates in the preheat section than are normally used; 3) Higher preheat temperatures than normal; 4) Maximum kiln temperature 2350°F. There was just cause for concern about balling problems that might occur. Approximately 10% of dry pulverized limestone was to be added to the specular hematite concentrate just ahead of the Pekay mixers on the belt feeding the balling drum. Large scale

Jan 1, 1963