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By J. W. Graham

For many years the author has been cognizant of the difficulty encountered by some in treating with the water influx formulas for unsteady-state fluid flow as pertain to the material balance equation. This has particularly applied in establishing reservoir performance and identifying reservoir pressure, which to the practicing engineer has entailed a trial-and-error procedure, and for others has necessitated resorting to computing devices and reiteration processes. In retrospect this difficulty stems from the fact that reservoir pressure in the material balance formulas, as well as associated with the water influx equations, is an inexplicit term, and the work reported in the past is irrefutable. However, what will be presented in this paper is another approach to the problem, whereby the entire material balance equation will be treated by the Laplace transformation, and reservoir pressure which hereto has been inexplicit, can now be isolated by mathematical procedure to relate that parameter with all the factors contributing to its change. This is the simplification entailed, that treats first with an undersaturated oil reservoir as an integrated effect from the inception of production. The second phase pertains to saturated oil reservoirs that encompass a survey traverse. Although both methods of approach are necessarily different in aspect, the most interesting fact is that the mathematics so deduced are identical. Both the linear and radial water-drive systems are incorporated. for which an illustrated factual example is offered for the latter, treating with a saturated oil reservoir. INTRODUCTIO N What is performed in this work is the simplification of an involved computation by advanced analysis. Although such may be construed as a contradiction when one treats with higher mathematics; nevertheless, when direction is given to such an undertaking the results car. be most revealing. Likewise, it is to be mentioned that the bases for these mathematics have been developed on the expediency of the occasion. This is not to be inferred as a qualification of this work, but rather the demands frequently placed upon the author in his private prac- tice in meeting a time limit. A situation, instead of being fraught with hazards, often has given emphasis to creative thought. What will be entailed in this work is the simplification of the material balance formulas by the Laplace Transformation., Although this reveals entirely new horizons that will be given expression in a forthcoming tract, it suffices in the present instance to limit our attention to this phase of the development that treats both with an undersaturated and saturated oil reservoir. To orient the reader's thoughts as to what is involved in this simplification is the recognition that reservoir pressure, as such, is an inexplicit term in the material balance equation. This is the independent parameter that defines the total history of performance in the author's' unsteady-state water influx formulas, as well as the basis for the physical dependency of fluid behavior within the formation as prescribed in the Schil-thuis' material balance equation. Therefore, to isolate reservoir pressure, which is the most essential factor in any reservoir study, is rather a cumbersome procedure entailing either a trial-and-error calculation for the engineer; or as some prefer, a reiteration process performed on a computing device. However, once such an equation can be transcribed as a Laplace transformation, this inexplicitness so expressed can be alleviated to identify reservoir pressure as an explicit function of all the factors contributing to its change. This is the simplification encompassed, that will treat first with an undersaturated oil reservoir as an integrated effect from the inception of production, and secondly, with a saturated oil reservoir as a survey traverse. Although the two approaches are necessarily different because of the uhvsics involved. it is an interesting commentary that the mathematics are identical, showing the interdependency of the two methods. In order to acquaint the reader with this development, the simplest case will be treated first; namely, an under-saturated oil reservoir subject to a linear water drive. However, what may be construed for this example as an idealistic case is actually a most practical application in certain parts of the world, where the size of the fields are so large that radial water-drive approaches the configuration of a linear drive. Further, to avoid the repetition of much symbolism, frequent references will be made to the work of the author and an associate on Laplace Transformations3,

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

THE annual winter meeting of the A.I.M.E., which is to open in New York on Feb. 14, will be charac-terized by a number of novel features. The most important is that the technical sessions will be dis-tributed over four days instead of three as heretofore. This makes it possible to reduce the number of conflicts between sessions and also will enable each member to attend a larger number. At the same time the ses-sions are so arranged by groups that those interested only in one or more that are related can, if necessary, cover all in that group in three days as heretofore. The general excursion to which the fourth day has, for some years, been devoted has been regretfully given up, mainly because of the uncertainties of the weather in New York in February. In its place a series of group excursions are being offered at various times during the meeting, arranged, so far as possible, so as not to con-flict with any technical session likely to be of interest to those taking part in a particular excursion. Among the places to be shown the visitors are: the construction work on the Eighth Avenue subway, a real mining job; the Vehicular Tunnel, the world's greatest ventilating project; the manufacture of 42-in. conveying belts; one of the largest and most modern steam plants; a coal terminal; manufacture of mining equipment; a cable-making plant; an oil terminal and refinery. Other en-tertainment features include a smoker Monday evening with a real chance to get together and talk; an informal dance and entertainment given by the Woman's Auxiliary on Tuesday evening; the dinner-dance at the Waldorf Wednesday evening, with no long speeches; a general session Thursday evening when the Petroleum Division will present a series of important reviews of the year. An extensive program has been arranged for enter-taining the ladies, and members are urged to bring their wives. There will be dinners, teas, theater parties, shopping and sight-seeing excursions as well as the dances. The usual general luncheons for members, guests and ladies will be served each day at headquar-ters, and various committees and groups will hold lunch-eons, dinners, and round table conferences as indicated in the schedule on the page opposite. The Mining and Metallurgical Society of America and the American Society of Steel Treaters are participat-ing in this meeting and their members will be welcome as guests at any session or function. A joint conference of the Mining and Metallurgical Society and the A.I.M.E. has been arranged for Tuesday afternoon, under the chairmanship of Clinton H. Crane, at which the whole matter of the mineral reserves of this country is to be up for discussion.

Jan 2, 1927

Several of the current concepts of brittle fracture involve consideration of, the existence of defects or flaws. Griffith 1 observed that the tensile strength of brittle materials was several orders of magnitude less than might be expected from the calculated strength of the molecular bonds. He was able to show that the stress concentration at the tip of an elliptical crack is sufficient to raise the local stress level many fold. He therefore proposed that real materials do contain such stress risers in the form of minute cracks and that this accounts for the rather large difference between theoretical and actual strengths of brittle materials. The degree of stress magnification depends to a great extent upon the orientation of the crack with respect to the general stress system, and to the general geometry of the crack. It is but a small step to extend the theory to include flaws and defects of other sorts which, though they may be less tractable mathematically than cracks, may still function as stress risers in a real sense in real materials. Brace 2 proposed that the application of the Griffith theory to rock material could be tested in two ways: "(a) by finding the orientation of cracks from which macroscopic fractures have developed and (b) comparing failure strengths from tests at different conditions of loading." In 1963 the author and coworkers at the Bureau of Mines, Twin Cities Mining Research Center, working on a problem involving relationships between strength, sonic velocity, and microstructure "eveloped an experimental technique to examine several somewhat similar questions; namely. does the frequency of occurrence of actual or potential stress risers dictate the relative strength of the material as proposed by Weibull;4 can actual flaws or defects in the rock structure be identified and related to strength and perhaps other properties in accordance with Griffith's theory; and is the anisotropic strength and elastic behavior of certain rocks related to the preferred orientation of these actual or potential stress risers? The experimental approach developed to answer these questions appears equally applicable to the testing of Griffith's theory as proposed by Brace. Basically the approach consists of a series of point-load tensile tests followed by petrofabric examination of thin sections prepared from the specimens in order to identify and apply a quantitative measure to microstructural defects which may have contributed to the failure process. In the point-load test, tensile stresses are induced by a compressive load applied to the center of a disc-shaped specimen by means of two opposing hemispherical indentors. Failure generally occurs as a single fracture parallel to the axis of loading and bisecting the disc. Because of the geometrical symmetrical the induced tensile stresses are symmetrical about the loading axis

Jan 1, 1967

By Walter V. Knopp, Laurence Delisle

The aim of this work was the preparation of nickel-steels from elemental metal powders by powder metallurgy techniques. It was known that plain carbon steels could be made from a mixtufe of iron powder and graphite and that the effect of carbon on iron in powder form was of the same nature as that produced in fusion metallurgy. The problem in making nickel steels from elemental powders consisted therefore in finding out whether sufficient diffusion of the nickel and other incidental metals . normally present in such steels could be induced in the solid state to modify the properties of plain carbon steels made from powders and produce the beneficial effect of alloying. The composition selected originally was that of an S.A.E. 2330 steel. Metal powders, in the proportion correspending to that composition, were mixed with graphite, pressed, and heated at different temperatures for different periods of time, to produce bonding of the metal particles and mutual diffusion of the various elements without melting. Temperatures up to 1325°C and sintering periods as long as 6 hr were first investigated because it was expected.that such conditions would produce maximum diffusion with an accompanying improvement in the properties of the alloy. It was found that, although diffusion proceeded to a large extent under the conditions investigated, it would not be complete unless sintering were carried out at a high temperature for much longer than 6 hr. Relatively high temperatures and long sintering times are objectionable from a practical point of view, particularly when a low COSt material is to be produced, because they necessitate the use of special, costly equipment. Work could be done to improve the diffusion of iron and nickel by changing conditions other than the sintering temperature and time, that is, finer primary or alloy powders could be used. However, a marked change in the properties of the steel had been observed even with only partial diffusion. It was thought, therefore, that instead of trying to improve the diffusion, advantage might be taken of its incompleteness to produce a special structure consisting, in the unquenched condition, of a hard constituent, rich in nickel, dispersed in a tough pearlitic matrix. Steels with such a structure, not readily obtainable by fusion, should have desirable mechanical properties. Besides, it should be possible to prepare them from elemelltal powders under economical conditions. This latter alternative was therefore adopted for the second phase of this work. This report is divided into four parts: I. General Procedure. 2. Effect of Sintering Temperature. 3. Effect of Varying the Nickel Content. 4. Effect of Alloying Elements. General Procedure The general technique of cold pressing as used in powder metallurgy was applied.

Jan 1, 1949

By Leendert de Witte, Fred J. Radd

In many areas caring failures can be directly related to electrical currents observed in the casings. It is the thesis of this paper that the observed casing currents are mainly due to electrochemical potentials of the type in evidence on spontaneous potential curves of electrical logs. The general nature of these potentials are discussed and an equivalent circuit is given for current and potential distributions around open holes. The casing forms a short circuit to these potentials and tends to average the effects of local cells. The case of casing corrosion opposite the Dakota water sands in the salt-mud area of Kansas is discussed anil used us a qualitative, illustration of the relation between SP's and casing currents. A method of quantitative derivation of casing current distribution frorn electric log SP curves, using linear transform theory, is described and results are compared with a measured current profile. The effects of hydrogen over-potentials at the cathodic portions of the pipe are considered and some laboratory data are given in support of conclusions regarding the over-1.01tuge.s. INTRODUCTION To date an appreciable amount of work has been done on the measurement of oil well casing currents and on the correlation of the anodic portions of the current profiles with corrosive casing failures. Speculations on the origin of the casing currents have, however, remained rather vague; and although almost every plausible cause has been mentioned, there is to the writers' knowledge no clear-cut expose' on the details of the causes of the corrosive currents in the literature. A study of current surveys and casing failures in the N.W. Burnett field, Ellis County. Kan.. indicated the probability that concentration cell emf's between the Wellington salt section and the relatively fresh waters in the Dakota sands were a major cause of the corrosion currents. A more general concept evolved upon analysis of the severe corrosive conditions in the Pleistocene sands in the Ventura Avenue and San Miguelito fields in California. In this area no major variations in the salt content of the formation waters occur and yet large casing currents are observed. An explanation is found in the fact that the local spontaneous potentials which are set up due to concentration contrast between the drilling fluid and the connate water are short circuited when casing is set. The very conductive path through the casing increases the magnitude of the currents and has the tendency to average local sources over fairly large intervals. Current will flow between the sections that are predominently shaly and the sections that are mostly sandy. At the places where the current leaves the pipe, corrosive attack will occur. This same phenomenon will be present wherever unprotected pipe is set through sections that show large SP kicks on the electric logs over reasonably thick interval~. GENERAL- NATURE OF THE SPONTANEOUS POTENTIALS When a sequence of sedimentary rocks is penetrated by a drill hole filled with a mud which has a different salt concentration from that in the formation waters, various types of electrochemical potentials are established between the formations and different parts of the mud column. Opposite clean sand sections. a simple liquid-liquid junction potential will be observed; while opposite argillaccous formations, a membrane potential, often referred to as shale potential, will be established. The first quantitative analysis of these emf's in terms of liquid junction and membrane potentials is due to Wyllie.1

Jan 1, 1956

John Chipman (Massachusetts Institute of Technology, Cambridge, Mass.)—After looking over the authors' shoulders for several years and after many discussions on the interesting diagrams of the types shown, it is a pleasure to see a formal paper published on this subject. There can be no doubt of the practical usefulness of the concepts shown. Inclusion formation in steel is such a highly complex matter that any system for understanding the subject is bound to be welcomed by those who must work with steels and who see in their day-to-day experience the good and evil effects of inclusions. A feature of the work with which the discusser has been concerned, and which he would now like to attempt to explain, is the relation between the schematic diagrams which the authors use and the phase diagrams for related systems. Obviously, the authors' diagrams are in no sense complete phase diagrams. However, there is a relation between this type of diagram and the true phase diagram, and the understand- ing of this relation ought to help in understanding the general picture which the authors are presenting. Consider the authors' Fig. 4, which shows the liqui-dus relations in the Fe-Mn-S-0 system. To show the complete relations between temperature and composition in these four ternary systems would require four triangular prisms, the vertical axes of which would represent temperature. The four triangles of Fig. 4 represent basal projections of certain lines from the four prismatic phase diagrams. Readers of the paper are all more or less acquainted with this type of projection and its usefulness and limitations are generally understood. In order to concentrate on the interesting parts and to minimize the less interesting features, the composition scale may be shifted to de-emphasize regions containing gaseous sulphur and oxygen. Such a diagram is shown in Fig. 16, which is a distorted version of the authors' Fig. 4. Here the oxide of iron is wiistite, denoted by W, and it is to be noted that between W and MnO lies the entire MnO-FeO "binary" system. Similarly, between MnS and FeS lies another binary whose

Jan 1, 1956

By T. M. Chance

THE term "low-sulfur coal," as used in this discussion, is limited to coals containing less, or very little more, than 1 per cent. sulfur. For certain purposes it might be advantageous to include coals that contain as much as 1.25 per cent. sulfur, because such coals have been considered as available for making metallurgic coke of fair grade; but the same reasoning might apply to coals containing as much as 1 ½ per cent. sulfur, if facilities exist for utilizing such coal by admixture with coal containing less sulfur. In Pennsylvania, it is not possible to define the exact geographic limits of the areas in which coals relatively low in sulfur exist, because variations in the percentage of sulfur occur irregularly and often abruptly. It is not uncommon to find areas, more or less circumscribed in extent, in which the coal is relatively high in sulfur although all the surrounding territory contains low-sulfur coal; and, similarly, small areas of low sulfur coal exist in districts where the coal is normally high in sulfur. These generalizations apply, With few exceptions, to the whole area underlaid with bituminous coal in the State of Pennsylvania, and also to each of the individual beds of coal in this state. Pennsylvania is poorly supplied with coals of the low-sulfur class. We find, however, as an offset to this condition, very large areas in which coal ranging from 1 to 2 ½ per cent. sulfur exists in beds of good workable thickness. This coal, by washing, can be reduced in sulfur low enough to make coke of a high grade. While a considerable tonnage of workable low-sulfur coal remains in the Pennsylvania bituminous dis-tricts, it has been necessary to turn to the areas of higher-sulfur coal for the supply of metallurgical coke. This utilization of the higher sulfur areas has been made possible either by washing or by selective mining. Washing.-Fine crushing of the entire feed is not generally necessary to the successful washing of Pennsylvania coals. This is due to the fact that the pyrite is rarely finely and uniformly disseminated throughout

Jan 8, 1919

By Frank H. Kneeland

Safety First is a popular motto—most mining companies have adopted it. It is probable, however, that in the majority of cases it is only a motto and gets no further than the office stationery or the bulletin board at the mine's entrance. In but few industries is there employed a greater diversity of machinery and mechanical devices than in coal mining. The list ranges all the tray from mechanical stokers to wood-working machinery and undercutters. Many of these devices, particularly those employed in wood working, are extremely dangerous. In 1913,23 per cent. of all fatalities occurring in coal mining in the U. S. were caused by machinery of some sort or other. Although the forms of accidents occurring with mining machinery are legion, they generally arise from one or more of five causes: (a) Falls from ladders, platforms, etc.; (b) coming in contact with moving machines or parts thereof; (c) electric shocks; (d) failure of some machine part; (e) mismanipulation of valves, levers, switches or other hand-operated controlling devices. The steps which may be taken to prevent accidents from the above causes are almost as numerous as the accidents themselves. There is, and can be, no panacea for all mishaps, nor for any one class of accidents. There is no mathematical or other formula that will bring immunity under any set of conditions. Common sense is the only guide. The remedy for the first-named class of accidents is simple and generally effective—namely, make the staging, ladder, platform, or other support, abundantly strong to carry any possible weight that it may be called upon to bear; provide ample railings on platforms or runways, and non-slipping feet on movable ladders. Coming in contact with moving machine parts is one of the greatest dangers met with in the operation and maintenance of mining machinery. Unfortunately, machine manufacturers have not as a class adopted the idea of thoroughly protecting and incasing the dangerous parts of their product. No one has, or should have, a better or more thorough knowledge of what the dangerous parts or elements of a machine may be than its builder. The desire to construct a piece of mechanism as cheaply as

Jan 1, 1915

By O. W. Ellis

BEFORE entering upon a general discussion of the fascinating, but at present rather controversial, subject of gases in copper, the author feels that some attention should be directed to the work which has been carried out on the solubility of gases in metals. The outstanding contributions to our knowledge of this subject have been made by Sieverts and his collaborators(1) t and by Iwasé.(2) Both the German and the Japanese investigators employed apparatus of the same general design in their investigations. Full reference need only be made, therefore, to the German scheme, which is diagrammatically illustrated in Fig. 1. This, to use the words of Sieverts, which he employed in describing his Burette arrangement of apparatus at the 1928 meeting of der Deutschen Gesellschaft fur Metallkunde(1g): shows a diagram of the usual mode of procedure. A quartz flask contains the metal (for high temperatures a highly refractory porcelain FIG. 1.-SIEVERTS' APPARATUS FOR INVESTIGATING SOLUBILITY OF tube is used) and is connected with the rest of GASES IN METALS. the apparatus by means of a stopcock. The other parts consist of a burette divided into 1/10 c.c., a leveling tube, and art adjus-table mercury reservoir. The burette is connected on one side with the gas inlet and on the other side with the absorption flask; the connection can be interrupted by means of suitable taps. Another tap permits the connection of the flask and the Töpler pump. In an experiment the quartz flask is first exhausted and then a meas-ured quantity of gas is let in from the burette. In the first place the volume of the flask when empty is found by calibration with an inert gas. The pressure is read off on the level tube of the burette, and the temperature measured by means of a thermo-couple whose welded junction lies close to the outside of the quartz flask, which is heated in an electric furnace. In several experiments the quantity of absorbed gas was transferred to a burette by means of a pump and measured.

Jan 1, 1932

By Jerry H. Service, F. L. Partlo

The following investigation was undertaken to develop a method for determining with reasonable accuracy the depth of overburdens of 100 ft. or less. Seismic methods seemed to offer good possibilities. The problem differed from that of the familiar salt-dome location in that the depth of overburden to be determined is much less than is encountered in oil prospecting. This means that a much shorter time interval must be measured with accuracy. Refraction methods seem at present to offer greater possibilities than reflection. The air sound persists for from 0.1 to 0.5 sec., because of echoes, and seismic reflections coming during this time are difficult to detect. A seismometer sensitive to vertical vibrations only offers possibilities and has been used here with some success. It is hoped that the application of this type of seismometer to reflection shooting in this region may be investigated still further. The apparatus used consisted of a carbon-button seismometer followed by a three-stage, transformer-coupled, vacuum-tube amplifier and a General Radio string oscillograph. Time marks are provided by a 1000-cycle, 600-r.p.m., synchronous motor provided with five spokes which intercept the light to the camera at 1/50 sec. intervals. This motor is driven by a two-stage vacuum-tube amplifier of 3 watt output, actuated by a tuning fork. The power supply for the seismometer amplifier is one 2-volt storage and one 45-volt B battery. The motor amplifier is powered by a 6-volt storage battery and 6 to 225-volt, 15-watt motor generator. The temperature-frequency characteristics of the tuning fork have been determined and for ordinary working temperatures the error in time that would be introduced is less than M millisecond for time intervals up to 100 milliseconds. The impact is produced by a sledge blow for surface distances less than 100 ft. and dynamite for greater distances. Two steel balls with wires attached form an electric circuit through a 1-ft. piece of railroad rail upon which they rest. When the rail is struck by the sledge the balls rebound, opening the circuit and indicating the time of impact by a break in the oscillograph record line as at A, Fig. 3. When dynamite

Jan 1, 1934

By O. W. Ellis

Before entering upon a general discussion of the fascinating, but at present rather controversial, subject of gases in copper, the author feels that some attention should be directed to the work which has been carried out on the solubility of gases in metals. The outstanding contributions to our knowledge of this subject have been made by Sieverts and his collaborators(1) † and by Iwasé.(2) Both the German and the Japanese investigators employed apparatus of the same general design in their investigations. Full reference need only be made, therefore, to the German scheme, which is diagrammati-cally illustrated in Fig. 1. This, to use the words of Sieverts, which he employed in describing his arrangement of apparatus at the 1928 meeting of der Deutschen Gesellschaft für Metallkunde(10): shows a diagram of the usual mode of procedure. A quartz flask contains the metal (for high temperatures a highly refractory porcelain tube is used) and is connected with the rest of the apparatus by means of a stopcock. The other parts consist of a burette divided into 1/10 c.c., a leveling tube, and an adjustable mercury reservoir. The burette is connected on one side with the gas inlet and on the other side with the absorption flask; the connection can be interrupted by means of suitable taps. Another tap permits the connection of the flask and the Töpler pump. In an experiment the quartz flask is first exhausted and then a measured quantity of gas is let in from the burette. In the first place the volume of the flask when empty is found by calibration with an inert gas. The pressure is read off on the level tube of the burette, and the temperature measured by means of a thermocouple whose welded junction lies close to the outside of the quartz flask, which is heated in an electric furnace. In several experiments the quantity of absorbed gas was transferred to a burette by means of a pump and measured. Care was taken by Sieverts to cool the ground-in joint between the reaction flask (or tube) and the rest of the system. Suitable precautions

Jan 1, 1934

By G. L. Tufford, R. L. Bleifuss

Low-grade manganiferous iron ores of Minnesota's Cuyuna Range, in general, do not respond to conventional mineral dressing techniques because of their fine-grained texture. Reducing these ores to magnetite with subsequent magnetic separation and flotation have not given satisfactory results because, in many instances, concentrate grade and manganese recovery are low. Metallization of iron and concurrent reduction of higher manganese oxides to MnO, as in the R-N process, followed by recovery of iron by magnetic separation and manganese by leaching, seems to be a technically feasible process. High-temperature x-ray diffraction studies show that solid-state reactions between iron and manganese, with the formation of intermediate iron-manganese oxides, occur during reduction and affect recovery of both iron and manganese from the final product. Solid state reactions also occur between FeO, MnO, and SiO, at temperatures as low as 900°C. The kinetics of these reactions are such that they become an important factor in the treatment of ores by the R-N process. These investigations suggest a temperature and gas composition cycle that would maximize both iron and manganese recovery. During the past ten years, iron ore shipments from the Cuyuna Range of Minnesota have decreased sharp1y. Because of adverse grade, structure, and cost, many Cuyuna ores are no longer competitive with high-grade foreign ores and domestic pellets. The low-grade manganiferous iron ores from the Cuyuna Range, in general, do not respond to conventional mineral dressing techniques because of their fine-grained texture. Reducing these ores to magnetite for subsequent magnetic separation and flotation has not given satisfactory results because concentrate grade and manganese recovery are often low. However, a technically feasible process appears to be metallization of the iron and concurrent reduction of manganese oxides to MnO with recovery of metallic iron by magnetic separation and extraction of manganese from the tailings by leaching. In 1962 the R-N Corp., with a grant from the Area Redevelopment Administration, conducted an amenability study of the metallization of manganiferous iron ore from the Cuyuna Range. The results of this preliminary investigation were sufficient to interest the Economic Development Administration in sponsoring further studies of the process with emphasis on secondary recovery of manganese from the nonmagnetic tailings. Inasmuch as the metallization process has considerable influence on the final form of the manganese - its texture and distribution between the magnetic concentrate and nonmagnetic tailings-the investigation included a study of metallization of the ore as well. Therefore, the investigation conducted at the Mines Experiment Station covered three interrelated phases: (1) laboratory R-N roasting studies and magnetic separation tests, (2) laboratory chemical extraction experiments of the nonmagnetic tailings, and (3) a mineralogical study of the crude ores and their various roast products. High-temperature x-ray diffraction investigation of the Fe-Mn-Si0,-0, system is the main topic of this paper and an extension of the mineralogical work. GENERAL GEOLOGY The Cuyuna Range is known for its complicated geologic structure, complex orebodies, and generally indifferent response to attempts at conventional beneficiation. Several geologists have made intensive studies of the Cuyuna Range, including Leithl (1907), ~darns' (1910), Zapffe3 (1925), Grout and Wolff4 (1955), and schmidt5 (1963), whose study was the most comprehensive of all. The Range is covered with glacial deposits - till, out-wash, and lake sediments -up to 250 ft thick. Bedrock stratigraphic units of the Cuyuna Range consist of three tightly folded Precambrian sedimentary formations. The lower unit is the Mahnomen formation, composed of 2000 or more feet of argillite, slate, siltstone, and quartzite. The middle unit is the Trommald formation, which varies from 45 to 500 ft in thickness and comprises the major iron-bearing formation. The upper unit is the Rabbit Lake formation, consisting of over 2000 it of argillite, slate, and interbedded lenses of lean iron formation. In the central part of the Cuyuna Range, the units have been folded into a series of

Jan 1, 1969

By C. S. Smith, L. Guttman

It is shown, from a study of geometric probabilities, that the average number of intercepts per unit length of a random line drawn through a three-dimensional structure is exactly half the true ratio of surface to volume. Since the surfaces can be internal or external, the area of grain boundary or of the interface between any two constituents in a micro-structure can be measured. Other metric relations are tabulated that may be of use in studies of the microstructure of polycrystalline, cellular, or particulate matter generally. IN many fields of scientific investigation the structure of cellular aggregates or random arrays of discrete particles imbedded in some matrix is observed on a two-dimensional section and inferences are drawn therefrom as to the real structure in three dimensions. The biologist's microtome slice, the petrologist's thin section, and the metallurgist's plane polished and etched sections are common examples, although the problem is a general one. Scientists have commonly limited their thinking to the same dimensionality as their structures, and the few attempts that have been strictly three-dimensional in character have been laborious and noteworthy. From a metallurgical standpoint it is often of considerable importance to know, in addition to the volume fraction of two or more components in an alloy, the amount of two-dimensional interface between crystals. Such grain boundaries (which may separate either two identical crystals differing only in orientation or two crystals differing in structure, and possibly also in orientation) have a determining factor upon the mechanical behavior. It is at these boundaries that melting commences, that stress-induced corrosion occurs, and that various precipitates (harmful or otherwise) first appear. The boundary is doubtless of equal importance in nonmetallic crystalline aggregates such as rocks, ceramics, and concrete, and the biologist is deeply concerned with the area of cellular membranes. Many synthetic cellular foams involve similar structural problems. The very term structure usually implies the presence of interfaces and a complete understanding of structure involves nothing but an analysis of the geometrical, metrical, and topological relations between the various interfaces (zero, one and two-dimensional) that exist in a three-dimensional structure. Even systems lacking sharp physical interfaces often have interrelated gradients of composition or velocity (as cored crystals or turbulence cells) in which a neutral surface can be treated as a two-dimensional interface. In an earlier paper by one of the authors' the question of cell shape was considered in terms of simple topological principles without regard to physical dimensions. The determination of the actual size of grains in two dimensions is carried out in a routine fashion in innumerable metallurgical laboratories (see, for example, the ASTM standard methods of grain size determination2), though this is done merely to check the uniformity of a product and has no relation to the actual three-dimensional shape or size of the grains. Some authors have discussed the three-dimensional problem but only on the basis of assumptions as to idealized grain shapes.:'-' Quantitative measurements of microstruc-tures to obtain the volumetric relations of various phases have been carried out by petrographers for many years and are of increasing popularity among metallurgists." The present paper will show how, on the basis of no assumptions other than randomness of sectioning (usually realizable in experiment), it is possible to learn a great deal about the three-dimensional structure. The relations to be derived will generally be used on random arrays of cells or other particles, although they are equally applicable to ordered arrays and even to isolated objects of complex shape provided that suitable random sections can be made. Total Area of Interfaces in a Sample Consider a typical microstructure of a single-phase polyerystalline metal, such as that shown pres- in Fig. 1. The plane cross section shown contains a network of lines which subdivides the area into two-dimensional cells. The lines, of course, represent merely the intersection of the two-dimensional plane of sectioning with the two-dimensional interfaces between adjacent three-dimensional cells. The structure also contains points at which two or more lines intersect: in three dimensions the points are, of course, lines. In the more general case there may be in three dimensions isolated particles surrounded by a single interface without contact with others, and both two and one-dimensional features which do not necessarily connect with others. On the two-dimensional section these will appear as areas delineated by a closed line (as at a and b, Fig. 2), as isolated lines

Jan 1, 1954

By P. Pietrokowsky, T. E. Tietz, J. E. Dorn

The amount of solid solution hardening in aluminum alloys was found to be dictated by two factors: the lattice strain, and the change in the mean number of free electrons per atom of the solid solution. To obtain this correlation it was necessary to assume that aluminum contributes two electrons per atom to the metallic bond. WHEN the modern scientific method of analysis was first being formulated, Francis Bacon recorded in his "Essays" (circa 1600) that "an alloy . . . will make the purer but softer metal capable of longer life." During the intervening centuries voluminous data have been reported which demonstrate that the additions of alloying elements do in fact increase the hardness and strength of the pure metals. Nevertheless, the significant details of this problem on the unique effect of each element toward enhancing the mechanical properties of alloys only recently have been subjected to systematic scientific scrutiny. The major objective of this investigation is to determine how minor additions of alloying elements affect the plastic properties of polycrystalline aluminum alloys. By means of such studies it is hoped to provide not only data on the solution strengthening of aluminum alloys, but also a body of facts which will supplement the knowledge already available on the factors responsible for solution hardening in general. A review1"10 and analysis1' of the existing data on the effect of solute elements on the plastic properties of solid solutions reveal that our current knowledge on solid solution hardening is somewhat meager, inconsistent, and inconclusive. Many of the inconsistencies are undoubtedly attributable to the influence of unsuspected factors, such as purity; or uncontrolled factors, such as grain size, on the plastic properties of alloys. Nevertheless the following conclusions might be tentatively accepted: 1. Addition of solute elements invariably increases the yield strength, tensile strength, and hardness of the host element. 2. The rate of strain hardening, in general, increases with the concentration of the alloying element. 3. The strengthening effect in ternary alloys is the sum of the individual strengthening effects of the two solute elements as measured in their binary alloys. 4. The lattice strain is one factor that affects the strengthening of the alloy but it is not the only factor. 5. A second factor might be the difference in valence between the solute and solvent metals. All of the available evidence is in complete agreement with the first conclusion; the remaining conclusions, however, are not in agreement with all of the published data, but, in each case, the major weight of the existing evidence favors these deductions. Additional investigations will be required before most of these tentative conclusions can be accepted without reservation. In the following report an extensive investigation of the plastic properties of binary aluminum alloys is described. This work was undertaken in an attempt to shed more light on the general problem of solid solution hardening. Materials for Test: Aluminum was selected as the solvent metal for the present investigation on the effect of solute elements on the plastic properties of alloys. This choice was made for several reasons: (1) There appears to be little fundamental data in the published literature on the effect of solute elements on the properties of high-purity aluminum alloys. In view of the ever increasing economic importance of aluminum, such data would be of basic interest to the metallurgists concerned with the development of new aluminum alloys. (2) Aluminum is thought to be only partially ionized in the metallic state1' and consequently it might provide more complex relationships of the mechanical properties with the concentrations of the solute elements than more simple fully ionized solvents would reveal. (3) The data on aluminum alloys will provide a broader basis for correlations between the mechanical properties of metals in general and the concentration and atomic properties of the solute elements than is now available. Some complications, however, attend the selection of aluminum: The solubility of the various elements in the alpha aluminum phase are quite restricted, and not always well known. Consequently, only dilute solid solutions are available for study. This, however, may be somewhat advantageous because the dilute solution laws presumably are simpler than those applying to concentrated solutions. In addition, strain-hardened pure aluminum is known to recover at atmospheric temperatures. Very likely its alloys exhibit slower recovery rates. Thus, the secondary factor of effect of alloying elements on recovery might complicate the data. Such compli-

Jan 1, 1951

By N. A. D. Parlee, N. M. El Tayeb

Fe-V alloys with small percentages of vanadium show no deviations from Sieverts' Law up to P~, = 1 atm in the 1600º to 1750ºC region. At somewhat under 8 pct V and up to at least 20pct V, at 1604" and 1661 °C, nitrogen absorption follows Sieverts' Law at low Pn2 values, but deviates from this law beyond critical values of pn2, due to formation of a nitrzde phase of approximately VN composition. The behavior below these solubility limits can be described at all temperatures by the equations: RAO and parlee1 suggested that the nitrogen absorption curve for liquid iron alloys takes the general form shown in Fig. 1 when an alloy nitride precipitate is formed. They showed that the precipitation of 6 titanium nitride from liquid Fe-Ti alloys follows this general scheme and dealt with the general theory involved. Recently, Evans and Pehlke2 reported their research on the precipitation of aluminum nitride from liquid Fe-A1 alloys. Fountain and Chipman's recent paper3 on the precipitation of boron nitride from solid solution contains a fine example of the analogous behavior which they have been studying in the solid state. Researches on the absorption of nitrogen by liquid Fe-V alloys have been described by various authors.1,4-7 Most of this work has been confined to fairly low vanadium concentrations and rather high temperatures because of difficulties variously described as, formation of surface scums, bridging, and so forth. This behavior and the rough thermo- dynamic calculations made by chipman,8 over eleven years ago, indicated that excessively high vanadium concentrations should not be required for vanadium nitride precipitation. It seemed desirable to look for and study this precipitation in order to fill out the thermodynamically interesting nitrogen absorption data on these alloys. EXPERIMENTAL METHOD The general method used was essentially the same as employed by Rao and parlee,1 in which a Sieverts type of apparatus was used and the precipitation of the nitride detected by the "break-point" in the Sieverts' Law line, and by the visual observation of the formation of the new phase on the surface of the melt. There were, however, a few differences in apparatus and technique as described below. The oil manometer used by Rao and parlee' to measure low partial pressures of nitrogen was not employed. The present authors sought to avoid as much as possible the exposure of the liquid alloy to low total pressures of gas during the 6 to 10 hr long runs because of the heavy iron evaporation-loss errors involved. This was achieved, partly by keeping evacuation times to a minimum with fast pumping but largely by the use of two burettes, one for argon and one for nitrogen, and using them to equilibrate the alloy with mixtures of argon and nitrogen rather than nitrogen alone. Each run involved a careful sequence of operations. After melting, de-

Jan 1, 1963

By Robert S. Dewey

AS a result of drilling operations during 1943, West Texas again added sufficient new oil reserves to replace the oil produced during the year, but failed to maintain its position in currently available reserves because the deeper discoveries will require years for development. Drilling failed to provide the additional oil necessary to meet the increase in current and anticipated market demand. Although 13.3 per cent of the total footage drilled was in wildcat exploration, the ratio of oil discoveries to total wildcats was less in 1943 than in 1942, but comparable to that in 1941. Of the 732 field wells completed, 270 were at Slaughter, 55 at Wasson, 45 at Mascho and 31 at North Cowden. As of Dec. 31, 1943, there were 361 drilling wells including 71 wildcat and 290 field wells; 19.7 per cent were wildcats. It is anticipated that the percentage of wildcats of the total wells will be higher during 1944 than in either 1942 or 1943. Tables 3 and 4 present a three-year comparison of drilling activity and illustrate the downward trend of development that has been in effect during that time. Because of development lag in the deeper Ordovician fields, several years elapse before 2 sufficient number of wells is completed to give a substantial producing rate. As these new oil reserves cost more to find, and will cost more to produce on a barrel basis than the oil marketed during the year, their reserve replacement value to the industry is less in money. Costs While complete costs for deeper drilling are not yet available for analysis, it is evi- dent from the data on drilling rates to comparable depths, contract prices, and general increases in costs, that the cost of drilling has risen approximately 20 per cent during the year. One representative drilling contractor estimates that the average drilling time on a 5000-ft. field well has increased nearly one third and that out-of-pocket costs have increased a dollar per foot. Three major factors contribute to this increased cost: (I) less experienced labor, (2) deterioration in mechanical equipment and expendable material, and (3) increased contract prices. In the past, when there were more drilling rigs than wells to be drilled, some contractors would cut their drilling profit to keep their personnel and rigs working. As this practice is no longer necessary, the contract prices are adjusted upward to assure a profit. On deep and difficult drilling, contracts are let on a cost plus basis. A number of mechanical difficulties have become evident. Inferior quality of steel used in drill pipe and rock bits has added appreciably to drilling time and cost. Contractors are experiencing delay in obtaining repair work and repair parts for prime movers. As the length of drilling time required an shallow-field wells has not increased in proportion to that on deeper wells, it seems that the medium-sized drilling rig is better adapted mechanically than the heavy one to the work imposed. One of the main deficiencies in the heavy rig equipment is inadequate pump capacity. Drilling Mud The increasing amount of deep drilling has emphasized the importance and relationship of good mud to efficient and suc-

Jan 1, 1944

By Robert S. Dewey

AS a result of drilling operations during 1943, West Texas again added sufficient new oil reserves to replace the oil produced during the year, but failed to maintain its position in currently available reserves because the deeper discoveries will require years for development. Drilling failed to provide the additional oil necessary to meet the increase in current and anticipated market demand. Although 13.3 per cent of the total footage drilled was in wildcat exploration, the ratio of oil discoveries to total wildcats was less in 1943 than in 1942, but comparable to that in 1941. Of the 732 field wells completed, 270 were at Slaughter, 55 at Wasson, 45 at Mascho and 31 at North Cowden. As of Dec. 31, 1943, there were 361 drilling wells including 71 wildcat and 290 field wells; 19.7 per cent were wildcats. It is anticipated that the percentage of wildcats of the total wells will be higher during 1944 than in either 1942 or 1943. Tables 3 and 4 present a three-year comparison of drilling activity and illustrate the downward trend of development that has been in effect during that time. Because of development lag in the deeper Ordovician fields, several years elapse before 2 sufficient number of wells is completed to give a substantial producing rate. As these new oil reserves cost more to find, and will cost more to produce on a barrel basis than the oil marketed during the year, their reserve replacement value to the industry is less in money. Costs While complete costs for deeper drilling are not yet available for analysis, it is evi- dent from the data on drilling rates to comparable depths, contract prices, and general increases in costs, that the cost of drilling has risen approximately 20 per cent during the year. One representative drilling contractor estimates that the average drilling time on a 5000-ft. field well has increased nearly one third and that out-of-pocket costs have increased a dollar per foot. Three major factors contribute to this increased cost: (I) less experienced labor, (2) deterioration in mechanical equipment and expendable material, and (3) increased contract prices. In the past, when there were more drilling rigs than wells to be drilled, some contractors would cut their drilling profit to keep their personnel and rigs working. As this practice is no longer necessary, the contract prices are adjusted upward to assure a profit. On deep and difficult drilling, contracts are let on a cost plus basis. A number of mechanical difficulties have become evident. Inferior quality of steel used in drill pipe and rock bits has added appreciably to drilling time and cost. Contractors are experiencing delay in obtaining repair work and repair parts for prime movers. As the length of drilling time required an shallow-field wells has not increased in proportion to that on deeper wells, it seems that the medium-sized drilling rig is better adapted mechanically than the heavy one to the work imposed. One of the main deficiencies in the heavy rig equipment is inadequate pump capacity. Drilling Mud The increasing amount of deep drilling has emphasized the importance and relationship of good mud to efficient and suc-

Jan 1, 1944

By H. E. Cook

The Ising model for the internal energy of a binary alloy has been used to obtain a general equation for the critical resolved shear stress of partially ordered crystals. The equation expresses the stress in terms of the Warren "alphas " and can be used to estimate the variation in strength with order without the assumption, present in the original formulation of this problem in terms of domain size, that order is complete within each domain and that the domains are of ungorm size and shape. In addition, it is the general equation, according to the Ising model, for strengthening by short-range order. Two applications of the equation are considered: One is an estimate of the variation in strength of CkAu with long-range order. The other is an estimate of the variation in strength of FeCo with quench temperature. Reasonable agreement is found with the variations reported in the literature. When the internal energy of an alloy crystal depends upon the distribution of solute, the strength of the crystal will also depend upon it because a portion of the applied stress for plastic deformation will be: where V is the volume of the crystal and E(E) is the energy change associated with the solute redistribution caused by the plastic strain, E. We expect T to equal zero for a crystal having a random arrangement of solute because the arrangement would remain random after plastic deformation. Likewise, we expect it to equal zero when the crystal is perfectly ordered because the motion of paired dislocations found in such crystals does not disrupt order. However, when short-range order exists or when long-range order is incomplete, plastic deformation will decrease the amount of order and additional work, proportional to the ordering energy, will be expended. Fisher' estimated T for crystals having short-range order by assuming an interaction energy between neighboring atoms and estimating the change in the number of unlike neighbors as a dislocation moved through the crystal. (His analysis was limited and several workers2"6 have since given more complete ones.) Fisher minimized the importance of a strengthening mechanism of this type for paired dislocations in a structure having long-range order. ~ottrell,' however, pointed out that T could be appreciable for ordered crystals having antiphase domains. He attributed the strengthening to the increase in surface energy of the domains as they were cut by paired dislocations. Ardley,' in his test of Cottrell's theory, found that r for Cu3Au crystals obeyed the equation: for 1 > t where 1 is the domain size, t is the domain wall thickness, and y is the surface energy of an antiphase boundary. His experiments represent the classic confirmation of the strengthening mechanism proposed by Cottrell. However, the assumptions involved in using Cottrell's theory are valid only for large domain size in CU~AU,~"~ i.e., when Eq. [2] reduces to: For small domains, ~linn~ has questioned Ardley's assumption that order was complete, and, indeed, Stoloff and ~avies" fpnd it incomplete until a size of approximately lOOA was reached. Even when the order within a domain is complete, it is not obvious how one determines the appropriate value for I in a structure where domains vary in size and are irregularly shaped. The purpose of this paper is to estimate T without restrictions upon the degree of order and domain shape. Our major assumption will be the use of a generalization of the model proposed by Bethe" (the Ising model) for the internal energy. This will in fact allow us to combine the theories for strengthening by short-range order and by antiphase domains into a single, general formalism. We will use the results to estimate the variation in strength of Cu3Au crystals with long-range order8 and the variation in flow stress of FeCo crystals with quench temperature.12'13 INTERNAL ENERGY For simplicity, we restrict our considerations to those binary solid solutions which can be described as an arrangement of atoms on a Bravais lattice. An atom site will be indexed by three numbers (PI, pz, p3) determined by the vector: from the origin fixed at atom (0, 0, 0) to the atom site where a', an, and a, are the lattice translation vectors. We write: For the energy of the crystal where pi(p) is the probability (either zero or one) of finding an atom of type i (i = 1, 2) at site (p), which is shorthand for (pl, pz, p3) and pj(p + r) is that for an atom of type j (j = 1, 2) at the site (p + r), which is shorthand for (pl + rl, The coupling parameter, resents the energy associated with the pair Pi(p), Pj(p + r). The crystal is assumed large enough so that surface effects can be neglected; therefore, trans-lational and inversion symmetry require the coupling parameters to obey the relations

Jan 1, 1969

By R. Didchenko

THERE are many methods described in the older literature which claim to produce anhydrous rare-earth chlorides in general. and cerium chloiide in

Jan 1, 1960