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By O. F. Thornton, D. L. Marshall

Results of the determination of the inter stitial water content of several core samples from oil reservoirs are presented. Data obtained by the capillary pressure method, which has recently been developed, are compared with water saturations measured in cores cut with oil-base mud and with values calculated from the electrical resistivity of the formation. The agreement between the capillary pressure and other methods, combined with the fact that similar agreement has been obtained by others, indicates that the capillary method properly applied yields results sufficiently accurate for most engineering purposes. In some cases, it may be possible to extend the utility of data obtained with the capillary pressure method by correlation of interstitial water saturation with more easily measured physical properties of the media. Introduction Several methods are in use for determining or for estimating the interstitial water saturation at given points within oil and gas reservoirs. The direct measurement of the water content of cores obtained with nonaqueous fluid in the hole is believed to be an accurate method under most conditions. The water saturation may be calculated by use of the resistivity curves of the electric log,' although this method is not applicable under conditions that exist in some reservoirs. Recently, a method has been developed and described3.' wherein the interstitial water saturation of cores is measured at a capillary pressure such that conditions existing in the reservoir are simulated. The purpose of this paper is to present data obtained by use of this latter method, and to compare the results obtained with determinations made by other means. Method The theory underlying the capillary pressure method applied to petroleum reservoirs has been discussed adequately in the literature by Garrison,2 Leverett,5 and Others.3,6,7 Briefly, and simply, capillary pressure is defined as the difference in pressure between two contacting fluid phases, such as oil and water. For the simplified sand, water and oil system illustrated in Fig I, the pressure difference can be stated as follows:6 where Pc is the capillary pressure in pounds per square inch, ? is the interfacial tension between oil and water in pounds per inch, r1 and r2 are the radii of curvature of the interface between oil and water in inches. Capillary pressure varies in a given reservoir with depth because of the greater density of the water phase as compared with oil or gas. The following equation expresses the difference in pressure between two points: p1- p2 - h?p/144 [2] where p1 — p2 is the capillary pressure difference in pounds per square inch, h is

Jan 1, 1947

By D. L. Marshall, O. F. Thornton

Results of the determination of the inter stitial water content of several core samples from oil reservoirs are presented. Data obtained by the capillary pressure method, which has recently been developed, are compared with water saturations measured in cores cut with oil-base mud and with values calculated from the electrical resistivity of the formation. The agreement between the capillary pressure and other methods, combined with the fact that similar agreement has been obtained by others, indicates that the capillary method properly applied yields results sufficiently accurate for most engineering purposes. In some cases, it may be possible to extend the utility of data obtained with the capillary pressure method by correlation of interstitial water saturation with more easily measured physical properties of the media. Introduction Several methods are in use for determining or for estimating the interstitial water saturation at given points within oil and gas reservoirs. The direct measurement of the water content of cores obtained with nonaqueous fluid in the hole is believed to be an accurate method under most conditions. The water saturation may be calculated by use of the resistivity curves of the electric log,' although this method is not applicable under conditions that exist in some reservoirs. Recently, a method has been developed and described3.' wherein the interstitial water saturation of cores is measured at a capillary pressure such that conditions existing in the reservoir are simulated. The purpose of this paper is to present data obtained by use of this latter method, and to compare the results obtained with determinations made by other means. Method The theory underlying the capillary pressure method applied to petroleum reservoirs has been discussed adequately in the literature by Garrison,2 Leverett,5 and Others.3,6,7 Briefly, and simply, capillary pressure is defined as the difference in pressure between two contacting fluid phases, such as oil and water. For the simplified sand, water and oil system illustrated in Fig I, the pressure difference can be stated as follows:6 where Pc is the capillary pressure in pounds per square inch, ? is the interfacial tension between oil and water in pounds per inch, r1 and r2 are the radii of curvature of the interface between oil and water in inches. Capillary pressure varies in a given reservoir with depth because of the greater density of the water phase as compared with oil or gas. The following equation expresses the difference in pressure between two points: p1- p2 - h?p/144 [2] where p1 — p2 is the capillary pressure difference in pounds per square inch, h is

Jan 1, 1947

By John F. Allan

This paper does not pretend to advance any facts or improvements not known to many members of the Institute, but is intended merely to give a few practical hints on preliminary tests, and to call attention to a possible enlarged field for the cyanide process in the treatment of some silver-ores, which merits investigation. Broadly considered, the choice of a process for the treatment of silver-ores in Mexico is confined to the following alternatives: (1) Concentration for treatment by smelting; (2) milling and pan-amalgamation; (3) the patio and Ortega process; [4) chloridizing roast and lixiviation; (5) chloridizing roast and cyaniding; and (6) cyaniding of the crude ore. These methods of treatment may also be combined, and cyaniding or concentration, or both, may be introduced, at what-ever stage it is found to be most advantageous. The characteristics of the ore (especially its gold-content) and local conditions, such as distance from railway, cost of fuel, amount of water available, vary so much that it is impossible to make general comparisons between the different processes, either as to extraction or cost. Concentration and subsequent smelting may be made very expensive by long-distance transportation of concentrates; pan-amalgamation is undoubtedly expensive; and the patio process is barred when the ore contains appreciable amounts of gold, by reason of its poor extraction of that metal; yet there are many ores for which each of these processes is especially adapted, and the expense of treatment is compensated by the results obtained.

Jan 1, 1905

By Roy A. Koski

INTRODUCTION Cleveland-Cliffs Iron Company, and its subsidiary companies, operate and manage mining, beneficiation, and pelletizing operations in the Upper Peninsula of Michigan, the province of Ontario, Canada, and the State of Western Australia, Australia. The concentrates and natural ores vary mineralogically, physically and chemically. This paper describes the techniques employed in pelletizing the various concentrates and ore fines. The plant operations described are the Republic, Humboldt, Tilden, Empire and Pioneer in Michigan, the Adams and Sherman in Ontario, and the Robe River in Western Australia. Table 1 contains further details regarding design and operating capacities, commissioning dates, and participant ownerships. Allis-Chalmers grate-kiln systems are utilized in Michigan and Ontario, and Dravo straight-grate systems in Western Australia. Currently, the Empire and Tilden operations are being expanded. At Empire the additional pelletizing unit, identified as Unit IV, will have a design capacity of 8 996 metric tonne/d and is scheduled for startup May 1, 1979. The Tilden operation is being doubled with the additional pelletizing unit, identified as Unit 11, having a de- sign capacity of 12 599 metric tonne/d. Startup is scheduled for January 1, 1980. MINERALOGY OF CONCENTRATES AND NATURAL ORES In the Upper Peninsula of Michigan, the operations process ores from the Negaunee iron formation of the Marquette Range. The

Jan 1, 1977

By J. B. Wagner, p. Hembree

The iron tracer diffusion coefficient of umstite has been measured at 110(fC across the phase field and at a single composition at 800°C. Assuming a simple cation vacancy model the tracer diffusion coefficient was found to be a linear function of the cation vacancy concentration at 1100°C. The equation is D = 3 x 20 29 where denotes the concentration of vacancies in numbers per cc. The tracer work at 800°C was carried out to investigate the reported "pinning" of tracer to the wustite surface at low temperatures. No evidence for the "pinning" of the tracer was found at 800°C in COz-CO gas mixtures. HIMMEL, Mehl, and Birchenall,&apos; Carter and Richardson,2 and Desmarescaux and La combe3 have measured the diffusion of iron tracer in wustite at several temperatures and compositions. The present work was undertaken to extend the measurements over a large composition range at 1100°C and to resolve certain apparent discrepancies in the data, expecially at lower temperatures. EXPERIMENTAL Wustite was prepared by oxidizing rectangular iron plates* in C02-CO mixtures. The samples were •The iron was supplied by the Battelle Memorial Institute courtesy of the American Iron and Steel Institute. The analysis is presented in Table I. quenched. Due to the inward flow of cation vacancies during oxidation, the center of the sample contained a thin void. The edges of the wustite slab were sanded until the sample could be split into two parts. Each part was then sanded on the front and back flat area until a smooth surface was obtained. The specimens were then replaced in the furnace and equilibrated at llOO°C in a predetermined COa-CO mixture by methods described elsewhere.4"6 The specimens were again quenched and the surfaces were lightly sanded to remove any roughness following the first equilibration. The specimens were then reequi lib rated in the same C02-CO mixture for thirty minutes in order to relieve any mechanical damage on the surface due to the polishing. The specimens were then quenched and the tracer was applied by an electroplating technique. The work of Carter and ~ichardson&apos; demonstrated that there was no systematic difference in the iron tracer diffusion coefficient in wustite if the tracer was plated, dried, or evaporated on the specimen. In the present study a piece of filter paper was saturated with an iron chloride solution of pH <* 3 that contained the tracer FeS5. The wustite was placed on the filter paper and made the cathode. A current density of 0.4 to 0.6 ma per sq cm was passed for about five to ten minutes. The thickness of the tracer layer was estimated to be about 7 x lom6 cm. This estimate was made by considering the area plated, the current flow, and time for plating and the activity of the iron in the plating solution. Different areas of the specimen were counted using a collimator to determine the uniformity of the tracer. Any specimen which exhibited a variation from the initial count rate (about 1500 cpm) by more than 15 pct was rejected. An estimate of the time necessary to convert the thin layer of iron tracer to wustite was made using the data of Pettit and wagner." he estimated time was 1 sec at 1100°C assuming linear oxidation kinetics. The shortest diffusion anneals were 1800 sec. The samples were suspended in the hot zone of a furnace by two platinum wires. Two separate specimens were run at the same time. Only the edges of each sample were in contact with the wires. The C02-CO gas of the same composition as that used in the pre-diffusion anneals flowed freely around the samples at a linear velocity of 0.9 cm per sec. To initiate a run, the specimens were lowered from the cold zone of a furnace to the hot zone by a magnetic lowering device." bout 60 sec were required for lowering. To terminate a run, the sample was withdrawn from the hot zone to the cold zone. Time zero for the beginning of the experiment was taken when the sample blended into the red glow of the furnace and conversely for the end of the experiment. The surface decrease method of measuring the tracer diffusion coefficient was used to collect the data. This method requires that counting geometry be reproducible because the specimen is counted before the diffusion anneal and after the anneal. A special jig was constructed for each specimen so the specimen could be removed from the jig and returned to the jig such that the well geometry was reproducible.

Jan 1, 1970

By R. W. Leonard

A method of accurately determining the value of gold-bearing ores and gravels with a compact field-outfit is much desired by prospectors, especially when the work lies in a district far removed from railways or good wagon-roads. We are all familiar with the fire-assay of gold-ores, and fully recognize its accuracy and value; but only those who have tried to determine the value of a gold-bearing vein as a commercial venture, from fire-assays of selected samples, know how misleading is the information thus obtained, however carefully and honestly the samples may be selected. The reasons are that, for the fire-assay a very small portion of ore is treated (rarely more than six assay-tons, or a little over one-third of a pound), and a minute particle of the precious

Jan 1, 1896

By E. A. Steigerwald

E. A. Steigerwald (Thompson Ramo Wooldridge, Inc.1— he authors&apos; results clearly indicate that cracking can be produced by the hydrogen pressure developed during a charging operation. This type of cracking or blistering has also been observed in polycrystalline materials24"28 when the charging conditions are sufficiently severe and is often referred to as irreversible embrittlement since it cannot be removed by a baking treatment. There are additional data, however, which must be considered before a pressure theory can be generally employed to account for all failures which occur as a result of hydrogen. In many cases, hydrogen embrittlement in a tensile test or in delayed failures under static loads is a reversible phenomena which cannot be simply explained on the basis of preexisting cracks generated by the charging operation. It is this aspect of the problem which has prompted many investigators to seek mechanisms other than hydrogen pressure to explain their results.24&apos;n728 Fig. 15 indicates an example where, under specific experimental circumstances, hydrogen embrittlement can occur at liquid nitrogen temperatures. In this case, which has been previously decribed,&apos;&apos; specimens were charged with varying quantities of hydrogen, immediately quenched, and tested in liquid nitrogen (-320°F). A companion set of identical specimens were charged, aged at 300°F to remove the hydrogen, and also tested at -320°F. When the current density was greater than lo-&apos; amp per sq in., embrittlekent occurred in both sets of specimens, indicating that cracking had occurred during charging and the embrittlement, as in the case of Fe-Si single crystals, was irreversible. At current densities between approximately 103 and lo-&apos; amp per sq in, the embrittlement was present only for those specimens which contained hydrogen during the testing sequence. The embrittlement was therefore reversible with respect to the aging and charging operations. Since extensive hydrogen movement would not be expected at -320°F, it is difficult to reconcile these data with a mechanism which requires pressure and pressure dependent growth of preexisting cracks. There are other features of hydrogen embrittlement such as the reversibility of the incubation time for delayed failure with respect to applied stressg0 and the influence of prestraining31 which are also difficult to explain using a pressure model. Any general mechanism of hydrogen embrittlement will have to consider the reversible aspects of the embrittlement data as well as the irreversible portion which has been clearly presented for the Fe-Si crystals and which is consistent with a pressure model. A. S. Tetelman and W. D. Robertson (authors&apos; reply)—he authors agree with Dr. Steigerwald that a general mechanism of hydrogen embrittlement must be applicable in all cases where embrittlement occurs. Dr. Steigerwald&apos;s experiments were performed on an iron alloy which has an extremely complex microstructure, and therefore does not lend itself to the direct and detailed observations that can be made in Fe-Si. The change in the characteristics of cracks as a consequence of annealing at 300°F is not really known in detail but it is probable that stress-relaxation (blunting) occurs, dislocations produced near the crack tips will be pinned by carbon atoms, and hydrogen will be lost to the atmosphere. Any, or all of these effects of annealing will alter the ease with which a crack subsequently propagates under applied stress. A quantitative treatment of the problem must take these effects into account. Since diffusional processes are presumably eliminated at -320°F, the general mechanism proposed by Dr. Steigerwald&apos;s colleagues cannot be operative at this temperature. A detailed discussion of the general&apos; inapplicability of this mechanism has been presented elsewhere. However, the data presented by Dr. Steigerwald in his discussion can be explained in terms of a pressure model. Crack propagation under internal pressure P and applied stress occurs when where is the total energy expended in creating new surface area and by plastic work at the crack tip. The total crack length increases with increasing current density, since we have shown that it systematically increases with hydrogen concentration and Dr. Steigerwald has shown that hydrogen concentration increases with current density. For large L (high current density) Eq. [I] can be satisfied even if P = 0 and the embrittlement process does not require the presence of hydrogen. Specimens charged at a lower current density will con-

Jan 1, 1963

By G. W. Powell

ACCORDING to crank,&apos; the accumulation equations for inter diffusion in a binary system whose molal volume is a function of concentration are

Jan 1, 1965

By C. B. Murray

"OUR experience from time immemorial has been that the furnace sampler and analyst usually find one or two, and sometimes more, points less iron than the Lake Superior shippers, but, fortunately, their contracts are `iron bound&apos;; and, generally speaking, analyses at this end are practically useless, for we are obliged to settle on basis figured out to a half dozen decimals, and, as a rule, without recourse in the event of flagrant discrepancies between the two analysts." The above is an extract from a letter received by the writer of this paper from the President of an iron company, discussing the question of sampling. It so well expresses the opinion of many blast-furnace owners and managers that it seems a suitable text for a discussion concerning the need of uniform methods of sampling. If all railroad cars were loaded the same, if all stock piles were the same shape, and if ore was received regularly each day, the problem of sampling would be comparatively simple. The conditions, however, vary widely at different places, and at the same place from day to day, and it is probably impossible to determine upon any one method of sampling which will apply at all times and in all cases. However, it would seem as though some general principles might be suggested which would tend to overcome these wide differences in samples of the same thing. The sampling of a cargo of iron ore begins at the breast of ore in the mine. The ore is sampled from the mine cars, from the stock piles, and from the railroad cars at the mines. At the lower Lake ports the ore is practically all sampled from the boat, occasionally from railroad cars. At the furnaces, the ore is nearly all sampled from railroad cars and occasionally from stock piles.

Jan 1, 1914

By Horace Pops

ThE shape of the primary solid-solubility limits in copper-rich Cu-Si-Zn alloys has been discussed recently1 in terms of the atomic size effects and the electron concentration, e/a. Although these limits are parallel to lines of constant e/a near the Cu-Zn binary system, they deviate and become sharply restricted near the Cu-Si binary system. Hence, it appears that the primary solid solutions with higher silicon contents are restricted by the presence of the intermediate phases, [, X, and p, which follow them in the ternary system. owever, a similar restriction in solid solubility might also result from an interaction in the copper matrix between silicon and zinc. Evidence for such possible interactions has been observed, for example, in the Al-Mg-Si systion.A where a contraction of lattice spacings in the ternary solid solution appears to correspond to an electrochemical interaction between the two solute elements, magnesium and silicon. The observed contraction is associated with restricted solid solubility. It was also shown1 that the extent of the primary solid solubility did not follow the trends predicted by the lattice-distortion oncept." This again suggested that the solubility limits are strongly affected by the stability of the intermediate phases, I, 1, and X . In order to test the above hypotheses, lattice-parameter measurements of the fcc @-phase alloys were determined within the ternary system at a constant electron concentration (e/a = 1.30) and also at a constant zinc content. Alloys of predetermined composition were prepared from high-purity metals and melted and cast under reduced pressures of helium in quartz capsules. Since the weight losses were very slight and did not exceed one part in 2000, the nominal compositions listed in Table I were accepted without chemical analyses. The ingots were homogenized

Jan 1, 1964

By Persifor Frazer

It was my intention to have directed the attention of the members of the Institute to a complete series of rocks representing the older and middle formations represented in Pennsylvania, but time has been insufficient for the purpose, and 1 have been unable, in the first attempts to reduce the sections of those rocks, which I have brought with me to this meeting, to the requisite thinness necessary for exhibiting the peculiarities of their constituent minerals. The rocks represented here belong to the various horizons already mentioned, and include gneiss, ferruginous gneiss, chlorite slate, quartzites, and hydro-mica slates, limestones, dolomites, ferruginous conglomerates, quartz conglomerates, " Potomac marble" (nether member of the Mesozoic series), dolerites, and a syenite. The order in which these are named is, roughly, the order .of geographical position in a section line from southeast to northwest, commencing at the intersection of the Northern Central Railroad with the Maryland line, and ending a few miles from the town of York, and a short distance within the marginal outcrop of Mesozoic red sandstone. In such a geographical section all the rocks above mentioned would be encountered in the given order except syenite, about which a few words are to be said in a moment. (But this is far from representing the rocks in their geological sequence.) There is nothing of unusual interest to present to your notice in these slates and quarteites. The limestones were carefully searched tinder 450 diameters microscopic power, but they show no signs of organic remaius. One section of a fine-grained Triassic sandstone contains a very beau- . tifully banded plate of quartz. But the objects of greatest interest at present are the specimens of trap. The more fine-grained and compact traps were collected from

By W. J. Reagan

Many factors enter into the manufacture of basic open-hearth steel of high quality. Perhaps the two most important are temperature and the iron oxide content of the metal. If we can control these two factors we can essentially control basic open-hearth practice. SOURCE AND EFFECT OF IRON OXIDE Earlier investigators, especially Herty and his associates, have shown that iron oxide is introduced into the open-hearth furnace in four ways:&apos; 1. By oxidation of the scrap by furnace gases. 2. By decomposition of the limestone. 3. By oxidation of the iron oxide in the slag by furnace gases. 4. By direct addition of iron ore to the charge. We also know that the speed of operation of an open-hearth furnace depends, for a given charge and given combustion conditions, on the rate at which iron oxide will diffuse from the slag into the metal. The rate of diffusion depends upon a number of variables, such as iron oxide content of the slag, slag viscosity, etc., which also depend upon the amount of iron oxide in the metal, amount of carbon present, temperature, and so forth. For a given carbon and a given temperature, the iron oxide content of the metal is in proportion to the iron oxide content of the slag. This fact can be easily verified by analysis of slag samples taken as described by Herty.2 It is preferable to take these samples just before deoxidetion. In killing the steel samples with aluminum it is desirable to use aluminum rod of 99 per cent purity; ordinary commercial aluminum rod with a purity of approximately 92 per cent is not satisfactory. In drilling these samples it is also essential to take the largest amount of drillings possible. This gives more accurate results because it eliminates spotty segregation of A12O3.

Jan 1, 1932

By John T. Norton, Robert W. Lindsay

A number of detailed investigations of the physical changes accompanying age-hardening have raised the question as to the possibility of some phenomenon preceding the actual process of precipitation. There is considerable evidence to indicate that in the first stages of the aging process there is a pronounced distortion of the crystal lattice. This is particularly marked in duralumin. It would be of considerable theoretical interest to know the nature of this distortion as compared with that produced in other ways and to find out whether, in supersaturated alloys, it is a necessary antecedent to the formation of a second phase by precipitation. It was believed that a study of the age-hardening char-acteristics of a normally aged alloy compared with one that had been mechanically distorted might supply some useful information on these points. In addition, information would be obtained regarding the effect of a mechanical distortion on any subsequent stage in the aging process. Duralumin was chosen as the material for this investigation because the various aspects of its aging behavior can be shown in detail by suitable variations of the aging temperature. Also, probably more work has been done on this class of alloys than on any other. In spite of the many published results, it was felt that the experiments would be significant only if all of the work were done on samples from the same source and if they were examined under identical experimental conditions. Previous Work The many studies of the mechanism of aging in duralumin have been more or less crystallized by a series of papers by Fink and Smith1~2~3 and a recent paper by Cohen.~ The former authors believe that a simple precipitation theory is adequate to account for the various phenomena

Jan 1, 1939

By John T. Norton, Robert W. Lindsay

A number of detailed investigations of the physical changes accompanying age-hardening have raised the question as to the possibility of some phenomenon preceding the actual process of precipitation. There is considerable evidence to indicate that in the first stages of the aging process there is a pronounced distortion of the crystal lattice. This is particularly marked in duralumin. It would be of considerable theoretical interest to know the nature of this distortion as compared with that produced in other ways and to find out whether, in supersaturated alloys, it is a necessary antecedent to the formation of a second phase by precipitation. It was believed that a study of the age-hardening char-acteristics of a normally aged alloy compared with one that had been mechanically distorted might supply some useful information on these points. In addition, information would be obtained regarding the effect of a mechanical distortion on any subsequent stage in the aging process. Duralumin was chosen as the material for this investigation because the various aspects of its aging behavior can be shown in detail by suitable variations of the aging temperature. Also, probably more work has been done on this class of alloys than on any other. In spite of the many published results, it was felt that the experiments would be significant only if all of the work were done on samples from the same source and if they were examined under identical experimental conditions. Previous Work The many studies of the mechanism of aging in duralumin have been more or less crystallized by a series of papers by Fink and Smith1~2~3 and a recent paper by Cohen.~ The former authors believe that a simple precipitation theory is adequate to account for the various phenomena

Jan 1, 1939

By C. H. Benedict

1. Shaking Tables 2. Fine Grinding 3. Hydraulic Classification 4. Mechanical Thickeners 5. Flotation ENTERING the profession of minerals beneficiation (it was plain garden variety "ore dressing" . in those days) I was fortunate that at that time the first major innovation in modern ore dressing practice was being introduced. I refer to the Wilfley table. You youngsters that came into the game only 30 years ago or even more recently, with flotation machines and reagents as your very ready tool in time of trouble, do not realize what the invention of the Wilfley table meant to us. We had but one physical property of ores to reckon with-specific gravity- and when there was but little difference in specific gravity between the mineral and the gangue, we were in trouble. The jig and the revolving table were our only mechanical equipment for recovering values and so that we might make even a reasonably satisfactory extraction, we had to classify and reclassify, and jig and rejig, and worry about the laws and advantages of free settling vs hindered settling and just tire the minerals out.

Jan 10, 1954

By W. C. Kerr

ThE distribution of gold is obviously much wider than is Commanly supposed. Resides the usual matrices, vehicles, or associates, such as quartz, pyrite, chalcopyrite, etc., I find it occurring in quite a range of common rocks. For example, at the Rhodes mine, in Gaston County, a body of 9 to 12 feet of decoroposed, light-gray gneiss was worked together with the strings of quartz, and yielded from six to ten dollars to the ton. A mine in Moore County yields its gold mainly from a feldspathic schist. In the famous King&apos;s Mountain mine, in Gaston County, the gold is obtained not only from the seams of quartz in a blue, hydromicaceous schist, but a 60-foot ledge of grayish-blue, fine-grained, schistose limestone is quarried out bodily and sent to the stamps. It is gold-bearing throughout. In Montgomery County the singular concretionary, conglomeritic, quartzite schist, which contains Emmons&apos;s palceotrochis, is gold-bearing over wide tracts of country. This fact was noticed by Dr. Emmons. But a still more striking and significant fact is, that a large part of the gold of Montgomery, Davidson, and Randolph counties,

Jan 1, 1882

By M. E. Wadsworth, T. L. MacKay

Sintered UO, samples were leached in sulfuric acid solutions of various concentrations. A pressurized system was used so that it was possible to investigate the kinetics of the reaction to 270°C with oxygen overpressures as high as 900 psi. The rate was observed to be a function of the concentration of hydrogen ions and directly proportional to the partial pressure of oxygen. Evidences are presented which indicate that a UO2 surface site reacts with a molecule of water to form a hydroxyl complex which in turn can dissociate with the characteristics of a weak acid. A rate determining step has been proposed which involves the reaction between an oxygen molecule and the hydroxyl complex on the surface of UO,. ThE 2 principal methods for uranium dissolution are carbonate and acid leaching. The sulfuric acid leach is the more popular and is used for the treatment of the majority of the ores of Africa, Canada, and the United States. Low recoveries in basic leach circuits led investigators at the University of British columbia1 to study leaching of uranium ores in pressurized vessels. Early in the study of dissolution of uranium it was found that only uranium in the hexava-lent state could be leached in acid or basic circuits. Therefore, the use of oxygen over-pressure in an autoclave offered an interesting approach to solving the low recovery problems of carbonate leaching. UO, was used in this study because it could be obtained in high purity and also because it is representative of the most refractory of the primary uranium minerals. A pressurized system was used to provide a means whereby important temperature and pressure parameters could be varied for the evaluation of the kinetic processes. The mechanism for the dissolution of UO2 should be similar for any of the uraninite type minerals. At the present all of the kinetic studies that have been conducted have been in carbonate media. Peters and Halpern2 carried out a kinetic study of the leaching of pitchblende. Their specimens were pitchblende ores selected on the basis of high grade and homogeneity. Pearson and wadsworth3 conducted a kinetic study of the dissolution of UO2 in carbonate solutions with results very similar to those obtained by Peters and Halpern. EXPERIMENTAL The UO2 as received* was found by spectroscopic *Mallinckrodt reagent, supplied by the Atomic Energy Commission. analysis to have a purity of 99.94 pct 0.03. It was ground in a mechanical agate mortar and screened through a 400-mesh sieve. Thin flat disks of UO2 were prepared by pressing the sized powder in a specially constructed die at a total pressure of approximately 25 tons per sq in. The pressed disks were approximately 0.25 cm thick, 1.6 cm diam, and 3.5 g in weight. As pressed, the samples were approximately 65 pct of theoretical density. It was essential that a binder such as poly-vinyl alcohol be added before pressing to prevent formation of cracks when fired. It was found by trial and error that pressed disks sintered close to 1870°C in a hydrogen atmosphere, reach densities between 91 and 91.5 pct of the theoretical density. At this density the samples had no measurable porosity based upon a 2-hr emersion in boiling water. An X-ray examination of these sintered UO2 disks showed them to be identical with the original UO2 received. Reaction of UO2 with the alundum furnace core was prevented by placing molybdenum between the samples and the core according to the method of Corwin and Eyerly.4 Leaching studies were carried out in a specially designed autoclave, the details of which have been presented e1sewhere.6 The main features of the equipment as applied to a kinetic study are: 1) solution samples may be removed during the course of a single run; and 2) temperature and agitation are carefully controlled. Two-ml samples removed from the autoclave during the course of a run were analyzed for U3O8 content with a Beckman model DK-2 spectrophotometer by the method of

Jan 1, 1959

By D. K. Das, P. A. Beck, S. P. Rideout

IN a previous publication1 1200°C isothermal phase diagram sections were given for the Cr-CO-Ni, Cr-Co-Fe, Cr-Co-Mo, and Cr-Ni-Mo ternary systems, in which the a phase formed narrow, elongated solid solution fields. The present investigation is concerned with the 1200°C isothermal sections of the Co-Ni-Mo, Co-Fe-Mo, and Ni-Fe-Mo ternary systems. A prominent feature of these systems is the presence of narrow, elongated µ phase fields. The crystal structure of the phase designated as µ both here and in the previous publication1 was determined by Arnfelt and Westgren.2 For the (CO, W)µ phase, named by them Co,W, (and also frequently designated as a), these authors found that the crystal system is hexagonal-rhombohedra1 and the space group is D53d — R3,. Westgren and Mag-neli3 later found that isomorphous phases exist in the Fe-W and the Fe-Mo systems (these phases are often referred to as < and E, respectively). Henglein and Kohsok4 stated that the phase described by them as Co7Mo,; (otherwise frequently designated as c) is also isomorphous with the above three. The Co-Fe-Mo system was investigated at 1300°C by Koester and Tonn,5 who found a continuous series of solid solutions between (Co, MO)µ and (Fe, MO)µ Koester6 also indicated similar uninterrupted solid solutions in the Ni-Fe-Mo system. However, since the Ni-Mo binary system does not have a phase isomorphous with F, Koester&apos;s diagram is expected to be erroneous. No data appear to be available in the literature concerning the Co-Ni-Mo system. The face-centered cubic (austenitic) solid solut,ions of iron, nickel, and cobalt, which are quite extensive in all three systems at 1200°C, are here designated as the a phase. The body-centered cubic (ferritic) solid solutions, based on iron, are designated in this report as the ? phase, in conformity with the nomenclature used previously.&apos; Experimental Procedure The alloys were prepared by vacuum induction melting in zirconia and alumina crucibles. The lot analyses for the metals used have been given.&apos; The number of alloys prepared was 46 for the Co-Ni-Mo system, 65 for the Co-Fe-Mo system, and 113 for the Ni-Fe-Mo system. The compositions of these alloys were selected with due regard to maximum usefulness in locating phase boundaries. The alloy specimens were annealed at 1200°C in an atmosphere of purified 92 pct helium and 8 pct hydrogen mixture. Alloys consisting almost entirely of the face-centered cubic austenitic a phase, or of the body-centered cubic ferritic c phase were double-forged with intermediate annealing. The double-forged specimens were then final annealed for 90 hr at 1200 °C and quenched in cold water. Alloys containing considerable amounts of any of the other phases could not be forged. Such specimens were annealed for 150 hr at 1200°C and quenched. Microscopic specimens of all alloys were prepared by mechanical polishing, in many cases followed by electrolytic polishing. Description of the polishing and etching procedures used and tabulation of the intended compositions of the alloys prepared are being published in two N.A.C.A. Technical Notes.7,8 , Many of the alloys were analyzed chemically and, in general, the results are in excellent agreement with the intended compositions. X-ray diffraction samples were prepared by filing or crushing homogenized alloy specimens and by reannealing the obtained powders in evacuated and sealed quartz tubes. After annealing for 30 min at 1200°C the tubes were quenched into cold water. X-ray diffraction patterns were made with unfiltered chromium radiation at 30 kv, using an asymmetrical focusing camera of high dispersion. X-ray diffraction and microscopic methods were used jointly to identify the phases present in each specimen. The amounts of the phases in each alloy were estimated microscopically. The phase boundaries were located by the disappearing phase method. The results were used to construct 1200°C isothermal sections for the three ternary phase diagrams. The accuracy of the location of the phase boundaries determined in this manner is estimated to approximately ±1 pct of each component. The portion of the three phase diagrams lying between the µ, P, and 6 phases on the one hand, and the molybdenum corner on the other, has not been investigated. Recently Metcalfe reported0 a high temperature allotropic form of cobalt on the basis of dilatometric results and of cooling curves. In the present work no attempt was made to search for the new phase in the cobalt corner of the Co-Fe-Mo and Co-Ni-Mo systems. No alloy was prepared with more than 80 pct Co; the alloys used were intended to locate the boundary of the a phase saturated with cL. The microstructures of the quenched a alloys near the cobalt COrner gave no suggestion of an in-suppressible transformation On quenching. The location of the boundaries of the a + ? two-phase fields in the Fe-Ni-Mo and Fe-CO-MO systems was determined entirely by the microscopic method. The face-centered cubic a alloys near the ? field transform partially or wholly into the body-centered cubic ? phase on quenching from 1200°C to room temperature. The ? formed in this manner has an

Jan 1, 1953

By F. R. Archibald, C. M. Nicholson

The present paper may be considered complementary to an earlier contribution on the same subject by F. R. Archibald and C. F. Jackson.1 It is particularly concerned with engineering and technological aspects of the operations at the Harleyville Alumina Plant during its period of operation from January 1945 to July 1946. The plant was built for and operated by Ancor Corporation, at Harleyville, South Carolina, as part of the government sponsored wartime program related to alumina production from domestic raw materials. The main purpose of the program was to secure technical and engineering data, based on actual plant experience, that might serve as a foundation for large scale production of alumina from raw materials other than bauxite. The Harleyville plant was directed specifically to treatment of clays found in very extensive deposits in the Carolinas and Georgia using the lime-sinter process developed by Ancor Corporation. It is considered that the purpose stated above has been served and this paper is to record and discuss some of the more important findings. The main factor in location of the plant at Harleyville was the presence in that locality of a rather remarkable deposit of high calcium limestone. The clay mining operation was centered near Aiken, S. C., and although a rail haul of ninety miles was involved there were, at the time, factors favorable to the Harleyville location offsetting, in part, the cost of transportation of clay, There are, no doubt, locations in the general area where clay and limestone deposits may be found in closer proximity hut they had not been proven up when the project was undertaken. Availability of power from the Santee-Copper development whose high tension line skirted the Property; ready access to rail and highway transportation; the promise, realized in actuality, of ample supply of soft water; and availability of labor supply were other factors of importance. Moreover, the general area has the decided advantage, for this type of operation, of a mild climate. Construction was begun in August 1943, and although stopped for a time priding review of the general situation that fall, it was resumed, albeit with less urgency, and substantially completed by the end of 1944. The total capital cost was approximately $3,460,000 The first alumina was turned out in April 1945 and from then until the plant was closed down in July 1946, the operations followed a succession of periods of production alternating with periods in which minor alterations were made in conformity with experience. Steady improvement was made and at the time Operations were discontinued it was considered that experience and the necessary engineering were in shape for removal of the remaining bottlenecks and a somewhat major revision in one section of the plant. Unfortunately this could not be carried out and it was necessary to discontinue the

Jan 1, 1949

By R. E. Smallman, J. C. Terry

J. C. Terry and R. E. Smallman (Llniuersity of Birmingham, England)—In a recent publication53 Wood and Westbrook have reported the results of an investigation of the tensile behavior of fl-phase AgMg alloys. These results agree in broad outline, but differ in the details, with those obtained in the above laboratory and, consequently, some discussion of their paper would seem appropriate. In our experiments, tests were carried out on extruded wires, 2 mm diam, in a hard-beam tensile machine, and while an oil bath was used for the tests up to 150°C, above this temperature the oil bath gave rise to serious contamination of the specimens and hence tests above 150°C were made in vacuo. This procedure is different to that adopted by Wood and Westbrook. The ß-phase alloys exhibit differences in mechanical behavior when they are tested in different temperature ranges. In agreement with Wood and Westbrook, three characteristic ranges are observed which may be classified as low, intermediate, and high temperatures, respectively. Our experiments show that in the low-temperature region, the shape of the stress-strain curves is similar to that reported. However, in addition, it is observed that the temperature at which the low-temperature region ends is markedly dependent on strain rate, and increase with increasing strain rate as shown in Fig. 18. The temperature at which a transition from the low to the intermediate temperature takes place is about 0.4 to 0.45 of the absolute melting point, Tm. This transition temperature coincides with that at

Jan 1, 1963