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By Sidney Powers

Contents Page Distribution of fields..................................................... 490 History of development.................................................. 492 Origin of oil............................................................ 493 Structure, accumulation and migration..................................... 494 Reservoir rocks......................................................... 495 Methods of drilling and exploration....................................... 496 Oil-field statistics........................................................ 498 Description by regions: United States: Appalachian region.................................................. 498 East-central states............................................. 503 Kansas............................................................ 504 Oklahoma.......................................................... 505 Texas........................................................... 510 Arkansas........................................................... 518 Louisiana.......................................................... 519 Mississippi......................................................... 520 Rocky Mountain region.............................................. 520 Cahforn~a ......................................................... 523 Canada.............................................................. 527 Mexico.............................................................. 529 Cuba............................................................... 532 Bibliography........................................................... 532 The purpose of this brief account of the occurrence of petroleum in North America is to make available to those who have a knowledge of geology, but who are not engaged in the petroleum industry, a few salient facts about the location of oil and gas fields, their productivity, the important structural types of accumulation and the age of the rocks containing petroleum. A few useful data and statistics are furnished, yet not complete statistics that are available elsewhere. Geology has been treated in simple terms because the reader is presumed to have little interest in the names of formations and of oil sands. Mineral deposits are more or less analogous. Whether oil or metals, minerals are found in rocks, largely in sedimentary rocks which carry water or have at one time carried it. A genetic or accumulative

Jan 1, 1931

By J. B. Newkirk, A. H. Geisler

Certain of the permanent magnet alloys provide ideal systems for the study of the kinetics of the precipitation reaction and the correlation of structure with properties. One such system, Cu-Ni-Fe, was found by Bradley1,2 to exhibit a coherent transition state in the precipitation process analogous to that reported for Al-Cu alloys somewhat earlier.3 The attractiveness of some perrnanent magnet alloys for study lies in the fact that vertical sections of the ternary phase diagram in certain regions of composition (Fig I) have as their prototype the binary Ni-Au diagram. Alloys of this type decompose into products that have the same crystal lattice type but only slightly different lattice parameters. The advantages that such alloy systems oA&apos;er for study over the usual in which an intermetallic compound is formed are many: 1. Since the precipitate has the same crystal strutture as the matrix, complex atomic movements are not required to form the new lattice. 2. Similarly, complex orientation relationships are not involved for both the matrix and the precipitate would be ex. petted to have the same orientation. 3, Small &,registry of the decomposition products at equilibrium (in contrast with Cu-Ag alloys) is conducive to extensive coherent growth in the transient state and thus the transition lattice can be detected by the usual X ray diffraction methods. 4. Finally, the relative quantities of precipitate and depleted matrix can be varied from 0 to 100 pet* thus permitting wide freedom for the study of the effect of cornposition on coherent growth and properties. In the Cu-Ni-Fe alloys of appropriate composition, the face-centered cubic precipitate and also the depleted matrix when first formed are coherent with the parent matrix.1&apos;2 The two have the same <Jo parameter as the original matrix but they are both tetragonal; the precipitate has an axial ratio c/a < I while that of the depleted matrix is c/a > I. When coherency is lost they assume the normal face-centered cubic structure with the depleted matrix having a lattice parameter greater than the original matrix and that of the precipitate less. Such a mechanism would also be expected for CU-Ni-CO alloys because of the similarity in constitution but this had not been demonstrated. The Present investigation was conducted on a CU-Ni-CO alloy. The constitution diagram and magnetic properties of these alloys have been fairly well established, however, no previous determinations of mechanism of precipitation and no correlation of structure with properties had been made. Thus, an alloy of this system Was chosen for a comprehensive investiga-

Jan 1, 1949

By B. W. Christ, P. M. Giles

Mossbauer effect measurewents have been made on I-mil-thick foils of commercial 1 wt pct C steel and Fe-2 wt pct C alloy. The experimental method required about 3 to 5 vol pct of a phase in the nzultiphase steel sample for detection. Room-temperature Md&apos;ssbauer patterns obtained on austenitized atid quenched samples exhibit fifteen, and possibly twenty-one, lines. A sharp parama&tetic singlet and a quadrupole doublet, poorly resolued from the singlet, are attributed to austenite. Remaining lines are due to tnartensite. Accurate evaluation of austenite line paranzeters is not feasible if significant amounts of other phases such as carbides or martensite occur simultaneously with austenite. This is demonstrated by comparison of hyperfine interactions determined for austenite in multiphase high-carbon samples with those reported for Fe-C austenite in a nearly 100 pct austenitic sanple. Lines from carbides are incompletely resolced from austenite lines, as demonstrated by comparison of austenite line positions with carbide line positions calculated frow published values of hyperfine interactions. One martensite line overlaps an austenite line in the pattern for commercial 1 wt pct C steel. Results of this study suggest that the usefulness of e M6ssbauer pectroscopy for quantitatizle analysis of austenite in bulk samples of quenched and tempered high-carbon steels is restricted by poor resolution. Use of Mossbauer spectroscopy for phase identification and for evaluation of atomic and electronic structures appears quite feasible, however, The Mijssbauer effect has been widely discssed,&apos;-and e Mossbauer effect measurements have been reported on materials of metallurgical interest.7"20 In particular, it has been proposed that e Mossbauer patterns of commercial steels and laboratory-made Fe-C alloys, in the quenched condition, are composed of lines originating in two phases, Fe-C austenite and Fe-C martenite.-&apos; Evidence accumulated in this study demonstrates that three absorption lines found in the central region of the e Mossbauer pattern obtained on quenched steels are attributable to retained austenite. This interpretation is supported by parallel decreases in the intensity of these three lines caused by subambient cooling of commercial 1 wt pct C steel samples after water quenching to room temperature. A second result of this study is to clarify effects of line resolution and sensitivity in the Mossbauer patterns of multiphase steels on the accu- rate determination of austenite line parameters. Experimental line widths (full width at half height) are generally 1.5 to 3 times larger than the natural line width of 0.19 mm per sec. At least two lines, and sometimes more, from a single phase such as cementite (Fe3C), other carbides, martensite, and austenite fall in the energy band, i0.85 mm per sec. hhis band width is employed simply for convenient reference. It represents approximately the energy interval between the + 112 to 112 transitions in ferrite and is expressed as the velocity needed to Doppler shift a 14.4kev 7 ray to the aforementioned ferrite energy levels. This energy band is referred to as "the central region of the Mossbauer atttern:: in this paper. Hence, due to the large number of lines from different phases in a multiphase steel falling in a relatively narrow energy band, absorption lines from the different phases may overlap. Analysis of available data, presented below, indicates that this occurs to a significant extent for phases which commonly occur in quenched and quenched and tempered high-carbon steels. One consequence of limited resolution in the Mdssbauer patterns from multiphase steels is difficulty in accurate determination of such line parameters as position, width, and intensity. In fact, it appears that quantitative analysis for retained austenite in quenched and tempered high-carbon steels is not practical with the present experimental method. Line resolution is influenced to some extent by sensitivity. We point out below that atom or volume fractions of less than about 3 to 5 pct are not detected by the present experimental method. Thus, the presence of a multiplicity of phases does not always lead to impaired resolution. Finally, we report in this paper room-temperature MGssbauer parameters determined for austenite in a freshly quenched, commercial 1 wt pct C steel and in a freshly quenched laboratory heat of an Fe-2 wt pct C alloy. These parameters are compared with others reported in the literature. Three types of hyperfine interactions are detectable in a Mossbauer effect measurement: isomer shift, quadrupole interaction, and magnetic dipole interaction. These interactions are evidenced by one, two, and six line patterns, respectively.&apos;-4 More than one type of interaction has been reported in certain metallurgical phases thus far studied by this method. Isomer shift is the experimentally measured displacement of line position from some arbitrarily defined reference position. In the case of a multiline pattern, isomer shift is given by the displacement of the centroid (center of gravity) of that pattern from the reference position. All isomer shifts measured at finite temperatures contain a second-order Doppler effect characteristic of that temperature. The isomer shift is related to the total s electron density at the nucleus, becoming more negative with increasing s electron density. The first-order quadrupole effect arises from the interaction between the nuclear quadrupole moment and any axially symmetric electric field gradient in

Jan 1, 1969

By W. Bonfield

A study has been made of the dislocation substructures produced in hot-pressed beryllium specimens strained to various levels in the range from 800 x 10-6 In. pev in. to fracture. A number of distinctive dislocation configurations were observed in this region which had not been noted at lower levels of strain. These included dislocation-dislocation interactions to form networks, dislocation "walls", subgrain boundaries and complex arrays, interactions between dislocations and large beryllium oxide particles, and the generation of dislocations from certain particles. The nature of these differences in substructure and their relation to the stress-strain characteristics of polycrystalline beryllium are discussed. In a previous study1 of the plasticity of commercial-purity, hot-pressed beryllium a transition was found in the deformation characteristics in the mi-crostrain region. The initial plastic deformation could be represented by a parabolic stress-strain equation, but above a critical stress there was a complete departure from this relation and a reduction in the strain-hardening rate. The dislocation configurations produced by various levels of micro-strain in this region were examined by transmission electron microscopy and a general correlation was established between the observed transition in deformation characteristics and the dislocation structure of the material. The two stages in the micro-strain region distinguished in these experiments were designated as Stage A&apos; and Stage B&apos;. Stage A&apos; type deformation generally was noted up to a plastic strain of -80 x 10"6 in. per in. and Stage B&apos; type from -80 x 10-6 to -800 x 10&apos;6 in. per in. The discovery of two stages in the microstrain region naturally posed pertinent questions as to the existence of any further distinct stages in the subsequent plastic deformation. The purpose of this paper is to present a study of the dislocation configurations produced in similar beryllium specimens strained to various levels in the range from -800 x 10 in. per in. to fracture and to discuss the relation between substructure and the stress-strain characteristics. It is concluded that this region of strain can be considered as a distinct stage in the plastic deformation of polycrystalline beryllium. Tensile specimens of gage length 1 in. and cross section 0.18 by 0.06 in. were prepared from commercial-purity, hot-pressed QMV beryllium and then annealed at 1100°C for 2 hr. 2 followed by a careful chemical polishing procedure.3 The specimens were strained at a constant rate to various levels of strain in the range from -800 x 10-6 in. per in. to fracture (at 0.5 to 2 pct elongation), using the Tuckerman strain-gage technique1 to measure plastic and total strain. Thin foils were obtained from the strained and fractured specimens by chemical polishing3 and were examined using an RCA-EMU 3 electron microscope. Considerable care waS taken to avoid both accidental deformation during the preparation of the thin foils and excessive heating during their examination. Selected-area diffraction patterns were determined for each micrograph. Tilting experiments were also performed whenever appropriate to establish the dislocation zero-contrast position and hence determine the Burgers vector. This operation was sometimes not possible due to the rapid contamination of the foils which occurred in the electron microscope. RESULTS AND DISCUSSION To enable the distinctions between the dislocation arrays at high and low strain levels to be adequately made, the main characteristics of Stage A&apos; and Stage B&apos; deformation are briefly reviewed. 1) Stage A&apos;. In the annealed starting condition there was a variable density (5 x 107 to 3 x 10&apos; cm per cu cm) of isolated dislocations within a grain. The initial deformation in a tensile specimen was heterogeneous, with the dislocation density increasing in a few grains to 5 x 10g to 1.5 x 101° cm per cu cm. The deformation occurred exclusively on the basal plane by the movement of one or more 1/3 (1130) type dislocation systems. The dislocations were long and regular in form and nearly all the intersections exhibited a simple four-point node configuration. No interactions between glide dislocations and beryllium oxide particles were observed. 2) Stage B. In Stage B&apos; there was a large increase in the number of grains exhibiting dislocation movement and also a change in the nature of the deformation, in which jogged dislocations and elongated loops became the characteristic feature. The splitting up of the elongated loops into smaller loops and the possibility of source action from the re-

Jan 1, 1965

Jan 1, 1951

By R. H. Oliver

The purposes, types, preparation, and testing of flocculants are discussed. A flocculation compendium is included, indicating choice of flocculant for a given set of conditions. An economic evaluation of the process is presented. Solid-liquid separation is a major expense in most mineral processing flowsheets today. Proper use of flocculation can often lower the overall cost of a solid-liquid separation by reducing the size of sedimentation or filtration equipment. PURPOSE OF FLOCCULATION When is use of a flocculant justified in terms of overall process economy? 1) when it results in process improvement, such as producing a clear liquor for electrolysis, precipitation, ion exchange, or solvent extraction; 2) when it results in satisfying requirements of pollution abatement ordinances; 3) when it results in increased recovery of values that would otherwise be lost; or 4) when it results in considerable savings in capital expenditure due to use of smaller equipment. When can the use of a flocculant adversely effect overall process economy? 1) when it results in increased filter cake moisture, 2) when it results in decreased filtration rates, 3) when it results in considerable bulking of sedimentation underflow, 4) when it contaminates either the supernatant or sludge, or 5) when the cost of using the flocculant is greater than the savings due to its use. First step in consideration of flocculants for a given application is establishment of desired goals in terms of increased clarity of effluent, increased recovery of solids, or decreased size of equipment. The most economical solution to a solid-liquid separation problem is that combination of equipment and flocculant costs which meets the established goals at the lowest total annual expenditure. This economic decision can be made only after technical data has been obtained as outlined in next four sections. TYPES OF FLOCCULATION Flocculation is a process wherein individual particles are united into more or less tightly bound agglomerates or flocs, thereby increasing effective particle size of solids suspended in a liquid. Degree of flocculation of a suspension of finely divided solids in a liquid is controlled by a combination of probability of collision between particles and probability of adhesion after the collision has occurred.&apos; Probability of collision can be increased commercially through use of a paddle-type flocculator, combination flocculator, and clarifier or flocculating-type feedwell. Probability of adhesion usually can be increased by addition of a reagent known as a flocculant. Reagents act as flocculants through one or a combination of three possible mechanisms. The first is electrolytic neutralization of inter molecular repulsive force due to Zeta potential. This neutralization enables Van der Waal&apos;s cohesive force to hold the particles together after they collide.&apos; The second is the precipitation, within a definite pH range, of voluminous metallic hydroxide flocs which entrap fine particles. This process is known as coagulation.14 Third is the bridging of two or more particles by either natural or synthetic long-chain, high-molecular-weight organic polymers. This bridging is accomplished by adsorption of two particles at different sites on the same molecule or by bonding of two molecules, each adsorbed to a different particle. Considerable effort has been expended in explaining the action of these polyelec-trolytes and detailed accounts are available in the literature. CHOICE OF FLOCCULANTS It is impossible, at the present time, to specify the optimum type or amount of flocculant for a given application from a knowledge of the material to be treated. The standard procedure is to choose reagents or combination of reagents most likely to be effective on the slurry; then test them.&apos; The accompanying Flocculation Compendium (Table I) contains details of all currently available reagents sold as flocculants and it should be used when selecting the group of reagents for tests. This selection can be based on information listed in columns 4 and 5. Column 4 presents industries in which each floc-

Jan 1, 1961

By Arthur C. Green

A group of 13 cities situated in Los Angeles and Orange counties in Southern California is engaged in constructing an aqueduct to carry water from the Colorado River at a point near Parker, Arizona, to a distribution point near Riverside, California. The aqueduct will have a total length of approximately 241 miles, and is designed to deliver 1605 cu. ft. of water per second, or a little more than one billion gallons per day. The aqueduct crosses a barren, desert waste and the project includes approximately 91 miles of 16-ft. tunnel. The large amount of tunnel driving that has been done in this country in the past few years has resulted in some remarkable developments in equipment and methods. The building of the Colorado River Aqueduct,, with its 91 miles of tunnels, has called on the best engineering knowledge in the country. New and better equipment has been designed for all phases of the work, and this equipment has been coordinated and adapted to the various conditions with a high degree of efficiency. The result has been that records for tunnel driving have been set under adverse natural conditions that exceed the estimates for progress under good conditions. All of the tunnels in the main aqueduct, except the Valverde and Bernasconi at the western end, have a finished diameter, inside the concrete lining, of 16 ft. Fig. 4 shows a section of the tunnel with the concrete lining in place. Fig. 5 illustrates the finished tunnel in three typical sections. The standard tunnel grade is 3.432 ft. per mile in the 16-ft. tunnels, but the Valverde and Bernasconi tunnels have a steeper grade and a finished diameter of 15 ft. 3 in. The rough bore of the large main aqueduct tunnels averages 12.95 solid cubic yards of material per foot of advance in timbered sections and 10.76 solid cubic yards per foot in unsupported sections. Tunnel Driving While the Conway mucker has been used on tunnel work for years, a larger and more powerful Conway was designed to meet the require-

Jan 1, 1937

By W. S. Sanner

Experiments were conducted to determine the quantity and purity of ultraclean anthracite that could be prepared in the laboratory, using conventional separating techniques. A low, a medium, and a high-volatile anthracite were studied. Specific gravity separation followed by grinding, screening, and refloating at lighter specific gravities yielded small quantities of material purified to 1.0% ash, as follows: from low-volatile anthracite, 0.7%; from medium-volatile coal, 1.0%; and from high-volatile coal, 2.3%. The reduction in ash had no appreciable effect on the volatile matter or sulfur content of the coal. The limited quantities of material containing 1.0% or less ash obtainable indicate that if ultraclean coal is desired, a practical approach should include the processing units as an integral part of a convc.ntiona1 dense-media washing plant. Anthracite preparation practices during much of the industry&apos;s history were geared to maximum recovery of the larger sizes, pea through egg, which were used in hand-fired, domestic furnaces. Those sizes were cleaned to meet trade requirements, and the smaller sizes were usually higher in ash content. The impression, thus, was that ash content of anthracite always increased as the sizes got smaller. It was presumed that it was impossible to wash the finer sizes to extremely low ash contents. Following World War 11, the classical domestic market began to decline and the finer sizes assumed an increasingly large share of the market. For example, in 1949l 61% of the production was still pea and larger. Fig. l2 shows that -by 1955 these sizes accounted for only 50%, and in 1965, they were only 39% of the total anthracite produced. With the reduction in the market, increased quality was demanded, especially in export markets, and an increasing number of dense-media magnetite washers were installed in new and existing cleaning plants. In 1965, the coarse coal prepared at 59 breakers in the anthracite fields was sampled by the U.S. Bureau of Mines (USBM); approximately 50% of these plants were equipped with dense-media magnetite washers.3 Since 1950, more attention has been focused on the use of finer sizes for numerous industrial uses, including iron-ore sintering, pelletizing, foundry coke-making, cement manufacture, production of calcium carbide, and of carbon electrodes, etc. Most industrial uses require relatively clean anthracite, such as 10 to 11% ash for sintering and foundry coke, 7% for aluminum melting-pot cathode carbon, and 5% for carbide production. Hence, cleaning methods have been improved to the extent that dense-media washers, hydraulic cyclones, and flotation cells have been introduced as fine-coal-cleaning devices. It is now possible to wash the buckwheat, rice, and barley sizes (9116 X 3132-in.) to ash contents as low as 8 to 10% in dense-media devices, but washing the -3132-in. sizes to those limits presents more difficult problems, due mainly to the fineness of the material. This USBM investigation was conducted to determine the amount and purity of ultraclean anthracite that could be prepared in the laboratory, using conventional separating techniques. The goal was to reduce the ash content to a level acceptable for industrial carbon uses, including electrode manufacture, which generally requires an ash content of 1% or less. While low-ash content is of primary importance in selecting industrial carbons, the amounts of other constituents are also important, including iron, silicon, titanium, nickel, vanadium, and sulfur. They were not considered in this work, since their occurrence in deashed anthracite has been studied elsewhere.4 The results of the present investigation were used to design a flowsheet, suggesting a method for producing ultraclean anthracite as part of conventional preparation practice, using dense-media vessels, crushers, pulverizers,

Jan 1, 1970

By B. Chalmers

THE practical importance of the phenomena of melting and freezing must have been recognized for a very long time. The difference between ice and water, for example, has had a profound influence on the history of mankind and the evolution of society. The possibility of melting a metal and allowing it to freeze in a mold of chosen shape has been an essential ingredient in our mastery of the art of shaping metals, and therefore in the evolution of the: machine age in which we find ourselves. The importance of melting and freezing, as applied to metals and alloys, has been so great, in fact, that empirical solutions have been found for the multitude of practical problems that have arisen. This approach has been so successful that relatively little attention has been directed to arriving at an understanding of the fundamentals of the processes. But metallurgy has come to a stage at which we may expect that some, at least, of the more complex problems that have not yet been solved (or perhaps even recognized) may be handled more effectively by scientific study, theoretical understanding, and logical experimentation than by trial and error. In this lecture, therefore, I propose to describe in outline what I think really happens when a metal freezes. In doing so I hope to explain many of the phenomena which have been observed, and in particular to account for the structures that are obtained in actual ingots and castings. The basic problem, to which this lecture represents a tentative partial answer, is this: a mass of metal, containing known proportions of various elements, is melted, heated to a given temperature, and then allowed to freeze under specified conditions. What will be the "structure" of the resulting metal? The term structure includes: 1—crystal size, shape, and orientations, 2—distribution of chemical elements, and 3-—shape, including cracks, cavities, pores, etc. The Solid-Liquid Interface We will first consider what takes place if a single crystal of a metal in the form of a rod is heated, not uniformly, but so that one end is hotter than the other. If this heating process is continued long enough, the hotter end will eventually melt; we will suppose that the rod is in a containing vessel so that the molten metal does not run away, Fig. 1. When some of the metal has melted, we have some solid, some liquid, and an interface or surface of contact between them. If the source of heat is now removed, the interface will move so that some of the liquid freezes, and if the supply of heat is suitably adjusted the interface will remain at rest. This very simple arrangement allows us to study the basic processes of melting and freezing, and if we fully understand this simple case, we may be able to account for what takes place under practical conditions where the heat does not all flow in the same direction, and where the heat flow is determined not by a controllable source of heat but by the heat capacity and temperature of metal and mold, and by the heat loss from the mold surface. The solid-liquid interface is evidently the region of the greatest interest to us; on one side of it there is crystalline solid, and on the other, liquid. In the solid, each atom has a well defined position, around which it vibrates as a result of thermal agitation. It only leaves this position in the relatively rare event of a "diffusion jump." The liquid is much less systematically organized. The atoms are about as far from their neighbors as in the solid, but the arrangement is much less systematic and is continuously changing. The solid and the liquid are represented diagrammatically in Fig. 2. The average energy of the atoms in the liquid is greater than in the solid by an amount that corresponds to the latent heat of fusion, i.e., the amount of heat that has to be supplied to convert unit mass of solid into liquid at the same temperature. The Two Processes As has recently been shown by Jackson and Chalmers,3 many of the features of the processes of freezing and melting can be understood if it is assumed that a continuous and rapid interchange of atoms between solid and liquid always takes place at a solid-liquid interface." It is necessary to con- sider two distinct processes, that of melting, in which atoms leave the surface of the solid and become part of the liquid, and the converse process,

Jan 1, 1955

By Kenelm C. Appleyard

In introducing to an American audience a description of the work done in dry coal separation in England and in Europe generally, it is perhaps desirable to give a short history of the development outside the United States of the particular processes with which the author is connected, and perhaps to stress a little the differences in the nature of the conditions to be faced. England actually presents one set of problems and the Continent of Europe another, since the character of the coals to be treated is entirely dissimilar, and the attitude of the coal industries towards coal preparation is also dissimilar. England for generations has been working by hand good seams of clean coal of the highest possible quality and has not felt any pressing need to clean its coal. Most Continental countries, however, especially in Central and Western Europe, have been working friable and often very dirty coals for so long that a washery is accepted as a part of the normal equipment of a colliery, with the result that the art of wet washing has reached a high state of perfection, particularly in Belgium and Germany. The advent of machine mining has intensified the problems to be faced in all countries, and in England has been coupled with the working out of the best seams in the older coal fields, thus bringing about the necessity of working thinner and dirtier seams with resultant difficulties as regards marketing the products, while Poland, with clean and well prepared coal, has in recent years been attacking established British markets in Scandinavia. In recent years, therefore, interest in coal preparation has been steadily gaining ground in England, although it has not yet reached Continental dimensions. Broadly speaking, the differences in preparation problems between England and the Continent boil themselves down to one of size. In England, for example, with the exception of the Kent coal field, the proportion of coal of a size less than ? in. to the coal less than 2 in. is very much less than on the Continent, and since the principal difficulties in dry cleaning lie in the fines it is easier to produce good figures on

Jan 1, 1931

By B. R. Queneau

[ ] B. R. QUENEAU-One of the difficulties in metallurgy has always been a lack of precision in measurement, and I think the authors are to be congratulated on developing a method which will give us an accurate and dependable quantitative estimate of the amount of retained austenite. O. ZMESKAL*-As Chairman Queneau said, this is indeed an ingenious and needed determination. We have seen figures presented of 1/2 pct retained austenite determined, and I would like to ask the authors the lower limits of this method. How far down do they feel they can go in improving the technique still more?

Jan 1, 1948

By W. L. Phillips

Stress-strain curves were obtained for single crystals of 70 pct Ag-30 pct Zn tested in tension and shear. Samples tested in tension and shear had comparable resolved shear stresses and stress-strain curves. The {111} <110> slip system was observed. It zoas found that the9.e is a barrier to slip in both latent close -packed directions and that the magnitude of these barriers is proportional to prior strain during easy glide. It was observed that cross-slip in tension and shear was most frequent in crystals with an initial orientation near <100> "Oershoot" zoas observed in tension. The amount of this "overshoot" was independent of initial orientation. AN idealized concept of plastic deformation indicates that a single crystal should yield at some stress that is dependent on crystal perfection and it should then continue to deform plastically by the process of easy glide which is characterized by a linear stress-strain curve and a low coefficient, d/dy, of work hardening. Hexagonal metal crystals generally conform to this ideal concept of laminar flow. In fcc metals the range of easy glide is always restricted in magnitude and it is strongly dependent on orientation, composition, crystal size, shape, surface preparation, and temperature. Since one of the principal differences between the two crystal systems, both of which deform by slip on close packed planes, is the existence of latent slip planes in the fcc crystals, it has been proposed that the transition from easy glide to turbulent flow, characterized by rapid linear hardening, is due to slip on secondary planes intersecting the primary plane.ls Several theories have been proposed to explain the linear hardening and parabolic stages of the stress -strain curve.6"10 The easy-glide region is the least understood of the three stages. The stress-strain characteristics of Cu-Zn, which shows a long easy-glide region, have been extensively investigated."-" In light of recent ideas on dislocations, cross-slip, effect of solute atoms, and stacking fault energy, it was felt that the certain features of this earlier work might be compared with another alloy, Ag-30 pct Zn, which also exhibits a long easy-glide region. Tension and shear stress at room temperatures were employed. The results obtained, together with some interpretation of the observations, are described below. EXPERIMENTAL PROCEDURE The silver and zinc used for mixing the alloys were 99.99 pct pure. The two components were weighed to within 0.1 pct of the weights required fo the alloy composition. They were then placed in a closed graphite mold and the mold and contents were heated in 100°C stages from 500&apos; to 900°C with sufficient time and vigorous agitation at each stage provided to dissolve the silver. The crucible was then heated to 1150°C and agitated violently before being quenched in oil. The resulting alloy rod was machined free of sur face defects and then placed in a graphite mold designed for growing single crystals. The graphite mold was closed with a graphite plug and was encased in a pyrex glass tube which was connected to a vacuum system. The tube and mold assembly were placed in a furnace; the tube was evacuated and the furnace was rapidly heated to a temperature sufficient for fusing and sealing the glass. The glass-encased evacuated mold and contents were then lowered through a vertical furnace. The top section of the furnace was held at 100 °C above the melting point of the alloy. The lowering rate was 1.5 in. per hr. The tension specimens were 1/4 in. diam; the shear specimens were 1/2 in. diam. These specimens were then removed from the mold, etched, and chemically polished with hot (60°C) Chase etch reagent (Crz03-4.0 g, NH4C1-7.5 g, NHOs-150 cc, HzS04-52 cc, and Hz0 to make 1 liter). In preparation for tensile testing, the specimens were carefully machined to a diameter of about 0.200 in. to permit a gage length of 6 in., annealed for 16 hr at 800&apos; to reduce coring, and then cleaned and polished. A modified Bausch-type shear apparatus which has been described previously18 were employed. The gage length was 1/8 in. This shear apparatus was placed in an Instron tensile testing machine. EXPERIMENTAL RESULTS A) Tension. Several specimens were extended at room temperature to determine the effect of initial orientation on the stress-strain curves of Ag-30 pct Zn. The initial orientation and the resolved shear stress supported by the active slip system at various total strains are plotted in Fig. 1. The critical resolved shear stress, t,, initial rate of work hardening, d/dy, and length of the easy-glide region are independent of orientation. The arrival at the symmetry line is shown by an arrow in Fig. 1. During the easy-glide region of the stress-strain

Jan 1, 1963

By H. M. Stewart, R. A. Grange

Man.; steel parts may crack if quenched directly into a bath near room temperature, but not if quenched at a temperature just above the range where martensite forms and then allowed to cool slowly to room temperature. This latter procedure, which is the basis for such modern hardening techniques as "martempering" and "isothermal quenching," may entail some sacrifice in depth of hardening but very little, if any, in intensity of hardening. In planning such treatments, it is necessary to know the upper limit of the martensite range, and often desirable to know the proportion of martensite that would form on cooling to any lower temperature; furthermore, the tendency of a particular steel to crack when quenched is unquestionably associated with the temperature range of martensite formation, and consequently knowledge of this range aids in selecting the optimum composition for a given application. Certain puzzling phenomena associated with the properties of quenched and tempered steel may be at least partly clarified as the manner in which martensite forms is more fully understood. Information on the temperature range of martensite formation, particularly with respect to how much martensite results from quenching to a given temperature, is lacking for most commercial types of carbon and low-alloy steel. These considerations led us to study martensite formation in 14 carbon and low-alloy steels. The resultant data may be directly used in the following ways: (I) for selecting the lowest quenching temperature at which no martensite will form; (2) for selecting the highest quenching temperature at which virtually all marten . site will form, thereby avoiding quenching to an unnecessarily lower temperature with attendant danger of cracking; and (3) in producing a mixture of tempered martensite and bainite, which in high-carbon steels has been found to possess somewhat better ductility than tempered martensite, yet does not require the full transformation time necessary for a completely bainitic (austempered) structure. PART I. OBSERVATIONS OF MARTENSITE FORMATION IN FOURTEEN CARBON AND LOW-ALLOY STEELS Transformation of austenite to pearlite or bainite can be conveniently studied by observing the change that occurs over a period of time at constant temperature; such studies are the basis of the isothermal transformation diagram (S-curve). This isothermal technique is not applicable to martensite formation, which occurs within a time interval too small to measure, at least by any ordinary means. For all practical purposes, therefore, martensite may be regarded as forming only during cooling and not during a period of time at constant temperature. As austenite is cooled below

Jan 1, 1947

By Carl Swartz

METALLURGISTS differ considerably in their opinions regarding the effect, if any, of small amounts of iron pyrites, or other iron compounds on zinc sulfide ores during the roasting operation. As a result, the literature on this subject expresses many conflicting ideas. The ore, previously crushed to pass through a one-millimeter screen, dries in the roasting kiln, losing water up to 200° to 300° C. At 150° C. iron pyrites begin to lose sulfur. As the temperature increases, while the ore is passing to the hotter part of the furnace, the sulfur burns to sulfur dioxide, leaving the metals as zinc oxide and ferric oxide. These two substances then interact to form zinc ferrite, a compound, yellow brown in, color, having the general characteristics of a spinet Like magnetite, another spinel, zinc ferrite is insoluble in alkalis and dilute acids. As a result, when leached with 10 per cent. sulfuric acid solution zinc values tied up in this compound remain behind. HISTORY In the electrolytic recovery of zinc from its ores, the roasted ores are usually leached with a 10 per cent. sulfuric acid solution. When the zinc ore contains iron pyrites as an impurity in an appreciable amount, the actual yield of metallic zinc is much lower than a theoretical calculation would indicate. Further, losses of zinc are, in a rough way, directly proportional to the amount of iron pyrites or other iron compounds present. When the iron is present in the ore in an isomorphous relation to the zinc, as in the case of a marmatite, a greater amount of zinc remains insoluble than when present as a true pyrite or marcasite. Work on the insoluble residues obtained from leaching of the calcines shows that the zinc lost is intimately tied up in this residue. Some investigators have suggested a definite compound, such as zinc ferrite, others merely a mixture of zinc and iron compounds.

Jan 1, 1927

By W. C. Browning

The influence of the hydroxyl factor is more damaging to formations penetrated and causes greater consumption of drilling mud additives than previously realized. This hydroxyl effect on clays is essentially independent of the cations present in the drilling fluid and thus differs from the base exchange reactions that have preoccupied mud chemistry with sodium and calcium bentonite concepts for nearly two decades. The new organic polyelectrolyte-con-ditioned muds haw made it possible to use materials other than sodium hydroxide to maintain the alkalinity of such muds. The properties of silicates, as indicated by their dissociation characteristics and buffering action, are such that they can control he pH and alkalinity of drilling muds at the desired level and, at the same time, minimize undesirable hydroxyl effects associated with sodium hydroxide. This use of silicate compounds is different and distinct from prior applications of silicates as deflocculants or shale preservers. Laboratory and field data presented in this report show that silicate compositions can be utilized to adjust the alkalinity of drilling muds and, at the same time, minimize hydmxyl-promoted clay cleavage. INTRODUCTION Studies for improving the efficiency of rotary drilling techniques must consider the chemistry of drilling fluids and of the formations being penetrated. The chemical aspects of drilling must be studied in conjunction with and in relation to the mechanical factors if, for example, penetration rates are to be optimized. Drilling fluid technology has been largely influenced by chemical reactions of the montmorillonite (bentonite) clay minerals. Most of the literature of mud chemistry concerns the properties of bentonite. Clays of the kaolin or illite type, which are nonswelling, are not generally regarded as sources of drilling mud problems. If these nonswelling shale clays are considered, they are commonly regarded as inert solids. Particularly noteworthy is the fact that the relation of surface and colloid chemistry to massive shale bodies has received only scant attention from drilling technologists. Clay studies reported in the drilling mud literature have dealt, for the most part, with the properties of clays in a finely divided state, and often in very dilute suspensions. Yet frequently during drilling, shale problems not related to the rheology of clay suspensions develop in massive non-bentonitic shale sections of zero or near zero permeability. This paper is concerned with surface chemical reactions that can influence the behavior of these non-bentonite clay masses in such a manner as to adversely affect drilling operations. Browning and Perricone1,2 have pointed out that some of the most troublesome shales to drill, such as the Atoka, contain no montmorillonites. They also pointed out that mud problems can frequently be mitigated by reduction of clay cleavage achieved by using drilling fluids with a minimum of available hydroxyl ions. If pronounced clay cleavage occurs during drilling, the borehole may soften, increasing the possibility of sloughing. In addition, the resulting increased incorporation of high-surface-area clay solids into the mud system can reduce penetration rates and necessitate greater chemical treatment. This increase of shale, of colloidal or near-colloidal dimensions, into the drilling mud is due to clay aggregate cleavage and not to base exchange or swelling reactions, such as occur with bentonites. Searle and Grimshaw3 point out the difference between cleavage or slaking reactions of nonswelling clays (such as illite and kaolinite) and the swelling of bentonite. They further state that the speed of slaking is increased in alkaline water. Eitel1 cites Salmang and Becker, who recognized that clay surface reactions impart plasticity and workability to clay masses. Their results clearly show that all liquids which contain hydroxyl groups in their molecules favor the workability of clays. The ancient technique of aging clays in the moist condition to increase their "workability" is evidence that these clay cleavage phenomena are of considerable importance. The same hydration cleavage that occurs during the aging of nonswelling clays for ceramic use also acts to break up cuttings and soften the borehole during drilling operations. The mechanism of cleavage of the crystalline aggregates of illitic, kaolinitic and other nonswelling clays; and the chemical means of controlling this cleavage are therefore of considerable significance to the drilling mud chemistry. Inasmuch as there is little reference in the drilling mud literature to the cleavage reactions of nonswelling clays, the structure of these clays and certain properties that relate to the mechanism of clay cleavage will be reviewed briefly. STRUCTURE OF NONSWELLING CLAYS Clays such as kaolinite, illite and montmorillonite are compmed of alternate layers of (1) silicon-oxygen tetra-

Jan 1, 1965

By R. G. Ward, D. R. Gaskell

Using the maximum bubble pressure technique, the densities of iron silicates at 1410°C have been measured blowing helium, nitrogen, and argon. By ensuring equilibrium between the melt and the blowing gas with respect to oxygen potential and by minimizing tempcrature cycling of the furnace, iron precipitation in the melt has been prevented. Thus the previously reported effect of blowing-gas composition on the densities of the melts has been eliminated. Consideration of the oxygen densities of the melts gives an indication of the structural changes accompanying composition change. The density-composition relationship of iron oxide-silica melts in contact with solid iron has been the subject of several investigations1-7 and considerable disparities exist among the various results obtained. Of these investigations, all except one5 have employed the maximum bubble pressure method. In the most recently reported of these investigations1 the density-composition relationship obtained blowing nitrogen differed from that obtained blowing argon. The measured densities obtained under nitrogen were greater than those obtained under argon, the difference being a maximum at the pure liquid iron oxide composition and decreasing with increasing silica content. This observation rationalized the disparities existing among the results of the earlier investigations, showing that two lines, one for nitrogen and the other for argon, could be drawn to fit all the earlier results. No explanation for this phenomenon could be offered. Chemical analysis of rapidly quenched samples of melt for dissolved nitrogen, and direct weighing measurements, excluded solution of nitrogen in the melt from being the cause of the increase in density. The range of blowing gases was extended by Ward and Hendersons who measured the density of liquid iron oxide bubbling helium, nitrogen, neon, argon, and krypton. The measured density was found to decrease smoothly with increasing atomic number of the bubbling gas. The work reported here is a continuation of the program initiated by Ward and Sachdev7 to study the densities in multicomponent melts in which the iron oxide-silica system is the solvent. As such it is necessary to explain or eliminate the anomalous densities of iron silicates under different atmospheres, and the present rede termination was carried out towards this end. EXPERIMENTAL The maximum bubble pressure method of density determination was again employed and the experimen- tal apparatus used was essentially the same as that used by Ward and Sachdev.7 A molybdenum-wound resistance furnace heated an ingot iron crucible of internal diameter 1 in. containing a 2-in. depth of melt. The bubbling gas was blown through a 1/4 -in.-diam mild steel tube onto the end of which was welded a 2-in. extension of 1/4 -in.-diam ingot iron rod, drilled out to 5/32 in., and chamfered to an angle of 45 deg. The blowing tube was introduced to the furnace through a sliding seal and its position was controlled by a vertically mounted micrometer screw which allowed the depth of immersion to be determined with an accuracy of ± 0.01 cm. A Pt/Pt-10 pct Rh thermocouple was located below the crucible and temperature control was effected initially by means of an on-off controller and later by a saturable core reactor. The bubble pressure was determined by measurement of a dibutyl phthalate manometer using a cathetometer. PREPARATION OF MATERIALS Iron oxide was produced by melting ferric oxide in an inductively heated iron crucible in air. The liquid was quenched by pouring onto an iron plate. Silica was prepared by dehydrating silicic acid at 650°C for 12 hr. RESULTS Before any measurements of the density of a melt were made, the density of distilled water at room temperature was measured bubbling helium and argon. Both gases gave the density as 1.00 ± 0.01 g per cu cm which showed that the density of the manometric fluid (dibutyl phthalate) was not affected by contact with the blowing gas. With the furnace controlled by an on-off temperature controller an attempt was made to measure the density of pure liquid iron oxide by bubbling argon. The furnace atmosphere gas and bubbling gas were dried over magnesium perchlorate and deoxidized over copper turnings at 600°C. It was found that the pressure required to blow a bubble at a given depth increased slowly with time, and thus it was impossible to obtain a unique value for the density of the melt. Inspection of the blowing tube after removal from the furnace showed that rings of dendritic iron had precipitated from the melt onto the immersed part of the tube. This is shown in Fig. l(a) where the various "steps" correspond to different depths of immersion. The precipitation of iron was considered to be due to one or both of two possible causes: i) The composition of the liquid iron oxide is that of the liquidus at the temperature under consideration and can be expressed by the equilibrium

Jan 1, 1968

By C. H. Samans, G. F. Tisinai, J. K. Stanley

The addition of nitrogen (0.10 to 0.20 pct) to Fe-Cr-Ni alloys of simulated commercial purity results in a real displacement of the u phase boundaries to higher chromium contents. The effect is small for the (Y + s)? boundary, but is pronounced for the (y + a +s)/(y + a) boundary. Although there is an indication of an exceptionally large shift of the n boundaries to higher chromium contents, especially in steels with nitrogen over 0.2 pct, the major portion of this apparent shift results from the fact that carbide and nitride precipitation cause "chromium impoverishment" of the matrices. The effect of combined additions of nitrogen and silicon to the Fe-Cr-Ni phase diagram is demonstrated also. Nitrogen can nullify the effect of about 1 pct Si in shifting the (y + o)/? phase boundary to lower values of chromium at all nickel levels from 8 to 20 pct. NItrogen can nullify this U-forming effect of about 2 pct Si at the 8 pct Ni level, but not at the 20 pct Ni level. The alloys studied were in both the cast and the wrought conditions. There are indications that the u phase forms more slowly in the cast alloys than in the wrought alloys if both are in the completely austenitic state. The presence of 6 ferrite in the cast alloys accelerates the formation of U. Cold working increases the rate of o formation in both cast and wrought alloys. THE major improvement in Fe-Cr-Ni austenitic alloys in recent years has been in the addition or removal of minor alloying elements to facilitate better control of corrosion resistance, sensitization, and heat resistance. One shortcoming of the austenitic Fe-Cr-Ni alloys, which never has been completely circumvented, is their propensity toward u formation. In the AISI-type 310 (25 pct Cr-20 pct Ni) and type 309 (25 pct Cr-12 pct Ni) steels, sufficient amounts of u phase can form, if service or treatment is in a suitable temperature range, to cause severe embrittlement. Also, there is a growing conviction that this phase may be contributory to some unexpected decreases in the corrosion resistance of certain of the 18 pct Cr-8 pct Ni-type steels. The present paper discusses the effect of nitrogen additions on the location of the (r+u)/d and the (y+a+u)/(y+a) phase boundaries in the ternary Fe-Cr-Ni system, for cast and wrought alloys of simulated commercial purity, and in similar alloys containing up to about 2.5 pct Si. The objective is to define compositional limits for alloys which will not be susceptible to u formation when used near 1200°F (650°C). An excellent review of the early studies of the u phase in the Fe-Cr-Ni system has been compiled by Foley.1 Rees, Burns, and Cook2 have determined a high purity phase diagram for the ternary system, whereas Nicholson, Samans, and Shortsleeve3 are- stricted themselves to a portion of the simulated commercial-purity phase diagram. Both groups of investigators show almost an identical position for the commercially significant (y+u)/y phase boundary. Further comparison of the work of the two groups indicates that, below the 8 pct Ni level, the commercial alloys have a decidedly greater propensity toward u formation than the high purity alloys. The two groups of workers agreed that both the AISI-type 310 (25 pct Cr-20 pct Ni) and the type 309 (25 pct Cr-12 pct Ni) steels are well within the (y+~) region and that the 18 pct Cr-8 pct Ni-type alloys straddle the U-forming phase boundaries. Nicholson et al.3 showed, in addition, that these boundaries shift toward lower chromium contents if greater than nominal amounts of silicon or molybdenum are added. The effect of nitrogen on the location of the s phase boundaries in the Fe-Cr-Ni system has not been known with any certainty. In 1942, an approach to this problem was made by Krainer and Leoville-Nowak,&apos; but at that time they apparently were unaware of the slow rate of s formation in strain-free samples and aged their samples for insufficient times, e.g., 100 hr at 650°C (1200°F) and 800°C (1470°F). For this reason, it would be expected that their (y+ u) /y boundary would be shifted toward lower chromium contents (restricted ?-field) when equilibrium conditions were approximated more closely. Procedure for Studying the Alloys The alloys used were prepared in the following way: Heats of 200 lb each were melted in an induction furnace. A 5 lb portion of each heat was poured into a ladle containing an aluminum slug for de-

Jan 1, 1955

By D. J. McAdam, G. W. Geil, D. H. Woodard, W. D. Jenkins

INTRODUCTION IN a series of papers, the authors and their associates have shown the influence of four important factors on the technical cohesion limit.3-16 By "technical cohesion limit" is meant the technically determinable resistance to fracture. The four important factors are the stress system, plastic deformation, temperature, and the strain rate. The influence of any one of these factors may be represented by a curve of cohesion limits, although only one point on the curve may represent actual fracture. As the term "fracture stress" has come into general use with the same significance as technical cohesion limit, the authors are here using the shorter term with the understanding that it does not always refer to actual fracture. The previously-mentioned series of papers contains ample evidence that plastic extension increases the fracture stress of any polycrystalline metal. In a recent paper of the series,15 moreover, it has been shown that the effect of plastic deformation on the fracture stress cannot be attributed to reorientation of internal flaws but is a work-strengthening effect, similar to the effect on the flow stress.[$] Plastic deformation of steels, however, may not only cause work hardening, but may result in additional hardness because of strain aging. Some evidence that strain aging affects not only the flow stress but also the fracture stress, has been presented in a recent paper.14 In that paper, a study is made of the influence of plastic deformation at room temperature on the fracture stress of ferritic steels at -188°C. The study is based on the results of two-stage tests. In the first stage each specimen was extended a predetermined amount at room temperature; in the second stage the specimen was tested to fracture in liquid air. In most of these tests the specimen remained in the testing machine during the interval of about one hour between the first and second stages, it was kept under a tensile load of about 500 lb and maintained at liquid air temperature. The effects of various amounts of plastic deformation on the fracture stress were thus determined and curves were obtained to represent the influence of plastic deformation at room temperature on the stress at brittle fracture in liquid air.14 Two specimens of ingot iron, however, were removed from the testing machine at the end of the first stage and several days elapsed before the specimens were tested to fracture in liquid air. As shown in Fig 8 of that paper," the points representing fracture of these specimens are far above the curve representing the results of two-stage tests without a rest interval between the stages. The evidence thus indicated that the fracture stresses of these two specimens were increased not only by the work-strengthening, but also by strain aging. The present paper presents results of further investigation of the influence of strain aging on the fracture stress. There are two kinds of aging of steel.

Jan 1, 1948

By Frederic L. Kadey

Diatomite is a siliceous, sedimentary rock consisting principally of the fossilized skeletal remains of the diatom, a unicellular aquatic plant related to the algae. Thus, it has-been formed by the induration of diatomaceous ooze, and consists mainly of diatomaceous silica, a form or variety of opal which is first formed in the cell walls of the living diatom. Diatomaceous silica is not generally regarded as a synonym or the equivalent for diatomite, although it has been so used at various times. Accurately, diatomaceous silica is the preferred name for the principal mineral component of which the rock, diatomite, is composed. The terms diatomaceous earth and kieselguhr are used as synonymous with diatomite. The designations tripoli, tripolite, infusorial earth, etc., were used at one time but are now obsolete. With the changing nomenclature, these terms that were at one time correct when proposed and used for generations would be considered incorrect if used today in the light of current knowledge. The designation diatomite is reserved for those accumulations of diatomaceous silica that are of sufficient quality, size, and minability to be considered of potential commercial value. Processed diatomite possesses an unusual particulate structure and chemical stability that lends itself to applications not filled by any other form of silica. Foremost among these applications is its use as a filter aid, which accounts for over half of its current consumption. Its unique diatom structure, low bulk density, high absorptive capacity, high surface area, and relatively low abrasion are attributes responsible for its utility as a functional filler and as an extender in paint, paper, rubber, and in plastics; and as an anti-caking agent; thermal insulating material; catalyst carrier; and chromatographic support; polish, abrasive, and pesticide extender to name a few representative applications. The United States is the principal producing country, although diatomite is found in numerous other locations.

Jan 1, 1975

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