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By John C. Branner

Five of the geologic horizons that yield oil in other parts of the world are represented in Brazil; namely, the Devonian, Carboniferous, Permian, Cretaceous, and Tertiary. Thus far, the first two have shown no evidences of being oil bearing within Brazilian territory. Not enough exploring has been done to permit trustworthy comparisons of the relative importance of the Permian, Cretaceous, and Tertiary as oil-bearing horizons in this country. The most important, indeed almost the only, information available relates to the locations of the areas and to the structural features of the several horizons. The theories regarding the physical conditions under which these rocks were laid down, however, I regard of the utmost importance. Permian Rocks of Permian age cover an enormous area in Brazil, extending from Rio Grande do Sul to Maranhao on the north, and to Matto Grosso on the west. These Permian rocks in many places are known to include oil-bearing shales and in some locations contain small veins of gilsonite. The geologic map of Brazil shows that the Permian area is widely distributed, but there is considerable doubt about the origin of some of the rocks. Some of the lower Permian beds in southern Brazil contain marine fossils, but in Minas no fossils have as yet been found in them, and in Bahia, at only one locality have a few Permian plants been found. Indications of oil have been found in the states of Sa0 Paulo, Parana, and elsewhere farther south, but wells drilled in the Permian of SaO Paulo near the Morro do Bofete did not find oil. One well has been started, by the Brazilian Government, in the Permian of Parana near Marechal Mallet, close to latitude 26" south, but thus far oil has not been found.

Jan 1, 1923

By PALMER H. TYLER

WHEN the Mid-Continent Section of the A. I. M. E. met at the roof garden dining room of the Tulsa Club on Monday evening, May 13, most of the members present came prepared with a credulity-stretching yarn of some sort or other, gathered from actual experience. Perhaps it was not realized at the time that such anecdotes would eventually burst into print, but while the excellent dinner was appeasing the inner man the word was passed around that informality and spontaneity of expression would characterize the meeting, with the result that the shackles of convention were eventually cast aside and the meeting waxed better and better until the hour grew ,late, and the chairman, L. G. E. Bignell, originator of the idea, brought to a close what was agreed to be a profitable and entertaining evening. The ball was started rolling by Paul Ruedemann of the program committee, who offered the following:

Jan 1, 1929

By W. A. Backofen, R. L. Fleischer

Single crystal, bicrystal, and polycrystal tensile tests of aluminum at 4.2°K, 77°K, and 300°K have been used to examine the role of grain boundaries in the deformation process. Results indicate that a grain boundary may affect the extent and slope of easy glide. The stage II hardening rate, on the other hand, is independent of the presence or absence of grain boundaries. This conclusion allows the size of the region of multiple slip caused by an incompatible grain boundary to be determined. For the size of bicyystal sample used in this study, multiple slip occurs in about half of the cross section. PREVIOUS studies of the stress-strain characteristics of bicrystals of face-centered-cubic metals have been limited to aluminuml-5 at room temperature. Recent results, however, indicate that the stress-strain curves of single crystals of such metals may be separated into at least three stages6 in which different deformation processes are occurring7 provided testing is done at sufficiently low temperatures.' Since for aluminum a well-defined stage II develops only below room temperature, previous studies have not been able to relate effects of grain boundaries to all of the three stages of deformation. It is therefore to be expected that low-temperature deformation of aluminum single crystals and bicrystals should clarify the effects of grain boundaries on the different processes of deformation. EXPERIMENTAL PROCEDURE Single crystals and bicrystals were grown from the melt by the standard techniqueg with aluminum reported by Alcoa to be 99.993 pct pure. Ridges in the boat were used to guide the grain boundary during growth, assuring that the boundary would bisect the sample.10 The rate of furnace motion during growth was 1.0 cm per hr. During growth zone purification resulted, as evidenced by the ability of the first material to freeze to recrystallize at room temperature following severe deformation. Samples were approximately 4.4 X 6.6 mm in cross section and 103.5 mm in length between grips. Samples were annealed at 635" i 5°C for 40 hr and furnace cooled over a 7-hr period. They were then electropolished in a solution of 5 parts methanol to 1 part perchloric acid at a current density of 15 amp per sq dm for about 30 min at temperatures below 0°C. Tensile testing was performed at 295" (room temperature), 77" (sample in liquid nitrogen), and 4.2"K (sample in liquid helium) on the hard-type machine indicated schematically in Fig. 1. The machine con- sists basically of a tube surrounding a rod; one end of the sample is attached to each member, and the rod is pulled up the tube to extend the sample. The rod is rigidly mounted and is moved vertically by a system described by asinski." The pulling force is measured continuously by an electrical strain gage load cell, and the relative displacement of the tube and rod is also recorded continuously by a soft cantilever beam with electrical strain gages. Maximum stress and strain sensitivities were ±2g per sq mm and * 3-10-5. In all tests the strain rate was approximately 5.10-5 per sec. The thin wires in the tensile apparatus introduce softness, which may be corrected for, however, by measuring load vs displacement with the sample replaced by an elastic member. For loads greater than 15 kg the spring constant is 1.875.106 g per cm. The flexible wires also served to reduce substantially the large shearing forces which may arise in the case of grips having horizontal rigidity.'' As in any gripping system, however, bending moments will arise in the course of deformation by single slip. Engineering stress, s = (load)/(original cross-sectional area), and strain, E = (increase in length)/ (original length), are used for stress-strain curves unless otherwise indicated. Tables list resolved shear stress, T=mo and shear strain ? = dm, where m is the usual Schmid resolved shear stress factor for the primary slip system at the start of deformation. The first group of samples to be described forms an isoaxial set, all of the crystals making up the single crystals or bicrystals having the same tensile axis, the orientation of which is indicated by the cross in Fig. 2. For this orientation the primary slip plane and slip direction make angles of 45 deg with the tensile axis and the Schmid factor m has its maximum possible value of 0.5. Rotations about the tensile axis are indexed by means of an angle 0 between the small-area surface of the samples and the projection of the primary slip direction onto the cross section, as defined in Fig. 3. In single crystals, values of 0 were 0 and 90 deg, while in bicrystals 0 values were (0 deg, 180 deg), (90 deg, 270 deg), and (0 deg, 90 deg) as indicated in Fig. 4.

Jan 1, 1961

By Theodore B. Comstock

The paper of Mr. S. F. Emmons on the structural relations of ore-deposits, presented at the Boston meeting in February last, having been, as I am informed, unavoidably delayed in publication, was not distributed in the preliminary edition to members until immediately before the sheets of Volume XVI. of the Transactions, containing it, were sent to press. Consequently, I saw it for the first time too late to offer any comments which might have accompanied it in that volume. This is my justification for present-

Jan 1, 1889

By John Branner

FIVE of the geologic horizons that yield oil in other parts of the world are represented in Brazil; namely, the Devonian, Carboniferous, Permian, Cretaceous, and Tertiary. Thus far, the first two have shown no, evidences of being oil bearing within Brazilian territory. Not enough exploring has been done to permit trustworthy comparisons of the relative importance of the Permian, Cretaceous, and Tertiary as oil-bearing horizons in this country. The most important, indeed almost the only, information available relates to the locations of the areas and to the structural features of the several horizons. The theories regarding the physical conditions under which these rocks were laid down, however, I regard of the utmost importance. PERMIAN Rocks of Permian age cover an enormous area in Brazil, extending from Rio Grande do Sul to Maranhão on the north, and to Matto Grosso on the west. These Permian rocks in many places are known to include oil-bearing shales and in some locations contain small veins of gilsonite. The geologic map of Brazil shows that the Permian area is widely distributed, but there is considerable doubt about 'the origin of some of the rocks:. Some of the lower Permian beds in southern Brazil contain marine fossils, but in Minas no fossils have as yet been found in them, and in Bahia, at only one locality have a few Permian plants been found. Indications of oil have been found in the states of São-Paulo, Paraná, and elsewhere farther south, but wells drilled in the Permian of São Paulo near the Morro do Bofete did not find oil. One well has been started, by the Brazilian government, in the Permian of Paraná near Marechal Mallet, close to latitude 26° south, but thus far oil has not been found.

Jan 6, 1922

By E. N. Harshman

Uranium mining and milling are rather new industries in Wyoming and South Dakota, but, in the past 15 years, ore valued at more than $400,000,000 has been mined and milled in the region. The major uranium deposits are in structural and/ or erosional basins or on the flanks of uplifts. The principal host rocks are medium- to coarse-grained sandstones that were deposited in continental or brackish-water environments and were derived in large part from the granitic cores of the uplifts and the sedimentary rocks that flank the cores. The ages of the host rocks range from Cretaceous to Miocene, but more than 95 per cent of the known reserves in the region are in rocks of early Eocene age. The bulk of the ore in the region is unoxidized and lies below the water table; some oxidized ore has been mined in the Powder River Basin and Black Hills districts. The unoxidized ore comprises pyrite, uraninite and/ or coffinite, marcasite, hematite, jordisite(?), and selenium. Minerals in the oxidized ore include hydrous uranium carbonates, phosphates, and sulfates and hydrous uranium and/ or vanadium silicates. The deposits are in the form of ore rolls that contain from a few hundred to a few hundred thousand tons of ore, ranging in grade from 0.1 per cent to 1.0 per cent U3O8. The rolls are at the margins of large tabular bodies of sandstone that has been altered by the orebearing solutions. The deposits are believed to have resulted from the interaction of an alkaline; oxidizing, ore-bearing ground water and a reducing environment. Exploration guides include the spatial relations of ore to altered sandstone, favorable lithology in the host rock, the content of certain elements and/ or compounds in ground water, and the relation of deposits to major paleodrainages.

Jan 1, 1968

By Arthur L. Hall

The purpose of this symposium is to challenge industry to better air classification, and as a first step toward fulfillment, to spotlight three fairly recent, aerodynamically designed, highly efficient air classifiers. This discussion does not intend to imply that present practice is bad. Actually, when present air separators are used for the jobs for which they were originally designed, they give high production and uniform operation, with a minimum of maintenance. The customers of nonmetallic mineral pigment producers, however, are making increasing demands for finer products, such as 99.9 pct -20µ, which appears to be beyond the economic capabilities of standard air separators industrially used over the last 10 to 30 years. Here is an actual example. A 10-ft diam pebble mill is in closed circuit with a conventional 12-ft diam centrifugal air separator, grinding 20-mesh wollastonite to a series of fine grades up to 99.97 pct - U.S. No. 325 mesh (44µ). Fig. 1 shows variations in fineness of mill discharge (or air separator feed), recycle for regrinding (or air separator tails), and product as measured by a wet rotating sieve test. For example, when the mill is turning out a product 80 pct -325, the mill discharge or separator feed is 30 pct -325, and the coarse tailings or recycle is only 5 pct -325. Hence 25 pct of the 30 pct available is accepted as product. This is efficient separation, and the ratio of recycle to feed is only about 2: 1. How- ever, to make a product testing 99.97 pct -325 the separator feed is 62 pct -325 and the coarse tailing 60 pct -325. In this case the recycle ratio is about 13: 1 and the economic limit to produce fineness has been substantially reached with this given equipment and process arrangement.

Jan 10, 1957

William Clinton Brown, Brooklyn, N. Y.: The demand for an apparatus for cooling water for condensers, refrigeratingmachinery and air-compressors, as well as water-jacketed furnaces, has led manufacturers to put such an apparatus on the market, so that it is now possible to purchase a cooling-tower, properly designed and constructed, by simply stating the amount of water to be cooled and the temperatures of the hot and the cold water. The principle is similar to that described by Mr. Henrich, but wood is not used in the best apparatus. There are two great objections to wood: First, it cannot last long under the very trying conditions to which it is subjected; and second, it absorbs the organic matter with which water in constant use becomes impregnated, and the resulting odor is very disagreeable. A few days ago I saw a cooling-tower and condenser, built by the Henry R. Worthington Co., in operation at the Edison electric-lighting station in Brooklyn, N. Y., cooling the water for a 700 horse-power condenser. It consisted of a large stack of iron, about 15 feet in diameter by about 30 feet high. This stack was filled with tiling through which the water falls. A whirligig distributes the water evenly over the top, and a large fan, about 6 feet in diameter, driven by a 10 horse-power electric motor, blows air into the bottom, thus giving a positive circulation. The water, in running down the sides of the tiling, is met by the blast of air, and enough is evaporated to cool the rest. The vacuum-gauge on the condenser showed 26 inches; so the condenser was undoubtedly getting sufficient cool water.

Jan 1, 1896

By Paul E. Melancon, Vincent C. Kelley, Dale F. Kittel

Uranium of the Grants region occurs predominantly in continental sandstones of the upper part of the Jurassic Morrison Formation, but significant lesser deposits are found in limestone of the Jurassic Todilto Formation and in black shale of the Cretaceous Dakota Formation. The deposits are disseminations that form runs ranging from a few hundred tons to several million tons. The ore consists mainly of uraninite, uraniferous carbonaceous material, coffinite, and such secondary oxidized minerals at tyuyamunite, carnotite, and uranophane. In sandstone, the ore runs were locallized by mudstone, interstitial carbonaceous material, and primary sand channel trends. In limestone, ore deposition was related to folds and fracture zones. The great bulk of production has come from the Ambrosia Lake mines in the Grants district and the Jackpile and Paguate mines in the Laguna district. The ores, which generally have been 0.20 to 0.30 per cent U3O8, are treated at mills operated by Kerr-McGee Corporation, Homestake-Sapin Partners, and The Anaconda Company, all in the Grants district. In 14·years after discovery in 1950, the deposits had yielded concentrates valued in excess of $800,000,000. Since deposition of the Jurassic host rocks, a geologic history involving tilting, faulting, erosion, changing ground-water environments, and oxidation has considerably influenced the existence and character of the deposits. It is evident that their ongm is not simple. However, a degree of agreement appears probable for a pre-Dakota age for the original ore runs, and, at Ambrosia Lake, two principal stages of ore formation, separated by Laramide faulting, are recognized. All earlier ores have been modified by Quaternary oxidation, solution, and enrichment during which time much secondary tyuyamunite, metatyuyamunite, carnotite were formed.

Jan 1, 1968

By A. W. McReynolds

E. OROWAN*—I observed the phenomenon of jerky yielding many years ago with zinc25 and cadmium single crystals. A significant point was that the jerks occurred not only when the stress was raised but also (sometimes, after a pause of many minutes during which no trace of creep was observable) at constant stress. The phenomenon may be closely linked with the inertia of the testing machine and of the specimen, although the inertia alone cannot account for it. If, during the test, the resistance of the material to plastic deformation suddenly diminishes while the applied force remains constant, a sudden deformation follows until the yield stress has risen, by strain hardening, to the level of the applied stress (= the value of the previous "upper yield point."). When this is reached, the rate of deformation has attained a maximum value because, up to this moment, the applied force was higher than the plastic resistance of the specimen, and the difference was used for accelerating the moving parts of machine and specimen. The kinetic energy accumulated is now transformed into plastic work by further deformation; that is. the deformation overshoots the point at which the plastic resistance equals the applied static force. When the kinetic energy has been used up, therefore, we are left with a specimen the yield stress of which is higher than the applied stress, and no further deformation can occur (apart from a little creep) until either the applied stress has been raised to the new yield stress level, or the yield stress has fallen by thermal recovery to the level of the applied stress. While this occurs, a new upper yield point can develop, for example, by precipitation.26

Jan 1, 1950

By Walter J. Mead

By American tradition, if not by rational decision, publicly owned natural resources have been transferred to private industry for processing. The process of transfer requires specific determination of the price which the patentee, buyer, or lessee must pay to the government in exchange for the right to develop a resource, and selection of the patentee, buyer, or lessee from among several possible contestants. Pricing of natural resources owned by the government presents a set of problems quite different from ordinary commodity pricing. Natural resources in situ are not homogeneous commodities. Within any class of natural resources, specific leasable parcels will differ in value by reason of location and accessibility, as well as quality and quantity. Thus, there is no "going price;" every lease within a specific resource class will have a different value. To complicate further the pricing and buyer selection problems, competition may not be reliable. Natural-resource markets are characterized by oligopsony conditions. In a significant number of cases, as will be shown later, there has been only one bidder for a given lease, and in most lease sales the number of bidders is equal to or less than three. As a further complication, there is great uncertainty regarding the value of specific resources, even among the best-informed buyers, as well as within the leasing agency. In some instances, particularly with regard to oil and gas resources, there may be uncertainty about the presence of resources, as well as the quantity and quality of any resources contained in the tract offered for lease. In other cases, such as oil shale and some deep ocean minerals where new technologies are involved, the presence of the resource is clearly established. There may be a relatively high degree of knowledge about the quantity and quality of the resource, but there is great uncertainty concerning the cost of production. These problems in total make it difficult for the leasing agency to appraise accurately the resource to be leased, as well as for the potential bidder to calculate a bid price that will yield him a normal profit. The pricing goal of the federal government as the seller or lessee may be to capture the economic rent; that is, the price of a resource might equal its discounted present value. A required price substantially above this amount would either generate no bids, or, in the long run, would bankrupt the buyer. A price below this amount is a disguised subsidy to the lessee. A subsidy to mineral lessees, as to any other economic interest group, as a minimum should be justified by a clear showing of net external benefits from the economic activity. In the case of timber sales by the U.S. Forest Service, the Forest Service Handbook asserts that "the aim in national forest stumpage appraisal is to determine market value,"8 and "market value" is equated to "fair market value." Regarding minerals, there is no reference in legislation or regula-

Jan 1, 1976

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

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

Jan 1, 1965

By Leo J. Vogel, E. D. Hummer, David J. Akers

INTRODUCTION An efficient refuse-disposal system is a necessary part of the modem cleaning plant. The large-scale refuse system and disposal area, engineered for the lifetime of the plant, has become more important due to the greater tonnages of refuse produced from increased quantities of mechanically mined and prepared coal. Laws and increased government regulations have affected the design and operation of disposal systems. THE EFFECT OF MINE AND PLANT OPERATION Refuse disposal starts at the mining face. The mining system, the type of roof support, the machinery used, and the degree of discipline at the face contribute to the amount and type of refuse that must be removed through the disposal system. Economies gained through modification of the mining system or mining machinery may be partially offset by increased dilution of the mined coal with impurities from associated rock formations. In some cases the change in the mining system and equipment has reduced the dilution. In all cases the ratio of impurities that must be removed from the raw-coal feed to the plant not only affects the maintenance and

Jan 1, 1979

By J. W. Givens, P. B. Crawford

A potentiometric model study has been made of the effect of vertical fractures existing in the matrix of the reservoir on the flooding or cycling performance. Fractures can have unusual flow characteristics. Fluid entering one side of a fracture can emerge on either the same or opposite side of the fracture, depending on the particular streamline. Fracture orientation has a great influence on the sweep efficiency. However, sustained fluid injection may still permit large areas to be swept. INTRODUCTION One can find considerable information available in the literature on the effect of fractures originating at the wellbore on sweep efficiencies of water-flooding or gas cycling programs.1-5 However, there arc few, if any, quantitative data reported in the literature on the effect of vertical or horizontal fractures existing out in the reservoir matrix on secondary recovery performance. Several papers have been presented on the effect of vertical and horizontal fractures on the productivity or conductivity of waterflood and gas injection patterns, but in all cases the fractures initiated at the well and simulated commercial fractures.6,7 It is believed that natural fractures may exist out in the reservoir matrix and would effect the displacement performance. The purpose of this report was to study the effect of a few isolated vertical fractures existing out in the reservoir matrix on the performance of waterflood or gas injection patterns. DESCRIPTION AND EQUIPMENT Since the potentiometric model was described by Lee8 it has been widely used to study numerous types of fluid displacement problems. The potentio- metric model can be used for fluid displacement studies when the following assumptions are valid: (a) steady-state conditions exist; (b) the mobilicy ratio is one; and (c) the capillary and gravitational effects can be neglected. Five-spot and direct line drive square patterns were studied using a copper strip of the desired length and orientation to simulate a vertical fracture in the reservoir matrix. The 20 x 20-in. model was considered to represent only one element of an infinite array of similar patterns. DISCUSSION AND RESULTS FIVE-SPOT PATTERN — ONE FRACTURE BETWEEN INJECTION AND PRODUCING WELLS Fig. 1 shows a quadrant of a five-spot pattem with the vertical fracture existing out in the matrix along a line connecting the injection and producing wells. Length of the fracture was equal to 35.4 per cent of the distance between injection and producing wells. In this particular pattern it is noted that fluid breaks through from the injection well to the producing well when the dimensionless time is equivalent to 26.9. Dimensionless time is defined as volume of fluid injected divided by the volume of displaceable fluid in the pattem expressed as a per cent. The cross-hatched areas of this

Jan 1, 1967

By Charles L. Mantell, Kurt Straler

The hydrogen reduction of Cr2O3 to chromium metal was found to be feasible at very low water-vapor concentrations, corresponding to dew points of -38° to -24°C, over a temperature range of 1130" to 1490°C. Hydrogen reduction under these conditions was predicted by the calculated equilibrium curves which also indicated that CrzOs is reduced directly to chromium without forming the intermediate oxide, CrO. This reduction path was confirmed by X-ray diffraction analysis. The percent reduction of Cr2O3 at each reaction temperature was constant with time, suggesting an inhibiting effect of water vapor. A small increase in the residual water-vapor concentration of a single temperature, 1490°C, strongly retarded the rate of reduction This effect was expressed by an empim'cal equation which indicated a direct relationship between "distance from equilibrium" and the rate of reduction. me effect of temperature over the range of 1130" to 1490°C was expressed in an Arvhenius plot of log rate vs reciprocal absolute temperature. From this curve the apparent enthalpy of activation was found to be 29,600 cal. Based on the hypothesis that the rate of reductiun is contvolled at the oxide-metal interface, an over-all rate equation consistent with the experimental data and the thery of absolute reaction rates was formulated. A simplification of this expression to an Arrhenius equation was justified by the overriding effect of temperature on the rate of reaction for the minimum water-vapor concentration range. MOST of the metals in Subgroup V1 of the periodic table can be prepared commercially by direct reduction of their oxides by hydrogen or carbon monoxide, at temperatures considerably below the melting points of both the metals and their oxides. Chromium is an exception, being generally reduced from its ore, Cr2O3 . FeO, by silicon in an electric arc furnace which operates above the melting point of the Fe-Cr alloy or above the melting point of chro- mium if a chromium oxide be the starting material. In reduction of chromium oxide by hydrogen, either reduction does not occur at all or the rate of reduction is extremely slow. Theoretical considerations based on the high, exothermic, free energy of formation of Cr2O3 compared to the oxides of the other Subgroup VI metals, molybdenum, tungsten, and uranium, would also suggest a slow rate of reaction and a high activation energy. Interest in the direct gaseous reduction of fine-powdered ores in fluidized beds was considered justification for examination of this reaction. In order to develop a basis for a continuing study of the commercial feasibility of the direct gaseous reduction of chromite, a study of the kinetics of the reduction of Cr2O3 with hydrogen was undertaken. To the authors' knowledge no accurate kinetic data for this reaction have been obtained. Neither has an activation energy been determined nor has an attempt been made to establish a mechanism of reaction. LITERATURE Maier10 compared the data of I. Y. Granaat,6 H. von Wartenburg and S. Aoyama, and G. Grube and M. Flad7 with that derived from calorimetric and ther-modynamic properties for the equilibria for the reduction of Cr2O3 with hydrogen. These results, plotted as the log of the equilibrium constant vs absolute temperature for the reduction of Cr2O3 and the intermediate oxide, CrO, to chromium, show agreement between the differently derived data. In both cases the equilibrium constants were extremely low. Maier showed that, over a temperature range of 1000° to 2000°K, Cr2O3 is more readily reducible than CrO. Granat assumed that CrO was preferentially formed from Cr2o3 above 1100°C. Grube and Flad's analysis of their reaction products in the 895" to 1000°C range indicated the coexistence of only Cr2O3 and chromium. The hydrogen reduction of the other Subgroup VI metals, molybdenum, tungsten, and uranium, shows that reduction of the higher oxide proceeds through all of the intermediate oxides before being reduced to the metal. Since evidence pointed to an anomaly in the reduction behavior of Cr2O3, the authors investigated the reduction path of Cr2Os.to chromium. This was done theoretically with more recently available free-energy data and experimentally by X-ray diffraction analysis. This work reinforces Maier's conclusion.

Jan 1, 1964

By C. H. Samans, G. F. Tisinai

HARDENING and embrittlement of the ferritic chromium stainless steels at temperatures near 885 °F have been known for a long time.' However, no satisfactory explanation has been given. Both ordering and precipitation hardening have been suggested. Fisher, Dulis, and Carroll2 discovered a chromium-rich body-centered-cubic precipitate in embrittled alloys. Subsequently, Williams' and Wright4 also have found evidence of this body-centered-cubic constituent. William's hardness, electrical resistance, and magnetic studies led to his proposal of a new constitutional diagram for the Fe-Cr alloys. The new feature of this diagram is the eutec-toidal decomposition, below about 970°F, of the s phase into two stable body-centered-cubic solid solutions, one rich in iron and the other rich in chromium. An observation of Heger5 that the amount of s phase has increased and the amount of chromium-rich body-centered-cubic phase decreased in the interval 5000 to 32,600 hr at 900°F, even though the alloy increased in hardness, casts some doubt on this diagram. If precipitation hardening causes the embrittlement, the precipitate probably is always coherent with the matrix, since no evidence of overaging has been reported. It cannot be stated positively, however, that Fisher's body-centered-cubic constituent is the embrittling phase. According to Preston's data,6 such a chromium-rich phase should have a parameter less than about 0.5 pct larger than that of the iron-rich matrix lattice. Moreover, the constitutional relationships whereby Fisher's constituent forms, and whether it is stable, metastable, or a transition phase, are not yet completely clear. The recent studies of Wright4 and of Lommel,7 as well as the earlier studies of Becket8 and of Hochmann,9 have shown that 885°F hardening occurs in relatively pure Fe-Cr alloys. No evidence of its occurrence or absence in chromium itself has been reported. The rate of hardening in high purity alloys seems appreciably slower than that in alloys containing larger amounts of impurities (chiefly carbon and nitrogen). This may be due merely to the absence of hardening and straining effects from precipitated carbides and/or nitrides. These observations on high purity alloys make it seem unlikely that 885 °F hardening is caused by a constituent containing other than iron and chromium atoms, e.g., carbides and/or nitrides. Wright,4 Lommel,7 and Lena and Hawkes10 emonstrated the accelerating effects of a finely dispersed precipitate of (probably) chromium nitride on the hardening reaction. This appears to be evidence that lattice straining increases the rate of nucleation of the hardening constituent. Some new observations on 885°F hardening are reported here. They show an effect of preheat treatment that should contribute to a better understanding of the 885°F hardening phenomenon. They also clarify a discrepancy which exists in the literature. Some investigators have reported most rapid hardening at 885", whereas others have reported it at 930°F. The present work also shows that 885°F hardening does not occur in electrolytic chromium, and that any long range ordering type of reaction affecting any sizeable part of the volume is unlikely. Materials Studied Table I shows the currlposition of the alloys used in this investigation. In these alloys carbon and nitrogen are present in roughly similar amounts. Presumably both elements precipitate, as carbides and/or nitrides, during the heat treatments given.

Jan 1, 1958

By U. N. Bhrany, N. Arbiter

Over the last one hundred years the problem of assessing the efficiency of energy consumption in producing rock breakage has been studied by many investigators from a variety of viewpoints. Their contributions fall into three main categories: (1) those characterized by a priori assumptions of a relation between the energy required for fracture and the degree of fragmentation produced (e.g. Rittinged(l), Kick(2) Bond(3)); (2) those studying simple systems with controlled energy applications (Gross(4)?(5) ); (3) those treating operating data to develop practical relative measures of efficiency (Coghill(6), Taggart(7)). Closely involved in the efficiency problem is the characterization of size distributions produced by comminution. Unless an experimental size distribution can be approximated by a distribution function and its constants, it becomes difficult if not impossible to develop quantitative energy-particle size relationships. While many such functions have been proposed, none are both completely adequate and convenient. The simpler fonns usually describe only a part of the sizing data, while those which apply to a greater extent are cumbersome(8). The thesis underlying the study here reported can be stated as follows: Size reduction in a tumbling mill subjects ore particles to a relatively constant fracture-producing environment. The intensity of the forces is determined by such factors as the mass of the breaking bodies (rods, balls, rock), and the speed and dimensions of the shell. For a particular ore the extent of size reduction will depend both on the intensity and on the duration of exposure. The latter is the residence time in a batch mill, or is determined by the effective volume and the flow rate in a continuous mill. Size reduction can thus be regarded as a rate process in which the weight of material in size intervals varies as a function of grinding time. Although both the rates of disappearance of coarser sizes and

Jan 1, 1961

By Raymond C. Boettner

The present work had for its purpose: 1) the identification of crack nucleation sites in AISI 4340, quenched to martensite and tempered over a range of 'temperatures; and 2) the comparison of fatigue processes in AISI 4340 with processes observed previously in pure metals From constant def1ection-bending fatigue tests, martensite boundaries were identified as the favored crack nucleation sites in quenched and tempered AISI 4340. It, also, was concluded that the fatigue processes operating- in this lous-alloy steel were similar to Processes observed in pure tnetals. ALTHOUGH much engineering data has been accumulated on the fatigue properties of quenched and tempered martensitic steels,' fatigue as a process is not as well understood in martensite as it is in pure metals.' Important features of the fatigue process, such as the identity of the nucleation sites, have not been determined in the commercially important high-strength low-alloy structural steels. The present work had for its purpose: 1) the identification of crack nucleation sites in a low-alloy steel, i.e., AISI 4340, which had been quenched to martensite and tempered over a range of temperatures; and 2) the comparison of fatigue processes in the AISI 4340 with processes observed previously in pure metals. This comparison of the fatigue processes in the different tempers was restricted to the high-strain low-cycle part of the S-N curve. Under these test conditions, previous work on a number of metals has shown that a large number of cracks are nucleated in less than 30 pct of the fatigue life.3 Furthermore, crack nucleation sites are not restricted to inclusions but are also associated with intrinsic structural characteristics of the metal. MATERIAL A 20-lb ingot of vacuum-melted AISI 4340 (for composition see Table I) was hot-rolled to 1-in.-diam rod and then cold-rolled to a 1-in.-wide strip, 0.08 in. thick. Fatigue specimens, see insert of Fig. 1, were machined from the strip with the long dimension parallel to the rolling direction. m this orientation, the stringers of 1 to 2 p inclusions present in the sheet lay parallel to the stress axis in the specimens. The specimens were austenitited at 2050°F in order to obtain a large prior austenite grain size, i.e., 2 mm, which facilitated the subsequent identification of the prior austenite boundaries. A helium atmosphere was used to minimize decarburization. After austenitiza-tion at 2050°F, the specimens were transferred to a 1450°F furnace so that specimen distortion was held to a minimum in the subsequent oil quench. Previous work4 indicated that refrigeration in liquid nitrogen prior to tempering reduced the percentage of retained austenite in the quenched specimens to less than 5 pct. Tempering was carried out in air over the temperature interval of 200°to 800°F to produce a range of mechanical properties, Table I. The preparation of the fatigue specimen was completed by grinding about 0.005 in. from each surface and electropolishing in a chrome trioxide-acetic acid solution for 30 min. Examination of etched cross sections of specimens prepared in this fashion showed the foregoing specimen preparation to be adequate for the removal of the decarburized layer present after the heat treatment. Transmission electron microscopy showed that the as-quenched microstructure of this alloy consisted of a mixture of martensite plates containing either a high density of dislocations or microtwins. Previous work5'6 indicated that in the course of oil quenching autotem-pering resulted in the formation of E carbide on the martensite and microtwin boundaries. Tempering for 2 hr at temperatures up to about 400°F resulted in further precipitation of the E carbide. Finally, at about 400°F, cementite began to replace the E carbide on the martensite and microtwin boundaries in addition to forming a Widmanstatten structure within the plate matrix. EXPERIMENTAL S-N curves were obtained using electropolished specimens cycled at 1800 cpm as cantilever beams in fully reversed bending at selected constant deflections. The deflections were translated into surface strains by means of a calibration curve obtained through the use of strain gages. An argon atmosphere was used to minimize environmental effects. To investigate the development of fatigue slip bands, the specimens of the different tempers were unidirec-tionally bent to a surface strain of 0.005 to 0.007, photographed to record the location and appearance of slip bands so introduced, and then cycled to failure

Jan 1, 1968

By C. J. Beevers

Tlze influence of zirconium hydride precipitate mprphology on the fructure of Zr-H alloys tested at strain rates of 10- sec at 20° and - 196°C and at strain rates of -500 sec.-1 at 20°C has been inves-tigated. The critical stage in the embrittlement of these alloys was the fracture of the zirconium hyhide precipitates to form large interval cracks at a stress of 25,000 10 137,000 psi. In specimens con-temping up to 100 ppm H the preciptates existed as isolafed platelets in the zirconium matrix and their fracture as enhanced by low temperature (—196°C) and high strain rate (-500 set-f) loading. These resl~lts lead to the conclusion that the rate of strain hardening of the zirconium metal controls the frac-tzrm of the hydride platelets. Increased hydrogen contents of 500 to 2000 ppm resulted in an increase in the 1)volume fraction and size of precipitates and crlso led to crack propogation in the hydride at both 20 and —196C at the low strain rates (10'* sec-'). Quenching led to refinerment of hydride precipitate size and reduced the degree of embrittlement at — 196°C; this effect is attributed to the absence of fracture of the fine precipitates. The formation of zirconium hydride precipitates has been shown to be the cause of hydrogen embrittlement of zirconium.' Several investigators'-" have studied the problem in broad outline, demonstrating that impact-loading conditions, testing temperatures below room temperature, and increasing hydrogen content produce increased brittleness. For example, Muehlenkamp and schwope2 showed that the transition temperature for notched impact tests was raised from 150" to 350°C on increasing the hydrogen content from 45 to 490 ppm. The degree of embrittlement is also controlled by the morphology of the zirconium hydride precipitates. The solubility of hydrogen in zirconium decreases from 600 ppm at 550°C to 10 ppm at 20"C,~ so that the form of the zirconium hydride precipitates (ZrH2) can be modified by varying the cooling rate through the Zr-aZr + ZrH2 phase boundary.= Forscher showed that quenching a specimen containing 35 ppm H from above 315°C resulted in a reduction in area of 70 pct at -196"C, whereas slowly cooling from above 315°C resulted in a ductility of half this value. The role of the hydride precipitate in the fracture process has been examined by Young and schwartz6 and more recently by westlake.' From metallo-graphic observations on slowly cooled Zr-H alloys they have suggested that cracks are nucleated in the hydride precipitates by the interactions of twins in the zirconium metal with the hydride. The experiments reported in this paper show that crack propagation in the zirconium hydride precipitates is the critical stage in the embrittlement of Zr-H alloys. The factors influencing fracture of the hydride precipitates and crack propagation in the zirconium metal will be related to the problem of embrittlement. EXPERIMENTAL TECHNIQUES The zirconium used in these experiments was produced from an ingot of vacuum arc-melted iodide zirconium forged down to 1 in. diameter at 800' to 850°C. The 1-in.-diameter bar was surface-machined and cold-swaged to 0.375 in. diameter. After a vacuum anneal at 800°C for 1 hr the hardness was 60 to 70 Vdh. The total impurity content was approxi-

Jan 1, 1965

JOHN W. BELL, *Montreal, Quebec, Canada (communication to the Secretary?). The test results in Mr. Taggart's paper will, I am sure, be recognized as a notable contribution, and of great assistance in the study of the performance of the Hardinge mill. I regret, however, being obliged to note that Mr. Taggart still retains. such confidence in the Kick-Stadler method of computing the ?relative mechanical efficiency" of crushing machines. The Rittinger-Kick graph submitted by Mr. Gates and the tests made at McGill University disclosed precisely the same fundamental defect in the Kick-Stadler theory. Consequently, I have been obliged to recalculate in terms of Rittinger surface units the results obtained in the 28 rock-crushing tests cited by Mr. Taggart, in order to find- out what the relative efficiencies really were. In order to show the large discrepancies between the Stadler and Rittinger R. M. R's, the most, efficient result disclosed by each method is represented by the number 100, and the R.. M. E.'s for the other tests have been recalculated on this basis. The results will be found in Table 1. Personally, I look forward to the time when we shall cease to talk about "relative mechanical efficiency" and merely refer to the "efficiency" of a crusher. All that is required to accomplish this is to agree on a standard method for determining the "crushing constant" of a given rock and a standard method for calculating the efficiency. The figures in the fourth column of Table 1 have been derived by assuming a constant of 2,000 for the quartzite crushed in the Yale tests. The Stadler method sometimes indicates changes in efficiency produced by, changes in operating conditions, as I pointed out in a paper describing rock-crushing tests made at McGill University. It is, however, not enough to determine that certain changes increase or decrease efficiency; surely it is equally important to determine the magnitude of these variations. By examination of Mr. Taggart's results, I have been obliged to conclude that the size of feed and amount of reduction greatly influence the Stadler R. M. E. figures, that they are positively misleading. It should be mentioned that since the majority of the tests have been made at the least efficient feed rates, and since, moreover, it is one of the evidently very important factors affecting efficiency, it is possible that different results might be obtained by a high-tonnage feed series, and that

Jan 8, 1917