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By Ira B. Jorafemon

In the interesting Institute symposium of the preservation of peace by force, through mineral control, one important aspect of the question was not presented. This is the responsibility the United Nations, and particularly the United States, will incur the through limitation of the economic activities of nations that are now friendly to us, as well as of nations that are enemies or are under the control of enemies. After the war all nations, friends as well as enemies will be poor. Hunger and bankruptcy will, will like the sword of Damocles, hang over the heads of all of us on this blundering planet. When the actual fighting is over, there will be a universal attempt to squirm out from under the sword by resuming production of peacetime goods, for trade as well as immediate consumption.

Jan 1, 1944

By John C. Cook

Long-wave short-pulse radar has been shown capable of exploring to distances of several hundred feet through massive, dry rock salt. Exploration distances of 30 to 60 ft through bituminous coal and massive limestone, respectively, have also been demonstrated with low-power experimental radar equipment in underground mines. Working ranges up to 250 ft in limestone and coal are considered feasible. Radar reflections should be produced by all large electrically contrasting objects such as fault gouge masses, wet shattered ground, metallic mineralization, adjacent mine workings (dry or flooded), and abandoned drill holes. It is believed that radar can locate such obstacles in advance of underground mining through all massive rocks of low free-water content, including many igneous and metamorphic rocks. Three years of studies and experiments in radar exploration through rocks are reported.

Jan 1, 1974

By R. M. Hays

At the present time, oxidized taconite and semitaconite are not processed on the Mesabi Range except in vely limited tonnages. However, it is estimated that by 1990 shipments from the Range will approach 75 million tons of iron ore per year. To achieve this and future production, either additional magnetic taconite reserves must be proven or oxidized taconite and semitaconite must be processed. One beneficiation process which uses high-intensity magnetic separation and flotation for concentrating oxidized taconite and semitaconite is described. Detailed metallurgical results are given and an economic evaluation of the process is presented with comparison to other processes. The results of the present study indicate that the high-intensity magnetic separation and flotation process appears nearer commercialization for the processing of Mesabi Range semitaconite. The disadvantages of the process are nearer solution and are being solved by well-defined programs. During the twentieth century, the Mesabi Range in northeastern Minnesota has been the main source of iron ore for American steel mills. The Mesabi Range, which is about 120 miles long and up to 3 miles wide, is the pre-glacial outcrop of a group of sedimentary iron-bearing rocks known as the Biwabik formation. The formation, which is 200 to 650 ft thick and dips 50 to 10° to the southeast, is divided into four stratigraphic units. From top to bottom, these are the Upper Slaty, Upper Cherty, Lower Slaty, and Lower Cherty. Since its deposition in Precambrian time, most of the original Biwabik formation has been subject to alteration. Thus, although the iron content of the original formation was quite uniform, major variations in mineral composition now occur both laterally along the length of the formation and vertically within its units. Details of the mineralogical variations in the Biwabik formation have been described by Wolff,' Gruner, 2 and White.3 The unaltered portion of the Biwabik formation includes the magnetite taconites which are being commercially processed by Reserve Mining, Erie Mining, Eveleth Taconite, National Steel, Butler Taconite, and U.S. Steel. These six operations have a capacity of 32 million tons of iron ore pellets per year and have produced approximately 170milion tons of pellets since 1956. Capacity for another 30 million tons of pellets per year is being considered by the industry for the next ten years. This increase will be obtained by constructing new plants and by expanding present operations. Thus, by ! 978, it is estimated that approximately 60 million tons of iron ore vellets will be produced each vear from the magnetite taconites of the Biwabik formation. The portions of the Biwabik formation subjected to intense alteration resulted in direct shipping, wash, and heavy-media ores. Since 1892, 1.8 billion tons of direct shipping ore have been shipped from the Mesabi Range. This ore has been the major source of iron ore for American steel mills. In 1967, about 11 million tons of direct shipping ore and 13 million tons of wash, jig, heavy-media, and other gravity concentrates were shipped from the Mesabi Range.4 These products generally have poorer physical and chemical properties than the iron pellets produced from magnetic taconite. It is predicted that the shipment of these materials will decrease from 24 million tons in 1967 to 6 to 8 million tons in 1975.' This decrease will

Jan 1, 1970

By D. S. Tannhauser, I. Bransky

Measurements of the electrical conductivity, the thermal electromotive force, and the deviation from stoichiometry by thermogravimetry were made on ferrous oxide (wüstite) single crystals as well as on poly-crystalline samples in the temperature range of -900" to 1330°C. In the region defined by T 2 1000°C and 1.05 5 O/Fe 5 1.10 the electrical conductivity was shown to be proportional to the sixth root of- the oxygen partial pressure and to be linearly dependent on the deviation from stoichiometry. The absolute Seebeck coefficient of single and polycrystalline wüstite was shown to be independent of temperature in the above region and a p to n transition of the Seebeck coefficient was observed at O/Fe = 1.09 in polycrystalline wüstite. Analysis of the results showed that the predominant defects in wüstite in the above region were doubly ionized cation vacancies. The analysis also ruled out the existence of complexes of the type postulated by Roth, except that below 1000°C there is some evidence of 'association of defects. Of the three oxides of iron (FeO, Fe3O4, Fe2O3) only FeO (wüstite) can exist within a wide range of the ratio O/Fe. This has been shown by several investigations of the phase diagram using for instance chemical analysis of quenched samples'-4 or thermogravimetric measurements. 5,8 Darken and Gurry's1 data for example in the temper- ature range 1100o to 1400°C show that the lowest O/Fe ratio obtainable for FeOl +. is about 1.045 and that the existence range extends to O/Fe = 1.20 at 1400oC. On the basis of detailed analysis of thermogravimetric measurements made by Vallet and Raccah6 the existence of three varieties of wüstite at elevated temperatures was suggested by these authors and by Kleman. It is well-established that wüstite has a NaCl structure with vacant cation sites.3, 8 From a neutron-diffraction study of wüstite samples quenched to room temperature Roth9 concluded that defects in wüstite are mostly complexes composed of two cation vacancies and one interstitial cation in a tetrahedral site. The atomic arrangement in the vicinity of such a defect is similar to that in magnetite, where each occupied tetrahedral site is surrounded by four vacant octahedral positions disposed at the corners of a tetrahedron, so arranged that each vacancy is shared by two tetrahedral cations. Thus there is an average of two vacancies per interstitial. Recent X-ray diffraction measurements made by Smuts10 on quenched wüstite samples confirmed the results of Roth's neutron-diffraction experiments. Roth's model of defects in FeO can be regarded as a solid solution of Fe3O4 in FeO; salmon1' used this defect model to calculate the activity of Fe3O1 in FeO at high temperature and claimed good agreement with the results obtained experimentally by Darken and Gurry.' Each missing cation in wüstite is accompanied by two trivalent cations, thus preserving charge neutrality. The "holes" which differentiate between the Fe 2+ and Fe3' states of the ions in octahedral positions can overcome the attractive field of the cation vacancies, and are then free to move through the crystal as charge carriers. A similar picture holds for COO, NiO, andMnO.l2, 13 Localization of the charge carriers in transition

Jan 1, 1968

By L. S. Darken

Measurements of the electrical conductivity, the thermal electromotive force, and the deviation from stoichiometry by thermogravimetry were made on ferrous oxide (wüstite) single crystals as well as on poly-crystalline samples in the temperature range of -900" to 1330°C. In the region defined by T 2 1000°C and 1.05 5 O/Fe 5 1.10 the electrical conductivity was shown to be proportional to the sixth root of- the oxygen partial pressure and to be linearly dependent on the deviation from stoichiometry. The absolute Seebeck coefficient of single and polycrystalline wüstite was shown to be independent of temperature in the above region and a p to n transition of the Seebeck coefficient was observed at O/Fe = 1.09 in polycrystalline wüstite. Analysis of the results showed that the predominant defects in wüstite in the above region were doubly ionized cation vacancies. The analysis also ruled out the existence of complexes of the type postulated by Roth, except that below 1000°C there is some evidence of 'association of defects. Of the three oxides of iron (FeO, Fe3O4, Fe2O3) only FeO (wüstite) can exist within a wide range of the ratio O/Fe. This has been shown by several investigations of the phase diagram using for instance chemical analysis of quenched samples'-4 or thermogravimetric measurements. 5,8 Darken and Gurry's1 data for example in the temper- ature range 1100o to 1400°C show that the lowest O/Fe ratio obtainable for FeOl +. is about 1.045 and that the existence range extends to O/Fe = 1.20 at 1400oC. On the basis of detailed analysis of thermogravimetric measurements made by Vallet and Raccah6 the existence of three varieties of wüstite at elevated temperatures was suggested by these authors and by Kleman. It is well-established that wüstite has a NaCl structure with vacant cation sites.3, 8 From a neutron-diffraction study of wüstite samples quenched to room temperature Roth9 concluded that defects in wüstite are mostly complexes composed of two cation vacancies and one interstitial cation in a tetrahedral site. The atomic arrangement in the vicinity of such a defect is similar to that in magnetite, where each occupied tetrahedral site is surrounded by four vacant octahedral positions disposed at the corners of a tetrahedron, so arranged that each vacancy is shared by two tetrahedral cations. Thus there is an average of two vacancies per interstitial. Recent X-ray diffraction measurements made by Smuts10 on quenched wüstite samples confirmed the results of Roth's neutron-diffraction experiments. Roth's model of defects in FeO can be regarded as a solid solution of Fe3O4 in FeO; salmon1' used this defect model to calculate the activity of Fe3O1 in FeO at high temperature and claimed good agreement with the results obtained experimentally by Darken and Gurry.' Each missing cation in wüstite is accompanied by two trivalent cations, thus preserving charge neutrality. The "holes" which differentiate between the Fe 2+ and Fe3' states of the ions in octahedral positions can overcome the attractive field of the cation vacancies, and are then free to move through the crystal as charge carriers. A similar picture holds for COO, NiO, andMnO.l2, 13 Localization of the charge carriers in transition

Jan 1, 1968

By D. G. Westlake

Resistance was measured as a function of temperature, 77° to 350°K,for niobium with hydrogen concentrations up to 3.76 at. pct. Cooling curves exhibited a discontinuity in slope that was attributed to the initiation of hydride formation. A thermal hysteresis was explained in terms of diffusion and the effects of mechanical constraint on nucleation and growth. The heat of solution of hydrogen in saturated Nb-H solid solution was 2. 737 * 0.045 kcal per g-atom, including an unknown stress contribution. The critical ternperatures for hydride formation during cooling and for embrittlement are correlated but not coincident. This, too, has been explained in terms of mechanical constraint and stress-itlduced tratzsfomtation. Nb-H alloys undergo a ductile-brittle transition with decreasing temperature.'-3 Similar behavior has been noted for v-H.1,5 For the latter system, there is evi-dence6 suggesting coincidence of the temperature of minimum ductility and the critical temperature T, for initiation of metal hydride precipitation during cooling. A decrease in ductility due to the presence of brittle hydride particles is readily explainable. The fact that ductility begins to decrease at some temperature higher than T,4,5 has led us6 to suggest that precipitation may be strain-induced locally during tensile testing. Wood and Daniels' have reported that a plot of temperatures for 10 pct reduction in ductility vs hydrogen concentration in niobium is not coincident with, but parallels, the solvus.7,8 They believe this indicates a correlation of precipitation and embrittlement. Unfortunately, the two reported solvuses 7,8 to which Wood and Daniels refer are not in agreement with each other. Furthermore, neither solvus was determined experimentally: each was a plot of calculated solubilities. Thus. neither is highly dependable for determining whether embrittlement coincides with initiation of hydride precipitation. Longson 9 studied phase relations in the Nb-H system between 77° and 473°K by dilatometry. Comparison with metallographic observations convinced him that discontinuities in the slopes of his dilatometric plots were coincident with the initiation of hydride precipitation. Plotting the logarithm of the hydrogen concentration vs the reciprocal of the temperature at which precipitation was initiated during cooling, he obtained a straight line shown in Fig. 1. Walter and chandler,'' using X-ray techniques to detect the for mation of a second phase? have obtained three experimental points in the temperature range 295° to 338°K which fall within Longson's experimental error for this plot. A similar plotg of temperatures at which dissolution was completed during heating was a parallel line shifted toward higher temperatures. A straight-line plot was obtained, also, for the temperatures of the ductile-brittle transitions,9 but it was shifted toward still higher temperatures. Longson calculated an activation energy of 2.980 * 0.300 kcal per mole for the hydrogen embrittlement mechanism, compared with 3.180 * 0.400 kcal per mole for hydride formation. Despite this agreement, he concluded, "It seems unlikely that embrittlement results from hydride formation..." because hydrogen embrittlement was observed at temperatures above the solvus. It is our contention that embrittlement is correlated with precipitation of the hydride.6 Because only Longson has investigated Nb-H phase relations at sub-ambient temperatures, we deemed it advisable to re-determine the temperature dependence of the solubility using the resistometric technique already proven successful for the V-H system.6 Coincidence of our solvus with temperatures for embrittlement would

Jan 1, 1970

By C. G. Dunn, F. W. Daniels

IN recent publications1-5 the existence and behavior of subgrain boundaries in high-purity metals has been clearly brought to light. Lacombe and Beaujardl by means of special etching methods disclosed in polycrystalline sheets of aluminum the existence of substructures differing in orientation by small amounts (about 1/4"). Boundaries of these structures at relatively high temperatures had the remarkable property' of moving about while the ordinary boundaries remained stationary. Cahn2 also observed substructures in bent and annealed single crystals of aluminum, zinc, magnesium, and rock salt. The position of subboundaries could be explained in terms of a dislocation mechanism of polygonization in which dislocations move into lines at right angles to the bent glide planes thereby relieving elastic stresses in these planes. Guinier and Tennevin8,6 disclosed the further interesting feature that polygonized structures coarsened significantly upon prolonged annealing. Somewhat similar subgrain phenomena have been observed in silicon iron of commercial purity. Although some evidence for the development of macro-mosaic structures in silicon iron already has been reported by one of the authors6,7 under the phenom-enological term "crystal recovery," much better evidence recently has been obtained due to improved etching techniques. In addition, phenomena regarding structural changes have been uncovered. The present investigation is divided into three parts: (1) The phenomenon of Laue spot sharpening on annealing cold-rolled crystals, (2) the phenomena of polygonization and subgrain coarsening The material used in the present investigation was high-grade commercial silicon iron sheet of nominal composition, 3.3 pct Si, 0.004 C, 0.011 P, 0.010 S, 0.04 Mn, 0.01 Al, 0.04 Cu, 0.01 Sn. Large single crystals of this material Were prepared for cold-rolling or bending as scheduled. Cold-rolling of 12 pct was carried out on a laboratory 8-in, diam rolling mill. The bending deformations were performed by pressing the crystals between a solid Fig. 2—lllustrative foue patterns to show Laue spot sharpening. a (Left)—Specimen as cold rolled, b (right)—After 48 hr at 1400°C. round bar and a mating half cylinder, both heavily greased. Individual specimens were cut from the deformed crystals, and the cut edges were deeply etched prior to annealing. Laue photographs were made using 40-kv tungsten radiation. The technique used to disclose the various subboundaries was an electropolish and electroetch in a bath of chrome-acetic acid.' The anodic polishing done at 22 v was immediately followed by etching at a reduced voltage, which was dependent upon the nature of the subboundaries. Phenomenon of Laue Spot Sharpening on Annealing Cold-Rolled Crystals Fig. 1 gives the initial and final orientations of the specimens cold-rolled 12 pct. Each specimen was annealed at a temperature and for a time which caused significant structural changes as evidenced by alterations in Laue patterns. Representative Laue patterns and micrographs showing the essential changes are given in Figs. 2, 3, and 4. The essential points to be derived from these illustrations follow: 1. Annealing at 950°C clearly develops a substructure with the orientation of the cold-rolled specimen. 2. The subboundaries formed obviously separate regions of nearly the same orientation. Some of the subboundaries appear as a sequence of dots similar to those observed in aluminum by Lacombe and Beaujard,' but whether this is due to extremely small differences in orientation is not known at present. 3. The substructure coarsens upon prolonged annealing. 4. Prolonged annealing also causes a decrease in orientation spread according to Laue spot sharpening'

Jan 1, 1952

By E. O. Wagner, V. F. Parry, J. B. Goodman

The low-rank coals containing 10 to 50 pct natural bed moisture represent over half of the tonnage reserve of the available solid fuels of the United States, but only about 2 pct of United States coal production is derived from these fuels. Increased utilization of these large reserves will result if the bed moisture can be removed at the mine in high-speed low-cost processes. This paper presents a theoretical and experimental study of the factors affecting high-speed drying of coal dusts. The time required to heat particles of coal is proportional to the square of their diameter, and it is calculated that the probable time in minutes is equal to 6D2. In other words, a 1/16 in. coal particle should be heated to drying temperature in 1.5 to 2.0 sec. Likewise, 1/8 in. particles should be heated in about 6 sec. The net heat required to dry subbituminous coal and lignite varies from 240 to 375 Btu per pound, depending upon the moisture removed, and this heat can be obtained from 42 to 61 cu ft of hot gases at 600°F. The necessary heat also can be obtained from 7.5 to 11 cu ft of gas at 2000°F. A description of the design and operation of a pilot plant for flash drying coal dusts is presented. This plant dries 1/16 in. by 0 coal dust in suspension in 1.5 to 2 sec with 600°F gas at a rate of 1300 lb per hour per square foot of column area and operates continuously at an efficiency of about 85 pct. The design and operation of another pilot plant for drying 1/8 in. by 0 coal dusts Is also described. This unit dries coal in the fluidized state using the sensible heat of gases introduced at 2000°F and processes coal at a rate of about 1500 Ib per hour per square foot of grate area at 85 to 90 pct efficiency. Over 90 pct of the bed moisture of low-rank coal dusts can be removed by the methods described. The heating value of lignite can be increased 45 pet and that if subbituminous coal 25 pct in a few seconds. The physical and chemical properties of coal dusts before and after drying are presented in the report, and it is shown that the bulk density of the dried coal is equal to that of the raw coal. This phenomenon makes it possible to ship 25 to 45 pct more heat in a railroad car with consequent savings in freight costs. Introduction For several years the Subbituminous Coal and Lignite Section of the Coal Branch of the Bureau of Mines at Golden, Colo., has been concerned with upgrading low-rank coals by removal of natural bed moisture. These fuels contain 10 to 50 pct total moisture, which reduces their industrial value considerably. In 1938, investigations were initiated in cooperation with the University of North Dakota to study drying of lignite by the Fleissner process with heat derived from high-pressure saturated steam. Two pilot plants were built, and two reports were published giving the results of this work.l,2 It was demonstrated that lump lignite and subbituminous coal

Jan 1, 1950

By David A. Sterling, Roger C. Malan

The Atomic Energy Commission is investigating the distribution of uranium and thorium in the Precambrian of the western United States and the relationship of time-space-facies patterns of uranium and thorium enrichment in the Precambrian, to the major resources of umanium in Mesozoic and Cenozoic continental clastic sediments. The results of preliminary studies in the southwestern. United States are summarized. Approximately 50% of the uranium resource of the Free World is in deposits of Precambrian age, principally in lower Proterozoic conglomerates in Canada and South Africa (Uranium Resources, Joint Report, ENEA and IAEA, 1967). Most of the uranium resource of the United States is in Mesozoic and Cenozoic continental clastic sedimentary rocks that fill intracratonic basins. The Atomic Energy Commission (AEC) is investigating the distribution of uranium and thorium in the Precambrian of the western United States and the relationship of time-space-facies patterns of uranium and thorium enrichment in the Precambrian to the major resources of uranium in the Mesozoic and Ce-nozoic host sedimentary rocks. This paper summarizes the results of preliminary studies of the Precambrian in the southwestern United States including New Mexico, Arizona, southern Nevada, and southern California (Fig. 1). The host rock provenances for the major uranium resources in epigenetic deposits of Mesozoic and Ce-nozoic age in the western United States were in areas of extensive Precambrian exposure along the eastern margin of the Phanerozoic geosynclinal belt (Fig. 2). Mesozoic continental clastic sediments in the Colorado Plateau contain about two-thirds of the uranium resource of the United States. These sediments formed from detritus derived from the Mogollon highland in the southwestern United States where the Precambrian was extensively exposed1-1 (Fig. 2). A genetic relationship may exist between this provenance and the major uranium deposits of the Colorado Plateau. The Pre- cambrian might be equally important in the genesis of uranium deposits whether the most important process in the formation of these deposits was the leaching of low-order intrinsic amounts of uranium from Precam-brian granite or from Mesozoic pyroclastics derived from syntexis of the Precambrian basement rocks.' Precambrian Geochronology of the Southwestern United States The Precambrian geochronology of the southwestern United States is in an early stage of systematic study. Until recently, the only basis of correlation was through inconclusive field relationships. However, with the increased use of isotopic age dating, new data are becoming available for correlating regional and local events. As yet, there is no undisputed evidence of ages greater than 1.8 billion years (by) old in the southwestern United States. However, most geologists who have studied the region agree that volcanism and marine sedimentation of predominately eugeosynclinal facies took place in a northeasterly trending geosyn-cline prior to 1.7 by."' Because of insufficient evidence for a pregeosynclinal continental crust, some researchers believe the geosyncline may have developed on oceanic crust.' However, sediments metamorphosed to 1.7 by-old felsic paragneisses in the Panamint Range, California," and southeastward into southern Nevada are believed to have had a nearby continental provenance. The three Precambrian disturbances that are recognized in the southwestern United States are 1.6 to 1.8 by, about 1.4 by, and about 1.1 by-old (Fig. 3). In addition to plutonism, these disturbances are characterized by predominately lower-grade metamorphism. In this report, lower-grade metamorphic rocks include argillite, phyllite, slate, mica schist, and gneiss with relic sedimentary textures. Higher-grade metamorphic rocks, in this report, are recrystallized beyond megascopic recognition of the original rock type. Principal

Jan 1, 1971

By J. B. Clark, A. S. Yue

The zone-melting technique can be adapted for the de-termination of the eutectic composition in complex metal systerrzs. The application of this method is demonstrated in a simple eutectic system, Mg-AE, in which the eutectic composition is known and in a complex ternary system, Mg-Al-Zn, in which the literature is uncertain as to the composition of the ternary eutectic. The advantages and limitations of this unique approach for the determirution of the eutectic composition are discussed. ThE eutectic composition in phase diagrams is usually determined by thermal analysis of a series of arbitarily selected alloy compositions. The temperatures of the liquidus and eutectic arrests for each alloy are plotted and the eutectic composition is estimated by extrapolation to the entectic temperature of the curve formed by the liquidus arrest temperatures for the series of alloys. Although this approach readily yields the eutectic temperatures, several dekrminations are needed to estimate the eutectic composition, even in a simple system. In a complex ternary system, a great many determinations are often necessary to estimate, even approximately, the ternary eutectic composition. Thus, the conventional method is inherently tedious and time consuming. The application of zone melting provides a relatively efficient method of determining the eutectic composition.' As an illustration, consider the zone melting of an alloy composition C, in the simple eutectic system A-B, shown in Fig. 1, under the ideal conditions of infinitely rapid diffusion in the liquid, no diffusion in the solid, and ease of nucleation of both phases. As the zone moves along the bar, the composition of the zone is enriched by solute rejected during the freezing of the a phase and the zone composition approaches the eutectic composition CE.Once the zone composition attains the lowest melting composition, i.e., the eutectic composition, it remains at this composition as the zone moves along the bar and finally freezes as such at the end of the bar. Chemical analysis of the end of such a zone-melted bar then should yield the eutectic composition CE of the system A-B. A corresponding analysis can be made for a ternary eutectic system. Under the ideal conditions noted above, only one pass of the molten zone is required to yield the eutectic composition. Experimentally, however, a solute-rich layer forms at the solid-liquid interface2 and the composition of the zone does not attain the eutectic composition as rapidly or as uniformly as in the ideal case outlined above. But with agitation of the melt, the ideal conditions can be approximated experimentally. Also, as shown below, zone melting permits a cumulative build-up of the solute at the end of the bar to the eutectic composition. The purpose of this paper is to demonstrate this unique method for determining the eutectic composition. The method is here applied to two systems: first, to the binary Mg-A1 system, in which the composition is well established, and second, to the complex Mg-Al-Zn system in which there is doubt concerning the composition of the ternary eutectic. EXPERIMENTAL PROCEDURE The zone-melting apparatus used in this study is described in detail elsewhere.3 Briefly, the binary alloy rods (5/8 in. in diam and 9 in. long) and the ternary alloy rods (5/8 in. in diam and 6 in. long), with the compositions given in Table I, were zone

Jan 1, 1962

By P. Shahinian, R. L. Stegman, M. R. Achter

Creep strength has been determined as a function of oxygen pressure for nickel at 510" and 600°C. Creep-rupture life drops from its highest value at the ultimate vacuum of 10-7 torr to a high pressure plateau of nearly constant life which, at 600°C, commences at torr. This behavior is described in terms of a model that relates surface gas adsorption and the generation of fresh crack surfaces. In a calculation based a this model the predicted pressure beyond which the creep strength should not decrease further has been found to agree well with the observed value. The introduction of oxygen during creep in vacuum was found to cause a prompt rise of the creep rate. The magnitude of the environmental effect was much less than generally observed in fatigue and this is attributed to the diffarent crack morphologies in creep and fatigue. GASEOUS environments are known to affect creep resistance adversely1-5 but the effects have received less attention than the much larger ones in fatigue. At low temperatures it has been shown for nickel that the creep rates are faster and the rupture lives are shorter in air than in vacuum and that these environmental effects can be correlated with faster crack growth rates in the reactive environment.' In support of a mechanism of gas adsorption at the crack tip to explain the above effects, a calculation based on kinetic gas theory showed that surface coverage by gas was not as rapid as the exposure of fresh metal at the crack tip in the ultimate vacuum but was in air.7 In fatigue a number of investigations have demonstrated that the reduction of life with gas pressure usually follows a step curve with most of the reduction occurring in a transition range at intermediate pressures and little or no change at high and low pressure.8 There have been no studies, however, in which creep strength has been determined as a function of reactive gas pressure to see whether similar effects would be found. This investigation was undertaken to study the kinetics of the environmental effect in the creep of nickel. EXPERIMENTAL PROCEDURES The environmental creep apparatus was constructed to minimize many of the experimental conditions which can cause scatter in data. Dead weight loading is employed and weights are contained within the environmental chamber to eliminate bellows and the necessity for compensation for gas pressure changes. Elongation over the specimen gage length is recorded from a Riehle Model DV Controlled Environment Extensometer which provides readout to 2.5 x 10- in. Temperature is monitored and controlled from a thermocouple at- tached to the specimen gage length to +0.5oC or better. The freon trapped oil diffusion pump vacuum system included an auxiliary liquid nitrogen trap and, with a wide range variable conductance leak valve, pressures from the ultimate vacuum of 10"7 to l03 torr of any desired gas are obtainable. Pressure is measured by means of a hot filament ionization gage below 10"3 torr and a NRC Model 530 Alphatron Vacuum Gauge above 10-3 torr. The oxygen, which was leaked into the environmental chamber, was an Aviator's Grade of 99.5 pct purity with a dew point of -80°F. Analysis of the nominal 99.8 pct Ni showed the following percentages of major impurities: 0.02 C, 4.01 Mn, 0.005 Si, 0.01 Cu, 0.02 Fe, and 0.034 Mg. Cylindrical specimens were machined with a 0.180

Jan 1, 1970

By R. D. Nelson, F. E. Bowman

Evidence has been found for a (010)a?(111)B[102]a /,11[341]/B crystallographic relationship between the monoclinic a and B phases of plutonium during the a?B transformation. The results of an X-ray diffraction study, where [010] fiber textured a samples were used in the absence of suitable single crystals indicate that the (OIO)a planes become (111)B planes upon transformation under near-equilibrium conditions. The transformation strain along the fiber axis, which was the [010] direction, was measured dila-tomekically; the measured 8.5 pct expansion compares favorably with the 8.44 pct expansion in the in-terplanar spacing represented by the (010)a?(111)B relationship. From plots of the atom positions in each of the related planes, a correspondence was deduced between the [102]a, direction and the [341]B direction. Further analysis of the two lattice structures in the light of this relationship revealed a rotation about the [102] direction of 1 deg 43 min and a slight shearing in this same direction of about 30 min. THIS paper discusses the (B crystal structure of plutonium and the orientation relationship existing between the monoclinic a and B phases during the a?ß transformation. The kinetics of the a?ß and (3 — a transformations have received extensive consideration, and because of the crystallographic complexity of these phases, the question of the mechanisms by which these transformations occur is especially intriguing. Nelson and Shyne1 evaluated the existing experimental evidence and concluded, from the indirect evidence available, that both the ß ? a and a ? ß transformations occur by a martensitic process. Their data reveal the anisotropic nature of these transformations which suggests the existence of specific crystallographic relationships between the parent and product phases. In this paper, we are concerned with the confirmation of the existence of such a relationship resulting from the a ? ß transformation and the derivation of the crystallographic details necessary to specify it. EXPERIMENTAL RESULTS X-ray diffraction and dilatometric data were obtained from samples of a plutonium having a [010] fiber texture. These cylindrical specimens, approximately 1 cm in diam, were prepared by transforming the ß phase to a under the influence of a uniaxially applied compressive load.' The [0l0] direction is parallel to the direction of applied stress; it is also perpendicular to the (010) planes. This correspondence between the plane normal and the direction having the same indices is, in the monoclinic a plutonium structure, restricted solely to this (010)[010] combination. Such a specimen was mounted in an evacuated, elevated temperature specimen holder on an X-ray dif-fractometer so that the diffracting surface was perpendicular to the fiber axis. The a diffraction pattern, Fig. 1, taken at about 115ºC, revealed the predominance of the (020) reflection. This monoclinic, P 21/rn space group yields no (0k0) reflections when k is odd. The temperature was raised slowly to 160°C to effect the complete transformation to the phase; then it was lowered to 120°C so that a diffraction pattern of the ß could be obtained near the a = ß equilibrium temperature for direct comparison with the a at the same temperature. The (3 diffraction pattern, Fig. 2, obtained under these conditions showed a (222) reflection relatively much more intense than in the random pattern. The other reflections appearing with sig-

Jan 1, 1970

By W. A. Rachinger, C. Graeme-Barber, R. L. Bell, R. C. Gifkins, T. G. Langdon

R. L. Bell. C. Graeme-Barber, and T. G. Langdon (Imperial College. London)— The internal-marker technique developed by Ishida, Mullendore, and Grant has enabled them to make some interesting observations on the role of grain boundary sliding in creep. Certain of their conclusions are supported by our own similar experiments on Magnox AL80 (Mg-0.8 pct Al) specimens containing several markers, full details of which will be published shortly. In particular, we would agree that: 1) Using the internal-marker method, there is little difference between Egb, the contribution made by grain boundary sliding to the total strain, measured at the surface and in the interior of a specimen. 2) The measurement of the change in grain shape during creep leads to an underestimation of the grain strain, and hence an overestimate of Egb.. However, the discrepancies between the values obtained by this method and those obtained using markers are not as great as Tables IV and V of Ishida, Mullendore, and Grant would suggest; see below. The authors' Eq. [I] which is used to compute Egb from the transverse displacement ITt of longitudinal marker lines is not given in the reference quoted,'' where in fact only relations for Egb in terms of the longitudinal displacements of markers were developed. As first pointed out by Gifkins and Gittins,12 a problem arises in the use of longitudinal markers. and we will show that Eq. [1] underestimates Egb in the interior by a factor of 2. In Fig. 12, two grains X and Y have become displaced by the vector AC which lies in the plane of the grain boundary ABCD separating them. A longitudinal marker has been split by this displacement into the two parts LA and CAW. If these were surface grains the transverse displacement, Ut. could be obtained by viewing normal to the "top" surface. If interior, a section through CD parallel to the top surface would show the same result, provided the longitudinal internal markers delineated planes normal to the top surface. (This is an essential feature of the markers not pointed out in the paper.) The important point is that the quantity Ut tan B (=BE=DF) only gives the elongation due to the one component AB of the sliding. The elongation V/tan 8 (=GD) due to the component AD must be added to produce the total elongation resulting from the boundary displacement AC. If the grain boundaries in a poly crystalline specimen are randomly oriented with respect to the stress axis it follows that In the interior of a specimen the two sums depend for any difference simply on the definitions "top'' and "side". On the surface it is possible that the two sums could differ somewhat. In either event it is clear that the authors' Eq. [I] underestimates Egb, and in the interior, and perhaps at the surface also, the appropriate formula is given by The suggested modification probably makes little difference to the comparison between surface and interior values of Egb where both were obtained from marker measurements. For the estimation of the correction becomes extremely important where the boundary contribution is large. In our own work on magnox, for example, we have obtained values of as large as 70 to 80 pct, under conditions of high temperature and low strain rate. The use of planar markers transverse to the stress axis would simplify the comparison between surface and interior behavior, because measurement of the longitudinal offsets Us of these markers could be summed to give the total elongation di-

Jan 1, 1965

By A. W. Bethune, L. M. Pidgeon

The equilibrium vapor pressure of zinc has been determined over the systems: ZnS(s) + Fe(s) = FeS(s) + Zn (vapor) and ZnS(s) + 2Cu(s) = Cu2S(s) + Zn (vapor) by reacting the components in an evacuated tube containing a thin copper fiber, and allowing equilibrium to be established with respect to the brass formed and the zinc in the vapor phase. The composition of the brass formed was determined and equilibrium vapor pressure values obtained from existing data. Between 850' and 1000°C, values for the first reaction ranged from 8 to 58 mm Hg; for the second reaction from 1.8 to 22 mm Hg. THE direct reduction of metallic sulphides may be indicated by an equation of the form MS + X = XS + M [1] where X is some suitable reducing agent. In the case where M is a metal of relatively high volatility, the use of vacuum will displace the equilibrium to the right at comparatively low temperatures in the face of the usually unfavorable thermochemistry. For this technique to be feasible, MS, X, and XS, must of course be nonvolatile compared to M. In this regard, zinc becomes an obvious metal both from the point of view of its volatility and the fact that most commercial ore deposits of this metal occur as the sulphide, and its direct reduction would avoid the expensive roasting process necessary prior to present day reduction methods. Two reducing agents are of interest, namely copper and iron, with the former having the added attraction of being relatively easily regenerated by oxidation in the copper converter. The possibility of these reactions has been considered before. Imbert1 patented a process whereby zinc sulphide was reduced by either copper or iron. The process as described took place at atmospheric pressure and, at the high temperatures required, the system was molten, resulting in the formation of a matte with the consequent reduction in the activities of the reactants. Peterson2 did further experimental work on these reactions and, although promising results were obtained on a small scale, attempts to increase the size of the furnace led to excessive "blue powder" formation. The early workers failed to realize the large reduction in temperature afforded by the use of vacuum and its desirable results. More recently, the direct reduction of zinc sulphide by iron has been the subject of a thermody-namic investigation by Kelley,3 and Gross and War-rington' have studied the kinetics of the reaction in the temperature range 900" to 1000°C, their experiments being conducted using vacuum and indicating that the reaction would proceed practically to completion in 1 to 3 hr, depending on the temperature. A qualitative examination of the system ZnS-Cu carried out at this University indicated that 98 pct of the theoretical zinc in the charge could be recovered in 1 hr at 1000°C when operating under reduced pressure. The purpose of this research program was to study the equilibrium of the two reactions. During the investigation, reference to the experimental work of Schenk5 was found but, due to lack of detail in the report, it was felt that it would be desirable to continue the equilibrium measurements. Selection of Method The measurement of vapor pressure of metals presents obvious problems resulting from the high temperatures which must be employed. In the present case, the production of the "reaction pressure" introduces a further difficulty since a chemical reaction must proceed before any metal vapor pressure is produced, resulting in depletion of the re-

Jan 1, 1954

By P. E. Schauer

During the initial nine-year deple-tion of the McKamie-Patton pool gas-condensate reservoir, the pressure behavior and fluid analyses indicated pressure maintenance by gas injection would be attractive relative to continued pressure depletion. As a result, a gas cycling program was inaugurated in Aug., 1949, which has since maintained reservoir pressure. In order to evaluate the benefits of this program, the recoveries for natural depletion and for cycling followed by blowdown were determined by calculating the fractional balance of the molar quantities of vapor and liquid remaining in the reservoir and produced at the surface for various stages of depletion. The results of the investigation show theoretical ultimate recovery due to the cycling program will be 42 per cent greater than would be realized under pressure depletion type operation. INTRODUCTION The benefits of gas injection pressure maintenance programs in condensate reservoirs have been recognized and qualitatively described in several papers1-8 during the past 15 years. Some of these papers also describe methods for calculating the increased recovery realized from cycling; however, as a rule, hypothetical reservoirs were used as examples".'.. This paper presents an evaluation of the pressure maintenance program for the McKamie-Patton condensate reservoir and includes a description of the fractional balance method employed to determine the benefits. Reservoir Development and Characteristics The McKamie-Patton pool, Lafayette County, Ark., was opened in June, 1940, with production obtained from the oolitic Smackover lime at a depth of approximately 9,300 ft. The structure is an anticline 8 miles long by 1 to 2 miles wide, and is one of many productive Smackover structures in Southern Arkansas. Of predominant importance is the condensate-bearing gas cap portion of the reservoir, which covers approximately 4,000 acres, attains a maximum thickness of some 200 ft, and has an average thickness of 90 ft. Development of the cap was accomplished with 21 wells drilled on 160 acre spacing. An isopach map of the cap is shown in Fig. 1. In addition, an oil rim is present along most of the periphery of the pool. Production practice includes field separation of black oil, and a high pressure gathering system which carries total well stream from gas cap wells to a plant where condensate is separated and the gas is processed for recovery of natural gasoline, butane, and propane. Since the gas contains appreciable hydrogen sulfide, it is removed by amine contact, after which free sulfur is produced by the Claus process. Core analyses from 1,767 gas cap formation samples averaged 14.2 per cent porosity and 379 md dry air permeability. Connate water was restored on seven samples of gas cap rock by air-brine capillary techniques, from which the interpreted water saturation averaged 28.17 per cent. During the early life of the field, it was believed the recovery mechanism, based on several of the other regional Smackover reservoirs, might be a natural water drive. However, subsequent production and pressure history revealed that the gas cap would not be produced by water drive, but would behave as a closed reservoir. In this respect, during the nine-year period of natural depletion from initial production to Aug., 1949, the cap production of 84.3 billion

Jan 1, 1958

By Paul A. Beck, John Towers, W. D. Manly

Recent work on grain growth in high purity aluminum and in a solid solution type alloy of aluminum and magnesium1 showed that the isothermal increase of the average grain diameter D with time follows the equation D = K(tg + A)2 Eq 1 Here tg is that portion of the total annealing time 1, which is available for grain growth, that is the annealing time less the time necessary for complete recrystallization. The parameters A and n depend only on the temperature. A has the dimension of time, and is usually of the same order of magnitude as the time for recrystallization: R. In some instances R may be substituted for A in Eq I. This is the case for example at long periods of annealing or at high temperatures, where both A and R become small in comparison with t. In such instances Eq I is simplified to D = K, tn Eq 2 For high purity aluminum the exponent n increases in the ratio of about I to 5 in. the temperature range of 350' to 6w°C. 70-30 brass has been long known to exhibit grain growth of the continuous type, such as occurs in pure metals. For this reason, it was of interest to determine whether grain growth in brass also follows Eq I and 2 as it does in aluminum. Isotherma1 grain growth data for 70-30 brass were published in recent years by R. S. French2 and by H. L. Walker.' Fig I shows a log D vs. log t plot of French's data, together with the 500, 600 and 700°C data by Walker for 42.8 pct reduction by rolling. In such a log D vs. log t plot Eq 2 corresponds to a straight line with a slope of n. As seen in Fig I, the data of French and the 600°C data of Walker can be represented by straight lines. However, the 500 and 7c0°C data of Walker give curved lines and the average slope of his 500°C line is very different from the slope of the line representing French's data for the same temperature. Furthermore the curvature of the 700°C line suggests a tendency for grain growth to stop after 8 hr. If confirmed, this would constitute a definite deviation from Eq 2, not explainable on the basis of the specimen thickness effect found in high purity aluminum.' Walker's specimens were 0.125 in., or 3.18 mm thick, while the deviation occurs at a grain size of approximately 0.4 mm. A further point of divergence arose recently, when J. E. Burke suggested4 on the basis of Walker's data, that, instead of Eq 2, grain growth in 70-30 brass follows the equation D - D, = K . tgn Eq 3 Here D, is the grain size as recrystallized at the temperature in question. Although it was possible to show5 that, for pure aluminum, for which isothermal grain growth has been carefully investigated, Eq 3 is incompatible with the experimental facts, the situation remained somewhat obscure with respect to 70-30 brass. In view of the discrepancies between the published data on brass from different

Jan 1, 1949

By John Towers, Paul A. Beck, W. D. Manly

Recent work on grain growth in high purity aluminum and in a solid solution type alloy of aluminum and magnesium1 showed that the isothermal increase of the average grain diameter D with time follows the equation D = K(tg + A)2 Eq 1 Here tg is that portion of the total annealing time 1, which is available for grain growth, that is the annealing time less the time necessary for complete recrystallization. The parameters A and n depend only on the temperature. A has the dimension of time, and is usually of the same order of magnitude as the time for recrystallization: R. In some instances R may be substituted for A in Eq I. This is the case for example at long periods of annealing or at high temperatures, where both A and R become small in comparison with t. In such instances Eq I is simplified to D = K, tn Eq 2 For high purity aluminum the exponent n increases in the ratio of about I to 5 in. the temperature range of 350' to 6w°C. 70-30 brass has been long known to exhibit grain growth of the continuous type, such as occurs in pure metals. For this reason, it was of interest to determine whether grain growth in brass also follows Eq I and 2 as it does in aluminum. Isotherma1 grain growth data for 70-30 brass were published in recent years by R. S. French2 and by H. L. Walker.' Fig I shows a log D vs. log t plot of French's data, together with the 500, 600 and 700°C data by Walker for 42.8 pct reduction by rolling. In such a log D vs. log t plot Eq 2 corresponds to a straight line with a slope of n. As seen in Fig I, the data of French and the 600°C data of Walker can be represented by straight lines. However, the 500 and 7c0°C data of Walker give curved lines and the average slope of his 500°C line is very different from the slope of the line representing French's data for the same temperature. Furthermore the curvature of the 700°C line suggests a tendency for grain growth to stop after 8 hr. If confirmed, this would constitute a definite deviation from Eq 2, not explainable on the basis of the specimen thickness effect found in high purity aluminum.' Walker's specimens were 0.125 in., or 3.18 mm thick, while the deviation occurs at a grain size of approximately 0.4 mm. A further point of divergence arose recently, when J. E. Burke suggested4 on the basis of Walker's data, that, instead of Eq 2, grain growth in 70-30 brass follows the equation D - D, = K . tgn Eq 3 Here D, is the grain size as recrystallized at the temperature in question. Although it was possible to show5 that, for pure aluminum, for which isothermal grain growth has been carefully investigated, Eq 3 is incompatible with the experimental facts, the situation remained somewhat obscure with respect to 70-30 brass. In view of the discrepancies between the published data on brass from different

Jan 1, 1949

By Thomas L. Kesler

Present Raw Materials The lithium industry has had exceptional growth since publication of the last edition of this volume, and the present scale of mining and consumption of raw materials is a great many times that of 1949. The materials of present economic importance consist of four pegmatite minerals and lithium-bearing brine. Spodumene, a lithium pyroxene, occurs in greatest abundance, and is the chief source. It has the formula LiAlSi2O6 and theoretically may contain 8.03 pct Li2O, but in the more important deposits the content is 6.5 to 7.5 pct. The hardness is 6.5, the specific gravity 3.1 to 3.2, and the color mostly pale green to white although deep green, lilac, and yellow varieties exist. The crystals are prisms with strongly developed longitudinal cleavages, and crushing characteristically produces lath-shaped particles. Giant crystals up to 47 ft long are known, but in most occurrences the predominant size range is 0.5 to 12 in. long and 0.1 to 2 in. wide. Hypogene* alteration has formed lithia-bearing sericite and coarser muscovite and rarely eucryptite, while supergene* alteration yields kaolinite and hydrous mica. Lepidolite, of second importance, is a mica of varying composition approximating K2Li3-A14Si7O21(OH,F)3. It has lamellate cleavage, book structure, and a specific gravity of 2.8 to 3. The books range in size from microscopic to a diameter of several inches. The color is mostly violet, but other colors include pink, gray, yellow, and white. Most commercial lepidolite contains 3 to 4 pct Li20 and chemically is in the higher grade range of a series of lithium micas that includes polylithionite, zinnwaldite, and protolithionite. In this series, the content of Li2O is exceptionally as high as 7 pct. Petalite and amblygonite are also of economic importance, but are used in smaller amounts. Petalite has the formula LiA1Si4O10 and is white, gray, or pink. The hardness is 6, the specific gravity 2.4, the cleavage in two planes 114° apart, and the Li2O content commonly 3 to 4.7 pct with a maximum of 4.88. Amblygonite has the formula LiA1FPO4 in which OH may substitute for F to form montebrasite. It is white and has polysynthetic twinning in two directions at 90°. Amblygonite superficially resembles potash feldspar, but has a bluish or grayish tint unlike the cream or salmon tint of the feldspar.[t] The hardness is 6 and the specific gravity 3 to 3.1, and the content of Li2O is the highest among lithium minerals that occur in significant quantity, ranging mostly from 7.5 to 9 pct with a maximum of 10.2. The brine of Searles Lake in California30 has been a commercial source of lithium since 1938. See Chap. 7, p. 108. The "lake" is a saline evaporite deposit, and the exposed part has an area of 12 sq mi. To an average depth of 71 ft, this part of the deposit consists of crystalline salts with 50 pct interstitial voids. The voids are filled with brine that contains mainly sodium and potassium compounds, but the brine also contains 0.015 pct Li2O, which is recovered as dilithium sodium phosphate containing 21 pct Li20. This deposit overlies a

Jan 1, 1960

By J. A. Bowers

THIS investigation of the effect of bottom shape and life on slag volume was carried out in two Lectromelt top-charge furnaces whose rated capacity is 1000 lb per hour. Unfortunately, just as the work [ ] was started, our steel tonnage was reduced approximately one half, therefore we did not accumulate enough data from which to draw any definite conclusions. Furthermore, the life of the linings in these furnaces was greatly decreased by intermittent operation, which was a further handicap in making a study of this kind. The weight of the heats from which the data were taken varied 1200 lb but all the information was corrected to the standard weight charge for these furnaces of 4500 lb. Almost all the heats were plain carbon; a few contained a small percentage of added copper.

Jan 1, 1947

By John F. Havard, Armine F. Banfield

Sooner or later, we all get involved in the economic study and valuation of a mineral deposit. To communicate clearly the necessary information, we must scrupulously use various terms with specific meaning. All these terms-such as ore, exploration, development, production, reserves, proven ore, probable ore, possible reserves, resources, as well as similar terms applying to coal-are continually on the lips of anyone who reports on the economic aspects of a mineral deposit at the exploration, development, and production stages. The meaning of these terms is even more important in feasibility studies to determine whether a deposit should be put into production. Finally, careless use of these terms in reports published for public financing may, and sometimes does, lead to prosecution of the writer for misleading information.

Jan 7, 1975