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By E. T. Turkdogan, W. L. Worrell

The rate of reaction of hydrogen sulfide with ferrous sulfide was studied by measuring the initial rates of sulfidation of iron strips in hydrogen sulfide-hydrogen-argon mixtures at 670°, 800°, and 900" C. The time-dependent surface sulfur activity is derived from the instantaneous rate of sulfidation with the assumption that diffusion in the sulfide layer is in a pseudo-steady state with the gas-sulfide chemical reaction. The rate of sulfur transfer from hydrogen sulfide to the surface of iron sulfide is proportional to the partial pressure of hydrogen sulfide and inversely proportional to the activity of sulfur at the surface of the sulfide layer. The derived rate equation is based on the assumption that most of the surface sites on the chemisorbed layer of iron sulfide are occupied by sulfur atoms and that the slow rate-controlling reaction is the dissociation of hydrogen sulfide on the chemisorbed layer. The experimental results are in reasonable accord with this reaction model. 1 HE slow approach to parabolic growth rate in the sulfidation of iron in hydrogen sulfide-hydrogen mixtures is a manifestation of slow approach to surface equilibrium between the gas and the surface of the sulfide layer. For example, at 800°C and Fig. 7 in Part I, the parabolic growth rate begins after approximately 1 day of sulfidation time. With decreasing temperature and decreasing partial pressure of hydrogen sulfide, the time necessary to reach gas-sulfide surface equilibrium is much longer. These observations are similar to those reported previously by Turkdogan et al.' on the oxidation of iron to wustite in hydrogen-water vapor mixtures. The slow approach to gas-sulfide equilibrium is well-demonstrated by the results in Fig. 1 where the square of the weight gain per unit area, ( g S per sq cmI2, is plotted against time for gas mixtures having PH g//>H = 1.0 with 0, 25, 50, and 67 pct Ar at 800°C. The value of 1.5 X lo-' (g S per sq cm)' corresponds to almost complete sulfidation of the iron strip (- 0.05 cm thick) to iron sulfide. The points fall on S-shaped curves. If the inflection parts of the curves are considered to be linear, thus indicating parabolic growth rate and the establishment of gas-sulfide equilibrium, their slopes would have to be the same for a fixed ratio in the gas mixture. Such is not the case, and the slopes for the "linear" parts of the S-shaped curves are lower than the value when gas-sulfide surface equilibrium is established. The subject matter of this paper is the kinetics of the surface reaction of hydrogen sulfide with iron sulfide during the early stages of sulfidation of an iron strip. EXPERIMENTAL RESULTS The apparatus and materials used were the same as those discussed in Part I. In the present experiments of relatively short duration, a purified iron strip, 5 by 2 by 0.05 cm, which was suspended in the uniform hot zone of a vertical zircon tube, reacted with a flowing gas mixture of hydrogen sulfide-hydrogen-argon. The sample was suspended from a gold chain attached to a calibrated silica spring. The amount of sulfur picked up by the iron, which formed a layer of iron sulfide, was determined by measuring the displacement of a reference point on the silica spring, using a cathetom-eter. In all cases, the degreased sample was first annealed in a stream of oxygen-free dry hydrogen for several hours to remove any impurities such as oxygen, nitrogen, or carbon which might have been present on the surface of the sample.' The rate measurements were carried out at 670°, 800°, and 900° C in hydrogen sulfide-hydrogen-argon mixtures with pH2 s/Ph2 ratios from 4 to 0.1. In a few experiments of short duration no sulfur deposition was observed in gas mixtures with (comments concerning sulfur deposition at high pH s/ph ratios were made in Part I.) Typical examples of the results obtained are shown in Fig. 2 for two temperatures and two gas compositions. With the present experimental technique, reproducible rate data could be obtained only after a uniform

Jan 1, 1969

By F. W. Jr. Sperr

THE byproduct coke oven is the most important artificial source of fuels for metals melting. Its products are solid, liquid, and gaseous in form. The amount of coke and primary byproducts obtained per ton of coal varies with the nature of the coal. The following represents the results obtained in many plants: Metallurgical coke (over 3/4 in.) 69 per cent. of coal Domestic coke (1/2 to 3/4 in.) 2 per cent. of coal Breeze (under 1/2 in.) 4 per cent. of coal Surplus gas, cubic feet per net ton 6600 Gas for heating ovens, cubic feet per net ton 4400 Tar, gallons per net ton 9 Ammonium sulfate, pounds per net ton 25 Benzols, gallons per net ton 4 All of these products, except ammonium sulfate, have important fuel value. Part or all of the metallurgical coke may be crushed or screened to furnish additional domestic coke. If producer gas is used, there will be a surplus of 11,000 cu. ft. of coke-oven gas per net ton of coal. The use of coke in the metallurgical industries has been retarded by the mental attitude of writers who disregard the dependence of coke quality on the conditions of its manufacture. Terms like "byproduct coke,"' "beehive coke," "48-hour coke," and "72-hour coke" are only generally descriptive and tell nothing of the coke quality. For example, one writer1 stated that in brass-foundry practice, Connellsville coke is considered much superior to byproduct coke on account of the high sulfur content of the latter. Another2 says, "At equal prices for hard Connellsville coke and for byproduct coke at the foundry door, the hard coke is unquestionably cheaper. It will melt more metal per ton than the byproduct coke and requires less labor, as the byproduct coke is less dense and burns faster, thus requiring more frequent firing." A little study of the conditions under which coke is manufactured will show the error in mak-

Jan 10, 1920

By J. S. Kasper, R. M. Waterstrat, B. F. Decker

THE large difference in the X-ray scattering factors for molybdenum and manganese makes the o- phase in the Mn-Mo system an interesting one to study with respect to ordering of the atoms. Such a study has been carried out using data obtained from a powder sample, and the resulting evidence for ordering in this compound is presented here. It is not possible, of course, to obtain all the details of structure for a u phase from powder data only. Most difficult of all would be the determination of precise atomic parameters. There is reason to believe, however, that the atomic parameters do not vary greatly in the different s'S and that the precise values obtained from one s structure would then allow decisions as to the ordering of atoms to be made when there is a large difference in scattering factors. In particular, the powder intensities for Mn-Mo s are for the most part in good agreement with those observed for Co-Cr, for which single crystal studies have been made by the authors.' There are a few marked discrepancies in the intensity comparison of the two s's, and these cannot be removed by adjustment of the parameters. They are interpreted as resulting from a more pronounced effect of ordering of the atoms. Accordingly, the parameters of Co-Cr s' have been used for the calculations of the Mn-Mo intensities. For Co-Cr, the space group is D4h14-P4/mnm with atoms in the following positions: 1—2 in (b); 11—4 in (f), with x=0.1031; 111—8 in (i), with x= 0.3713 and y=0.0370; IV—8 in (i), with x=0.5662 and y=0.2396; and V—8 in (j), with x=0.3160Y and y — -0.250. The unit cell is tetragonal, with an==9.10A and cn=4.74A for the Mn-Mo u phase studied here.

Jan 1, 1955

By F. Weinberg

The relative concentration of 1" at grain boundaries in controlled orientation bicrystals has been examined by autoradiographic techniques, and by activity measurements of grain boundary surfaces exposed by preferential ,melting. The autoradio-graphs indicate that thallium is concentrated at grain boundaries in as-grown bicrystals, but not in zcell-annealed bicrystals. They also indicate that the solute concentration and the distribution on as-grown bicrystal surfaces are markedly different than that of the bulk material. The boundary surface measurements are in agreement with the autovadiographic evidence. On the basis of these measurements, as-grown bicrystals containing approximately 100 ppm of Tl, solidified at rates between 5 and 30 cm per hr and with tilt boundaries greater than 10 deg, exhibited grain boundary segregation equivalent to roughly 10 atomic planes of pure solute. Higher solute concentrations (equivalent to 140 atomic planes of pure solute) were obtained in bicrystals solidified slowly (0.6 cm per hr); slightly higher values were obtained in specimens containing a large angle nantilt boundary. Annealing for various times over a range of temperatures eliminated grain boundary segregation within the experimental uncertainty of the results (equivalent to 1 atomic Plane of pure thallium at the boundary). The results for the as-grown bicrystals can be qualitatively accounted for by assuming the presence of a groove on the solid-1iq;id interface, at the grain boundary. SOLUTE segregation at grain boundaries may be considered in two parts, namely, nonequilibrium segregation associated with the solidification process, and equilibrium segregation in fully annealed materials.' There is much indirect evidence for nonequilibrium segregation, based on preferential etching at grain boundaries and the mechanical properties of as-cast alloys. In addition, some direct observations have been reported in which radioactive tracers were used as solute additions and segregation detected at the grain boundaries by autoradiographic techniques. However, there is little detailed quantitative data on solute concentrations related to grain boundaries, particularly for different freezing conditions and grain boundary configurations. Equilibrium segregation at grain boundaries has been considered both theoretically and experimentally. cean' has made an estimate of the maximum equilibrium solute concentration that might be expected at a grain boundary, based on the lattice distortions in the boundary region. He arrived at a concentration which was equivalent t a monatomic layer of pure solute. A similar value, based on thermodynamic arguments, was calculated by Cahn and Hilliard for the segregation of phosphorus in iron. Experimentally, much higher values of solute concentration at grain boundaries have been reported recently by both Inman and iler' for phosphorus in iron, and Ainslie et 1.' for sulfur in iron. They observed concentrations equivalent to as much as 20 to 100 atomic layers of pure solute at the grain boundaries. However, in both cases it was shown that the observed segregation was not due solely to equilibrium segregation at the grain boundary. In the former case, precipitation effectss due to trace impurities in the material were believed to account for the large amount of solute present at the grain boundary. In the latter case it was shown that a high density of dislocations in the boundary region could provide a large number of additional sites for solute atoms, other than at the grain boundary. Thomas and chalmera have reported on the equilibrium segregation of po210 in grain boundaries of Pb-5 pct Bi alloys. Using autoradiographic techniques, they observed a concentration of polonium along the boundary trace on the surface of annealed bicrystal specimens grown from the melt. The concentration only appeared after annealing, and varied with boundary angle, increasing as the boundary angle increased. Their conclusions have been questioned by Ward," who pointed out that the segregation they observed along the boundary trace was much too wide to be compatible with the usual concepts of the thickness of a grain boundary of several lattice spacings. Also, Maroun et al.,l1 with specimens similar to those of Thomas and Chalmers, found that segregation could only be detected on the specimen surface, suggesting that Thomas and Chalmers' results were associated with an oxidation effect of polonium, and not equilibrium segregation. Thomas and Chalmers replied12 that they did observed segregation at the grain boundary in the bulk material and suggested further experiments were necessary to resolve the difference. The purpose of the present investigation was to examine both nonequilibrium and equilibrium grain boundary segregation in melt grown bicrystal specimens as a function of boundary angle, growth rate, and solute concentration, and to de-

Jan 1, 1963

By Charles E. Weaver

Discussion of the paper of CHARLES E. WEAVER, presented at the San Francisco meeting, September, 1915, and printed in Bulletin No. 103, July, 1915, pp. 1419 to 1427. MILNOR ROBERT, Seattle, Wash.-A year ago at this time, 12 wells were being drilled for oil in western Washington. Some excitement attended the operations; many thousand acres of land were leased to oil companies and stock was widely advertised. The location of the wells may be described by referring to the conclusions in Dr. Weaver's paper, in which the State is divided into four areas. In the area described first, which includes the Cascade Mountains and eastern Washington, where conditions are decidedly against the existence of commercial oil fields, no new drilling was reported. In the second area, the Puget Sound Basin, where conditions are unfavorable, but to a less degree, five wells were being drilled. The third region, covering certain parts of southwestern Washington, contained four drilling wells and several others projected or beginning operations, in spite of the absence of petroleum seepages. None of the wells mentioned is fully active today. On the western side of the Olympic Peninsula, along the Pacific Ocean, are three wells which have been the scene of operations for the past two to three years. The region they are prospecting contains seepages of light oils and is the fourth area described in the paper. The difficulties of transporting both men and supplies to the well sites have delayed operations and brought the costs up to high figures. The drilling of these three wells is interesting on account of the presence of oil in nearby seepages and its occasional appearances in the material penetrated. A. C. McLAUGHLIN, San Francisco, Cal.-The most important part of Washington is on the Olympic Peninsula. The geological conditions on the Peninsula are not similar to the conditions in California, and it would not prove to be a continuous belt of oil-bearing territory from there to here if oil should be found at either end.

Jan 12, 1915

By C. G. Dunn, M. Sharp

IN twinned crystals of the face-centered cubic metals the lattice of one twin is a mirror image of the other in a common twin boundary. When several twins appear within large grain in a sheet specimen, the twin one boundaries form a set of lines at the surface of the specimen which coincide with (111) planes of the large grain. Furthermore, for twins of the same orientation, these lines are parallel. Generally, the presence of identically oriented regions with straight parallel boundaries coinciding with a (111) plane of the surrounding crystal is strong evidence for identifying the island regions as twins of the parent crystal. However, Fig. 1, which shows the macrostructure of a large grain of copper with island regions that satisfy these conditions. is not an illustration of (111) twins. Since the reverse side of the specimen has much the same appearance, it was thought at first that these regions, which appear dark in the macrograph, actually were twins. According to X-ray data, however, these regions are second-order twins of the large crystal. With regard to their formation, these second-order twins formed by secondary recrystallization in a cube texture matrix. Growth occurred in the direction of the arrow (see Fig. 1) as the specimen moved slowly into a gradient temperature furnace as described previously.' Nucleation of the second-order twins occurred, therefore, on the ends facing opposite the arrow. If the origin of the second-order twins were due to repeated twinning, some first-order twin structure should be visible on these ends. This proved to be the case, as very small twins were readily found with the aid of a microscope, and probably could have been seen, in some instances, under ideal lighting conditions without aid of a microscope. Fig. 2 shows a cross-section view taken perpendicular to both the surface and the (111) trace of the parent crystal (visible as a straight boundary in Fig. 1) at the beginning point of growth of a second-order twin and where one first-order twin was relatively thick. In the micrograph, A is the large parent grain; B is the first-order twin of A; and C, which is a first-order twin of B; is a second-order twin of A. Between A and B and between B and C the major straight portions are traces of common (111) twin boundaries. The straight portion of boundary between A and C, however, is not a common crystallographic plane to the two lattices; it is a (111) plane of A and a (115) plane of C. Without considering the mechanism of twinning itself, the origin of the second-order twins may be accounted for in terms of repeated twinning and special growth characteristics. After each nucleation, a selective growth process can be thought of as favoring growth of the first-order twin in local spots only and favoring growth of the second-order twin to an extent comparable with that of the parent grain over relatively large areas in a way similar to that described for twinning in aluminum.' It has already been pointed out that the boundary between the large grain (A) and the second-order twin (C), which is responsible for the straight boundary portions in Fig. 1, involves a (111) plane of A and a (115) plane of C. The same combination of planes is not only possible in first-order twins, but actually appears quite frequently.3 Their prevalence in first-order twins and their presence here in second-order twins, together with the necessary occurrence of a large number of common lattice sites at the boundary, is an indication that this combination produces an "energy cusp"' boundary. (Energy cusp boundaries have been described by Shockley and Read.") The configuration of atoms near a {Ill), (115) boundary in first-order twins is of course different from the configuration near the same type of boundary in second-order twins. References 1 M. Sharp and C. G. Dunn: Secondary Recrystallization Texture in Copper. Journal of Metals (January 1952) Trans. AIME, p. 42. 2W. G. Burgers and W. May: Stimulated Crystals and Twinning in Recrystallized Aluminum. Recueil des travaux chimiques des Pays-Bas (1945) 64, p. 5. aD. Whitwham, M. Mouflard, and P. Lacombe: Discussion of W. C. Ellis and R. G. Treuting, "Atomic Relationships in the Cubic Twinned State." Trans. AIME (1951) 191, p. 1070; Journal of Metals (October 1951). 4 W. Shockley and W. T. Read: Dislocation Models of Crystal Grain Boundaries. Physical Review (1950) 78, p. 275.

Jan 1, 1953

By I. L. Dillamore

A purely geomentrical analysis based on oriented-growth relationships is presented to derive annealing-texture orientations in bcc metals from their- known deformation textures. The analysis takes as its starting point a description of- the bcc deformation texture and follows previous work on fcc metals in considering pvobable nurleation sites for recrystallization and the textural limitations on grains growing into a deformed matrix. The analy-sis accounts for the prominent and the minor coinponents of the annealing textures formed from two the deformation textures and can account for the ob-sem:ed temperature dependence of the annealing texture of bcc metals. THERE have been a number of investigations of annealing textures in bcc metals but few attempts to relate these textures to the deformation textures. This has been largely due to the lack of definition of both annealing and deformation textures, neither of which shows sharply defined orientations. It is, however, necessary to get a better understanding of primary recrystallization textures in bcc metals in view of increasingly exacting demands upon the quality of steel sheet for drawing purposes and as a necessary step towards the control of textures through processing. An analysis is presented here which relates annealing textures to deformation texture, by a purely geometrical method. This takes as its basis the oriented-growth theory of recrystallization and makes some reasonable assumptions regarding the make-up of bcc deformation textures and the limitations on growth relationships in bcc metals. Detailed information on this latter point is not available at the present time, and the present analysis may need to be streamlined or extended when such information is at hand. It is felt, however, that despite these limitations the analysis provides useful results and a valuable aid towards understanding the effect of processing variables. 1) BCC ROLLING TEXTURES Different workers have used a variety of descriptions for the texture developed in bcc metals by rolling. For the present purpose it will be assumed that two different deformation textures can be obtained: 1) a texture containing a major (112)[li0] component and a minor (001)[1i0] component for which increasing deformation causes the (001)[li0] component to increase at the expense of the (112)[li0] component, as suggested by Dillamore and ~oberts' (this is the texture predicted to arise starting from randomly oriented material); 2) a t~xture containing the above components and (111)[110] and (ii1)[112] components. This texture could arise from a material with an initial (110)[001] or (iil)[112] texture. It is well-known that the (ll0)[001] orientation rotates to (ii1)[112]that on roll-

Jan 1, 1965

By J. J. Jakosky

The strategic importance of the metallic minerals in our industrial economy, and the declining rates of discovery have focused attention on means of exploration for new mineral deposits. A consideration of exploration techniques leads to an attempt to evaluate the effectiveness of geophysics as a tool for mining exploration. One means of evaluation will be to compare the use of geophysics in petroleum exploration with its possible uses in mining. Geophysics in Petroleum Exploration During the past twenty years, the petroleum industry has established an effective exploration technique. Geology is the basic tool in those areas where reliable predictions can be made from surface conditions. In the other areas, where the geological studies are inadequate, they must be supplemented with geophysics or direct exploration, such as drilling. Since geophysical work is far less costly than any form of direct explbration, it is used almost exclusively as the means for obtaining the desired subsurface information. The geological and geophysical techniques are credited with locating sites which yielded one producer for three dry holes during the year 1947.' For the wells located without geology or geophysics, there is a ratio of one producing well to sixteen dry holes. From these figures it is seen that the geological and geophysical techniques are more than four times as successful as the nontechnical exploration. It will be in order to consider further this ratio of one producer to three dry holes. The geophysical methods in use today† do not pretend to locate oil directly; their function is to locate anomalies or structures favorable for the accumulation of oil. For a producing oil well we must have not only structure, but also other favorable conditions, namely: petroliferous source beds, the required porosity and permeability in the reservoir rocks, an impermeable cap rock over the reser- voir, and the necessary water or gravity drive to force the oil into the bore hole. Since the geophysical work can only detect and sometimes delimit the anomaly, these other necessary conditions can be determined only by direct exploration. The success of modern geophysical work in locating and limiting the structure itself is remarkably high, probably over 95 pct accurate. Geophysical work renders an important service in the delineation of the structurally unfavorable areas and their elimination from the drilling phase of the exploration program. When attempting to locate any material of scarce occurrence in the earth, it is of paramount importance to know where not to dig. This elimination of barren areas is the least appreciated but is of great economic importance. For illustration, the difference between one producer to three dry holes, and one producer to sixteen dry holes, represents a saving of thirteen drilled wells, which would require an expenditure many times the cost of the geophysical work that might have revealed the nonfavorable structural conditions. The percentage of geophysically-located wells necessarily will continue to increase in the statistics of future years, as the search for oil is extended

Jan 1, 1950

By R. E. Miner, J. K. Jackson, T. L. Wilson

A study has been made of the transformation kintetics and morphology in gas-quenched Fe-5 pct Ni alloys. Massive ferrite or nlurtensite was found to form at temperatures in agreement with earlier results. Surface Preparation appeared to have the greatest effect in determining the type of transformation Product formed. Grain size change, subgrain morphology, and dislocation densities of massive ferrite were essen-tinlly invariant functions of cooling rate. The mar-tens~tic structures were typical of transformation in austenite grains of the order of the sample thickness. BY introducing the idea of a massive transformation in dilute iron-base alloys, Gilbert and Owen in 1962 served to stimulate a closer inspection of phase transformations in ferrous systems.' A wealth of literature has followed concerned with the morphology,2-5 transformation mode,2'3'6-8 and thermodynamics of transformations.2,5,9 interesting controversies have resulted from the experimental observations; closer attention has been paid to the definition of massive transformations and still to be resolved is the Ms temperature of pure iron. The purpose of this note is to report some observations made in a detailed kinetic and metallographic examination of the transformations that occur in gas quenched Fe-5 pct Ni. The results are pertinent to the Ms extrapolations that have been made for pure iron and the observed substructure of massively transformed alloys. PROCEDURE The material used in this investigation was cast as a 5 lb vacuum induction melted, carbon deoxidized heat. The ingot was hot worked to a strip 0.10 in. thick, decarburized, and cold rolled to final thickness. Specimens were punched to sample shape and decarburized in wet hydrogen at 600°C. The chemistry of test specimens is indicated in Table I. Samples 1 by $ in., by thickness were resistance heated and rapidly cooled in an apparatus as illustrated in Fig. 1. Similar helium quenching apparatuses have been described previously;2,6'10 the distinguishing feature of this apparatus is the nozzle geometry. Twin nozzles with three convergent-divergent, sonic ports were mounted perpendicular to the specimen for quenching purposes. The specimen temperature was monitored with an intrinsic 3 mil chromel-alumel thermocouple spot welded to the specimen and con- nected to an oscilloscope. A single switch stopped the current flow through the specimen, opened a gas flow solenoid valve, and initiated an oscilloscope sweep. Cooling rates were read directly from a photograph of the oscilloscope trace and the quenching rates quoted later were made at a point immediately prior to transformation on the trace. All quenching studies were conducted either under a vacuum of 10"-5 torr or a helium atmosphere. The sample geometry was chosen large enough to permit optical and electron microscopy to be performed on samples. The samples were electropolished for both types of examination in a perchloric-acetic solution. Electron microscopy was conducted on a HU 11A microscope operated at 100 kv. Dislocation densities were determined at the same general operating reflection (110) on foils thick enough to produce Kikuchi patterns. RESULTS AND DISCUSSION Transformation Temperature Observations and OD-tical Microscopy. The quenching results of this study are illustrated in Fig. -2(a). Samples which were treated in the as-decarburized condition transformed in a manner similar to that reported previously—a decrease in transformation temperature occurred as the quenching rate increased until a plateau region was reached. Within the scatter of the results obtained here, there was no break in the transformation temperature-quenching rate plot. This suggests no change in transformation mode. Further metallographic examination confirmed this observation. A martensitic transformation was obtained for similarly treated samples except that the surface was first electropolished. The Ms temperature was approximately 85°C below the plateau determined for the unpolished samples and cooling rates as slow as 2000°C per sec were adequate for producing marten-site. The transformation temperatures are in gen- / STRIP SAMPLE / COPPER I SAX/-/}' / CONNECTOR-----A f, SON|C poRTS AC LEADS 3j ]j"I rofe[ \ Mf/yinK/iKj''^ THERMOCOUPLE X-(^—iie"s*c? ' LEADS 1 INCH Fig. 1-—Schematic scction of gas quenching apparatus

Jan 1, 1970

By Francis S. Kendorski

INTRODUCTION Nuclear waste has been generated since the time of the Curie's and continues to be generated worldwide at an ever-increasing rate as the world will (and should) rely more and more upon fission (and hopefully fusion) for power. Also, the needs for strategic weapons will also generate so-called defense wastes. The largest class of high level nuclear waste (HLW) is spent fuel, the tail end of the nuclear reactor fuel cycle. At present, spent fuel is stored at the reactors producing it or at a few accepting places for away-from-reactor storage. All such storage facilities, as presently constructed, will begin to run out of usable storage space during the next decade or so. Congress enacted and President Reagan signed into law in early 1983 the National Nuclear Waste Policy Act of 1982. This law provides for the permanent isolation of nuclear waste in deep geologic repositories. The Act sets 1998 as the date at which the first repository should be operational. This date is extremely ambitious, and the Department of Energy (DOE), which is charged with the responsibility of constructing and operating repositories, admits that this date will slip by at least a few years. The Act also provides for licensing of repositories by the Nuclear Regulatory Commission (NRC) in a fashion very similar to nuclear power generating reactors. This requirement imposes a very special rigor on the analyses, investigations, designs, construction, and operation of repositories so as to assure the protection of the public and the environment from radioactive contamination. In addition the states and affected Indian Tribes must be consulted, especially concerning siting, and, needless to say, no one wants a HLW repository in their back yard.

Jan 1, 1984

By George Smith

THE Secretary of the Interior in his recent report to the President has defined the new public-land policy, which is in fact "but a new application of an old policy." His words may be more acceptable on this subject of land classification than the repetition of phrases which have served some of us for several years. Secretary Lane says of the past: "Congress has always been most generous as to the disposition of the national lands. . . . There was land for all, and it was the government's glad function to distribute it and let those profit who could. . . . And this generous donor was not so petty as to discriminate between kinds of lands, the uses to which they could be put, or the purposes which those might have who got them. Land is land, save when it contains minerals; this was roughly the broad principle adopted. To classify was a task too difficult or not worth while. The lands would classify themselves when they arrived in individual ownership. And so the door was opened for monopoly and for fraud. Of the reaction and the evolution of a new policy, the Secretary continues: "A reaction was inevitable. If lands were to be withdrawn from public service, why might not the government do the withdrawing itself? The old philosophy that `land is land' was evidently unfitted to a country where land is sometimes timber and sometimes coal; indeed, where land may mean water-water for tens of thousands of needy neighboring acres. For the lands of the West differ as men do, in character and condition and degree of usefulness. We had not recognized this fact when we said `land is land.' Lands fitted for dry farming and lands that must forever lie unused without irrigation; lands that are worthless save for their timber; lands that are rich in grasses and lands that. are poor in grasses; lands underlain with the non-precious minerals essential to industry or agriculture; lands that are invaluable for reservoir or dam sites these varieties may be multiplied, and each new variety emphasizes the fact that each kind of land has its own future and affords its own opportunity for contributing to the nation's wealth.

Jan 6, 1914

By George Otis Smith

The Secretary of the Interior in his recent report to the President has defined the new public-land policy, which is in fact "but a new application of an old policy." His words may be more acceptable on this subject of land classification than the repetition of phrases which have served some of us for several years. Secretary Lane says of the past: 1'Congress has always been most generous as to the disposition of the national lands.... There was land for all, and it was the government's glad function to distribute it and let those profit who could.... And this generous donor was not so petty as to discriminate between kinds of lands, the uses to which they could be put, or the purposes which those might have who got them. Land is land, save when it contains minerals; this was roughly the broad principle adopted. To classify was a task too difficult or not worth while. The lands would classify themselves when they arrived in individual ownership. And so the door was opened for monopoly and for fraud." Of the reaction and the evolution of a new policy, the Secretary con. tinues: • ' " A reaction was inevitable. If lands were to be withdrawn from public service, why might not the government do the withdrawing itself? The old philosophy that land is land' was evidently unfitted to a country where land is sometimes timber and sometimes coal; indeed, where land may mean water—water for tens of thousands of needy neighboring acres. For the lands of the West differ as men do, in character and condition and degree of usefulness. We had not recognized this fact when we said 'land is land.' Lands fitted for dry farming and lands that must forever lie unused without irrigation; lands that are worthless save for their timber; lands that are rich in grasses and lands that are poor in grasses; lands underlain with the non-precious minerals essential to industry or agriculture; lands that are invaluable for reservoir or dam sites— these varieties may be multiplied, and each new variety emphasizes the fact that each kind of land has its own future and affords its own opportunity for contributing to the nation's wealth.

Jan 1, 1915

By W. C. Leslie, R. M. Fisher, K. G. Carroll

A nitride, believed to be Si3N, has been separated from three nitrided silicon steels. Germanium nitride, Ge3N4, has been prepared from pure germanium. Comparison of the diffraction patterns indicates that the two nitrides are isomorphous; on orthorhombic structure is suggested in place of the rhombohedral structure previously reported for Ge3N4. THE possibility that a nitride of silicon may, under appropriate conditions, precipitate in silicon steels or in steels killed with silicon makes it desirable to have some positive means of identifying such a compound. One such means is the X-ray or electron diffraction pattern of the nitride. A review of the meager data in the literature indicates that the nitride most likely to form is Si3N4, a conclusion supported by the results of a study of nitrided silicon steels to be published shortly by L. S. Darken and R. P. Smith, of this Laboratory. Unfortunately, there is available no diffraction pattern for this nitride. Data have been reported, however, for Ge3N4 which, judging from the similarity between germanium and silicon, might be expected to be isomorphous with Si3N4. An effort was made, therefore, to form such a silicon nitride, to determine its composition and diffraction pattern and, if possible, its structure. To this end a series of three silicon steels was nitrided under controlled conditions with the resultant formation of nitride particles which yielded an electron diffraction pattern in situ. The particles were then extracted from the steel and an attempt was made to determine their chemical composition. X-ray and electron diffraction patterns were also obtained from the extracted particles, which indicate that the nitride is isomorphous with Ge3N4, although a complete determination of the structure has not been possible. These results show that a silicon nitride with a well-defined diffraction pattern can form in silicon steels, and they suggest that this nitride is Si3N4. Materials and Procedures The sillicon steels investigated were In the form of thin sheet or strip and had the composition shown in Table I. The 0.58 and 1.21 pct Si steels were nitrided by holding them at 1110°F in an H2-NH3 atmosphere containing 3 pct ammonia for 48 hr. The nitride particle size was increased by subsequent heating at 1500°F for 13 1/2 hr in helium. The resulting microstructure is shown in Fig. 1. The steel containing 3.20 pct Si was nitrided at 1200°F for 16 1/2 hr after which it was held in helium at 1500°F for 4 hr. Its structure as seen under the electron microscope is illustrated by Fig. 2. As would be expected from the higher silicon content and the shorter holding time at 1500 °F, the nitride particles are smaller and more numerous than those in the 1.21 pct Si steel. The ammonia-hydrogen treatment reduced the carbon content of the steels to a very low level, so no interference was encountered from carbon or carbides. In the case of the 3.2 pct Si steel, the carbon was reduced to 0.003 pct before nitriding by heating in dry hydrogen. Attempts to obtain an X-ray diffraction pattern from polished and etched surfaces of the 1.21 and the 3.20 pct Si steels were unsuccessful. However, an electron diffraction pattern was obtained from the surface of the steels. The interplanar spacings obtained from these patterns arc shown in Table 11, col. 5. The nitride particles were then extracted from all three steels by dissolving the ferrite matrix in bromine-methyl acetate, the solution used in the Beeghly method for the extraction of aluminum nitride from steel. X-ray diffraction patterns of these residues, obtained by means of a spectrometer and by a 57 mm Debye-Scherrer powder camera using filtered cobalt or chromium radiation, are given in Table II along with the pattern obtained by

Jan 1, 1953

By S. F. Reiter, You-Chao Liu, W. R. Hibbard

Cyril Stanley Smith in his classic 1948 Institute of Metals Lecture&apos; noted in the case of annealing twins that: "It is well known that approximately the same number of twins per grain and the same general geometry are maintained in large grains as in small ones, a fact that certainly suggests a mechanism such as the above where boundaries and twins grow proportionately together. If this view is correct, a spherical grain should have no mechanism for keeping its twins." Such a constancy of twins per grain would be of particular interest as a tool for the study of the origin of annealing twins. It has been proposed by Mathewson2 and later by Barrett3 that in face-centered cubic metals slip occurs in the {111} Plane by <112> shears which combine in pairs to produce the macroscopically observed <110> movement. This proposal is schematically inviting since <112> slip permits the atoms of one plane to move along the interatomic valleys of its neighbor rather than up the hills across the atom sites. There is strong experimental evidence? that annealing twins result from the growth of nuclei in the form of "twin faults" produced by single <112> shears. It is possible that more twin faults would form at low deformation temperatures than at high ones, because the more rigid lattice may increase the tendency to "freeze" the twin faults and prevent their dissipation in slip. This is suggested by (1) the greater resistance to slip at low temperatures and (2) greater tendency toward mechanical type twinning at low temperatures (a summary of these factors is presented by Seigle and Brick5). These considerations would suggest the following: a. Constant twin/grain ratio for specimens deformed constant amounts at a constant temperature, but annealed at various temperatures above the recrystalliza-tion temperature. b. Larger twin/grain ratios for re-crystallized specimens previously deformed constant amounts at lower temperatures. The purpose of this investigation is to test these considerations. One half in. rods of phosphorous deoxidized electrolytic copper and 70-30 alpha brass (68.36 pct Cu, 0.005 pct Pb, 0.01 pct Fe, 31.62 pct Zn remainder) were rolled to a thickness of 0.350 in., milled to specimens 0.350 X 0.437 X 2 in., and annealed at 700°C to an average grain size of 0.065 and 0.090 mm, respectively. These specimens of each metal were then rolled 50 pct reduction in thickness and annealed one hour under conditions which were all combinations of the following: Rolling Annealing Temperatures. Temperatures. °C °C -70 400 25 500 200 600 Standard metallographic techniques&apos; were used to prepare specimens. By the method of lineal analysis7 using a minimum of ten samples of fifty grains each for each specimen, the ratios of twins* per total grains, twins per twinned grain, twin families* per total grains and twins per twin family were determined. Recrystallized grain size was determined by A.S.T.M. comparison methods.8 All observations were made on the rolling plane. The results are tabulated in Table 1.

Jan 1, 1950

While coal was undoubtedly seen by the Spanish explorers in Texas, no mention can be found of it in any of their available published records; it was likely noticed by the first Americans, and coal along the Rio Grande River was reported in 1834.1 The next record is that of brown coal in Bastrop County in 1837 by James Nicholson and Judge Pinckney Hill? Dr. Riddell saw brown coal along the Trinity River in 1839 and described it as follows: "In the banks of the Trinity, associated with the iron ore, and overlying the brown coal, whole trees and fragments of trees, piled sometimes one upon another, present themselves completely transformed into stone. In some logs a diversified metamorphosis is observable; one portion of the vegetable structure having been replaced with silex, another with brown oxide of iron, and a third is bitumenized or converted into coal. "In concern with Dr. F. B. Page, I took considerable pains in the exploration of the Trinity brown coal formation., As no excavations for working have yet been made, the best places for inspecting the formation are where the Trinity cuts its way through the highlands, or where its banks present themselves in bold high bluffs, as at New Cincinnati, and near the site of the projected town of Osceola. The coal lies in horizontal strata, dipping one foot in thirty to the northwest. The main stratum at the latter place, just above Bedias creek; is represented by the concurrent statement of W. C. Brookfield, surveyor, Mr. James S. Hunter, of Huntsville, Texas, Dr. Page, and some other persons whom I consulted, as between six and seven feet in thickness, the lower portion being between three and four feet above low water mark. Unfortunately, during my sojourn there, the river was unusually high and turbid for the season of year; I could not consequently verify the same by personal observation and measurements. The most considerable coal beds which I had opportunity fully to inspect, were in the Trinity bluffs, southwest side, at New Cincinnati, six miles lower down, and just below the mouth of Salt creek, near six miles above. The workable stratum of brown coal in each of these localities is about five feet thick, and situated some fifteen feet or so above low water mark. In quality it is said to be precisely similar to the coal in the seven feet bed."2 . Moore in 1840 mentioned coal in the vicinity of Great Salt Lake, through which the Brazos flows; lignite in Bastrop County; lignite in the banks of the Colorado River a few miles above Lagrange in Fayette County; a deposit of excellent coal in the bed of the Sabine River, 30 miles above the

Jan 1, 1942

By T. H. Alden

T. H. Alden (General Electric Research Laboratory)—This paper as well as earlier ones of Dr. Wood represent an important contribution to the experimental description of fatigue fracture. The mechanism of fracture proposed by the authors, however, is not established by this data nor supported by other data existing in the literature. Although taper section metallography provides a rather detailed picture of fatigue crack geometry, photographs so obtained must be interpreted with care. The narrow bands revealed by etching, frequently associated with surface notches, are labeled by the authors "fissures". Measurement shows, taking into account the 20 to 1 taper magnification, that the depth of these structures is at most 2 to 3 times the width. This distinction is important in the conception of a mechanism of crack formation. It is difficult, for example, to imagine a deep, narrow fissure arising from a "ratchet slip" model. A surface notch, on the other hand, may form easily by this mechanism. The notches observed in the present work are the subsurface evidence of the surface slip bands or striations in which fatigue cracks are known to originate.4-6 It is clear that an understanding of the structure of these slip bands is of key importance in understanding the mechanism of fracture. The evidence presented shows that these regions etch preferentially, possibly because they contain a high density of lattice defects, or as the authors state equivalently, because they are "abnormally distorted." However, it is not possible to conclude that the distortion consists of a high density of vacant lattice sites. The fact of a high total shear strain in itself does not assure a predominance of point defects as opposed to other defects, for example, dislocations. Other evidence in the literature which suggests unusual densities of point defects formed by fatigue7-&apos; refers not to the striations or fissures, but to the material between fissures (the "matrix"). If a choice must be made, the preferential etching would seem to be evidence for a high dislocation density, since dislocations are known to encourage chemical attack in copper;g no such effect is known for the case of point defects. A third alternative is that the slip bands are actually cracked, but that near its tip the crack is too narrow to be detected by the authors&apos; metal-lographic technique. In this case the rapid etching can be readily understood in terms of the increased chemical activity of surface atoms. Unless a vacancy mechanism is operative, the motion of dislocations to-and-fro on single slip planes will not lead to crack growth. Point defect or dislocation loop generation are the principal non-reversible effects predicted by this model. In any case, the nonuniform roughening of the surface in a slip band6 requires a flexibility of dislocation motion which is not a part of the to-and-fro fine slip idea. The same is probably true of crack growth by a shear mechanism. Either some dislocations must change their slip planes near the end of the band and return on different planes,&apos;0 or dislocations of opposite sign annihilate." The mechanism by which these processes occur in copper at room temperature or below is that of cross slip. Thus cross slip appears to be essential to fatigue crack growth.6&apos;10"12 The fact that a tensile stress opens the slip bands into broad cracks does not indicate the structure of the bands or the mechanism by which cracks form. The charactersitic concentration of slip into bands during fatigue shows a low resistance to shear strain in these regions. (This fact in itself may be inconsistent with a high concentration of vacancies.) The authors contend also that continuing shear produces an additional mechanical weakening so that the bands fracture easily (are pulled apart) under the influence of the superimposed tensile stress. It is equally possible that the only weakness is a weakness in shear, that the crack propagates by a shear mechanism, and that subsequently the tensile stress pulls the crack apart. Even the direct observation of bands opened by a tensile stress would not be conclusive since, as argued above, they may be fine cracks. The same argument applies to internal cracks, their existence in the presence of a tensile stress not indicating the mechanism of formation. Internal cracks originating in regions of heavy shear have also been seen following tensile deformation of OFHC copper,13 so that this mode of fracture is not unique to combined tensile and fatigue straining. The authors point out in their companion report14 that 90 pct of the cracks formed during pure tor-sional strain were within 8 deg of the normal to the specimen axis. If the tensile stress were an important factor in crack propagation, it is surprising that the cracks cluster about the plane in which the normal stress vanishes. Similarly, a study of zinc single crystals showed that for various orientations the life correlated well with the resolved shear stress on the basal plane,&apos;= and was not dependent on the normal stress across this plane. W. A. Wood and H. M. Bendler (Authors&apos; reply) -Dr. Alden&apos;s discussion emphasizes the essential point in the relation of slip band structure to

Jan 1, 1963

By D. Harrington

FROM 1870 to date, the coal production of Utah has been somewhat less than 85,000,000 tons. There have been at least three major disasters with total fatalities about 380; or approximately. 4.4 persons killed by mine explosions per million tons produced, a record that is decidedly bad. Even during the periods when there have been no disasters, such as the years 1914 to 1920, inclusive, the fatalities .in ordinary working ran about 5.4 per million tons produced, against 3.7 per, million tons. for the whole United States for the same years. The five-year period following the war, 1918 to 1922 inclusive, showed 4.7 fatalities per million tons, hence the fatality record in the coal mines of Utah has uniformly been in excess of the average of the coal mines of the entire country. Notwithstanding this poor record, Utah has given to the coal-mining world many excellent safety methods and practices and the Utah. coal mines in general take greater measures toward safe mining than do the coal mines of any other State; if practices and methods allowed and pursued in coal mines of other States were tried in Utah coal mines, there would be a succession of disasters. Utah&apos;s principal producing coal mines, operated by about eighteen companies and numbering less than forty, have comparatively thick seams. Very little coal under 5 ft. thick is being worked and practically none under 4 ft.; much, if not most, of the coal comes from seams in excess of 8 ft., some running as high as 30 ft. In thick seams in which coal is left on floor and roof, any dust found or made is entirely combustible. In addition, the thick seams induce the use of large capacity cars, handling which in rooms and other workings on fairly heavy grades (up to 10 or .12 per cent.) tends to cause haulage accidents. The thick seams give high ribs and roof, in which it is difficult to prevent slabs of coal or rock from dropping on workers and also difficult to keep free of gas and of coal dust. The coal is high volatile, running usually over 40 per cent and in some instances nearly to 50 per cent; hence is highly flammable. Most of the coals have very high resin content, the resin usually being in dust form, hence almost as highly flammable as black powder. At .least one-third of the mines give off methane and several give off other

Jan 8, 1925

By C. J. McHargue, J. C. Ogle

Lightly deformed columbiun single crystals which contained only parallel hoins or purullel and intersecting trains were annealed at 1000&apos; and 1600"C. No re-crystallizntion occurred in specimens hawing only parallel twins. Only noncoherent twin boundaries nzipated at 1000°C but both coherent and noncoherent ones moved al 1600°C. Recrystallization occurred within a few minutes at twin intersections at 1000°C. The orientation 01 the recrystallized grains differed front that of both the matrix and deformation twins, but could he derired by (110) and/or(112) rotations. ALTHOUGH twinning in metals has been extensively studied, there have been no definitive studies of the annealing behavior of crystals containing deformation twins. Some effects observed after annealing deformation twins have been summarized by Cahn1 and Hall2. Any or all of these phenomena are observed: 1) The twins may contract so that the sharp edges of the lens become blunted, and eventually the twin may disappear entirely. 2) The twins may balloon out at an edge, giving rise to a large grain having the same orientation as the twin. 3) The specimen may recrystallize; i.e., new grains are nucleated and grow at the expense of the twins and the crystal immediately adjoining the twin. Such grains have orientations which are not present before. Contraction has been observed in iron,3 titanium,3, 4 beryllium,5 zinc,8, 7 Fe-A1 alloy,&apos; and uranium.9 Long anneals at high temperatures are required to have any appreciable effect in these metals and only thin twins are absorbed. Lens-shaped twins are absorbed from the edges: the thin, almost parallel-sided twins are usually punctured in several places and each piece contracts independently. Absorption is very gradual and no sudden cooperative jumps have been observed. The expansion of a twin into a larger grain of identical orientation is unusual, but such growth has been observed in iron,"&apos;" zinc,6 and uranium." Crystals which have been deformed simultaneously by slip and twinning recrystallize first in the area adjacent to the twin. New grains appear faster where the twins intersect: but isolated twins, especially if thick, can also give rise to new grains. This type of recrystallization occurs in zinc.6, 7, 12, 13 and beryllium.14 Reed-Hill noted, in a single crystal of magnesium, the nucleation of a recrystallized grain at a twin intersection which had the same orientation as the second-order twin and which grew into the highly strained matrix.15 Short-time annealing has been reported to cause no change in the deformation twins in vanadium,16 columbium, 17, 18 tantalum,19 tungsten,&apos;&apos; and zinc.7 The purpose of this investigation was to note the effects of annealing on the coherent and noncoherent boundaries of deformation twins in columbium and to locate the nucleating sites for recrystallization. The orientation relationships, which the new recrystallized grains have with the parent crystal and the deformation twins, were also determined. EXPERIMENTAL PROCEDURE Single crystals of columbium were obtained by cutting large grains from electron-beam-melted buttons which contained 10 to 50 ppm C, 10 to 100 ppm O,, 1 to 10 ppm H2, and 10 to 15 ppm N2. The crystals were hand-ground and chemically polished until all grain boundaries were removed. The specimens were mounted in an epoxy resin and a face of each crystal was mechanically polished on a Syntron polisher using Linde A and then Linde B polishing compounds. After all faces were mechanically polished, the crystal was electrolytically polished to remove all distortion due to cutting and grinding. Laue photographs were taken of all faces of the crystals to determine the quality and orientation of each crystal. The crystals were compressed about 10 pct at -196 C in a specially constructed compression cage with an Instron tensile machine. Each crystal was separated from the top and bottom anvils by teflon films which acted as a lubricant. With the specimen crystal in position, the entire cage was cooled to -196°C by being submerged in a Dewar containing liquid nitrogen. The crystals were compressed at a rate of 0.02 in. per min and the load was recorded on a strip-chart recorder. After deformation the crystals were mechanically polished on 600-grit paper and Pellon cloth with Linde A and Linde B polishing compounds. The crystal faces were chemically polished and then etched. The twin planes were identified metallographically from an analysis of the twin traces on two surfaces. Annealing was carried out by placing each crystal in a columbium bucket made from the same electron-beam-melted material as the crystal itself and suspending the bucket by a tantalum wire in a quartz tube. After a vacuum of 10-7 Torr was attained, a furnace at 1000" or 1600 C was raised into position and the crystals held for various lengths of time. The crystals were repolished and etched after annealing to remove any surface contamination. Approximately 0.010 in. was removed during this process. The resulting surface was examined metallographically for microstructural changes due to annealing. A microbeam Laue camera mounted on a Hilger Micro-focus X-ray unit was used to determine the Orientstions of the recrystallized grains. This X-ray micro-beam camera had a 0.002-in.-diam collimator and incorporated the ideas of both and and chisWik21 and Cahn.22

Jan 1, 1967

By George W. Riter

OUR mineral-land laws need revising so as to provide definite title at the outset to the mineral deposits within any definite piece of land. The laws as they now stand, especially those applicable to lodes, breed uncertainty as to rights of possession prior to patent; and to my mind this is the worst feature of all, worse even than the apex bugbear. It is now almost impossible for anybody to tell-with certainty what mineral rights exist within any area that is not covered by patent, or whether any valid rights exist at all. Our system is unique in permitting individuals to appropriate and exploit mineral lands of the public domain without notice of any kind to the Federal government, and to relinquish them without any ceremony at all. The result is a clouded record that cannot be cleared up until each claimant is put to some sort of final proof. In order to accomplish this, new Federal legislation will be required. The requirements for a mineral survey and the proceedings for patent have always been cumbersome and expensive; and perhaps out of regard for the poor claim owner, who can ill afford the outlay for that sort of thing, the law does not require him to go. through it unless he chooses to do so. Consequently, every active mining district has become encumbered with tangled groups of doubtful or conflicting locations, whose rights and boundaries, when any valuable ore is found, must usually be determined by lawsuits that are as expensive and as distressing as the stakes are high. So deeply has litigation entered into our mining system that a claim whose rights have never been disputed would probably be set down offhand, by $miner of the old school, as of no value. Think of the litigation over rights of possession on the Com-stock lode—12 leading companies involved &apos;in an aggregate of 245 suits within a period of less than eight years! Ambiguous local records; the chance of erroneously placed or obliterated monuments; doubt as to the sufficient performance of the statutory annual labor; uncertainty as to prior conflicting or overlapping locations; anxiety as to the changing attitude of the Department of the Interior and the Forest Service—such considerations as these make an unpatented mining claim an unclean thing in the eyes of possible investors. Is it any wonder that they keep themselvesand their money at a safe distance,

Jan 1, 1915

Planning for a surface coal mine includes selecting the best means and equipment for uncovering the coal, loading it, and transporting it to the preparation plant. The machines and methods that will ensure optimum production will depend upon the location and characteristics of the seam to be mined. Stripping Techniques The choice of stripping units is influenced primarily by the system of mining, such as contour or out-crop mining as contrasted to mining in a region of rolling terrain with relatively flat upland surfaces. Factors such as the life of the mining operations production requirements, types of overburden, local and regional dip of coal, and land reclamation are other important considerations.

Jan 10, 1967