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By J. E. Harris, J. A. Whiteman, A. G. Quarrell

The graphitizing reaction has been studied in a number of Fe-C-Si alloys in the temperature range 550° to 725°C. The TTT relationships exhibit "C" curve behavior except where nuclei, either foreign or graphite itself, are present before the start of the reaction. It is suggested that the rate -controlling process is diffusion of carbon through ferrite. For the reaction to proceed at the observed rate it is calculated that the matrix surrounding the particles must deform plastically; experimental evidence for this deformation is presented. It is well-established that the decomposition of austenite to pear lite occurs at a maximum rate at an intermediate temperature.l-5 This "C curve" be- havior, which has been reported in a number of other systems,5-10 is a consequence of the relatively low rate of nucleation of the pearlite at small degrees of undercooling of the austenite. The cemen-tite phase in the pearlite is, in turn, metastable with respect to graphite and if steels are held for prolonged periods at elevated temperatures decomposition of the pearlite occurs. It is difficult to predict the shape of the subcriti-cal graphitization TTT (time, temperature, transformation) diagram for, in this case, undercooling does not occur. However, the free-energy change for the reaction does decrease with increasing temperature" (Fig. 1) and it is thus anticipated that the rate of nucleation will fall as the temperature approaches that of the eutectoid. In addition, a decreasing growth rate with increasing temperature is predicted in some circumstances with pure Fe-C alloys. However, apparently similar conditions exist for first-stage graphitization in the austenite range (malleabilization) but no evidence for C curve behavior has been presented in the extensive liter-

Jan 1, 1965

By C. S. Barrett, A. Smigelskas

J. T. NORTON*—I think Mrs. Smigelskas Fischer has done a splendid job in working out the pole figures from rather difficult photograms which are common to beryllium. Is there not a mistake in Fig 2 in that the pole figures B and C have been interchanged? A. SMIGELSKAS FISCHER (authors' reply)—Yes, there is such an error in the labeling of the pole figures of Fig 2. The correct plane for Fig 2b and 2c is the plane in parenthesis above the figure numbers and not that in the figure subtitle. J. T. NORTON—Also, I would like to mention another method of obtaining the data for pole figures which would be particularly applicable to this problem. It is a method which has been published only

Jan 1, 1950

By Walter Showak

The published phase diagrams for the copper-zirconium system1,2 indicate that the solid solubility of zirconium in copper is not accurately known. Studies made on relatively impure alloys by Pogodin, Shumova, and Kugucheva3 yielded a maximum solubility value of 1 wt pct Zr at the eutectic temperature. Allibone and sykes5 reported that an as-cast 0.2 wt pct Zr alloy is single phase at room temperature. Limited results obtained by Raub and Enge14 indicated that zirconium solubility in copper is less than 0.13 wt pct Zr at 940°C. Tn 1960, on the basis of a microstructural examination of several copper-rich Cu-Zr alloys, saarivirta6 placed the maximum solubility of zirconium in copper at 0.15 wt pct at the eutectic temperature, 980°C. The present note describes results obtained during a re-investigation of the Cu-Zr system for the purpose of accurately establishing the solidus and solvus curves and the eutectic temperature in copper-rich alloys. High-purity copper (99.99 pet) and zirconium (99.64 pet) consolidated reactor grade sponge were used to prepare several alloys, containing up to 2 wt pct Zr, by induction melting in graphite crucibles in vacuum and chill casting into a split steel mold. The melting procedure consisted of first melting the copper charge and then adding the bulk zirconium wrapped in pure copper foil. Chemical analyses were made of both the cold-rolled alloy ingots after homogenization at 925°C for 450 hr in evacuated quartz capsules and of small specimens which had been used in the phase diagram studies. 'The carbon content of each alloy was also determined and was found to be less than 0.001 wt pct in every case. Metallographic and electrical resistivity measurements were used as the primary methods for this investigation, although some thermal analysis studies were also performed. Heat treatments of all the alloys were carried out with the specimens wrapped in molybdenum or alloy foil (of the same composition as the specimen) and sealed in quartz tubes either in vacuum or under a purified helium atmosphere. Following high-temperature anneals for long periods of time, slight depletion of zirconium from the specimen surface was observed. Therefore, careful preparation of samples for microscopic examination and chemical analysis of the samples themselves was necessary to check the composition of samples used in determining phase boundaries. Points on the solvus curve were determined on quenched specimens by both isothermal reaction after solution heat treatment at 950°C for 8 hr and by isothermal annealing of alloy specimens at successively higher temperatures for times ranging from 24 to 500 hr. Liquation studies for positioning of the solidus and eutectic temperatures were performed by holding a pre-

Jan 1, 1962

By Henry N. Doyle

Basic procedures in the mining industry have changed only slightly over the centuries since metals and fossil fuels became an essential part of man's economic and cultural life. Mining techniques of the 20th century bear a close resemblance to those of the ancients: exploration, ore breakage and removal, hoisting, and processing. The great advances, however, have been in equipment and machinery of greater size and speed which allow greater efficiency in each of these operations, with a corresponding reduction in manpower requirements. Yesteryear production was measured in pounds per man-day; today a giant and complex, but highly efficient, continuous mining machine can remove as much as eight tons of material a minute from the coal face. If our energy and metal demands of the future are to be met, and at this time it can be assumed that coal will continue to supply a significant part of the energy demand, other dramatic and spectacular technologic advances must be accomplished. Along with mechanization, however, public policy will require the industry to place greater emphasis on health and safety protection, as has been well demonstrated by recent actions of Congress. Together, fossil fuels and metals formed the basis for the industrial revolution-coal to develop power and metals to transform power into useful energy. Strangely enough, however, the mining industry the world over has lagged behind the continuous social changes brought on by the industrial revolution, such as preventive health and industrial hygiene services, and other programs directed to the well-being of the worker. In some countries this resistance, to change may have led in part to the nationalization of the coal industry. Whether this disinclination to social change in the industry of the United States reflects managerial attitudes, inept labor leadership, government neglect, or economic relationship would be the subject of an interesting study. Doubtless the mores of miners and their resistance to change, as well as their geographic isolation from other industrial groups, may have had a strong influence on these factors. In every major coal mining country the accident rate in the coal industry is substantially higher than other industrial groups, and the cost of pneumoconiosis compensation in some countries is greater than the combined costs for all other occupational diseases from all other industries. The high social cost of occupational accidents and diseases may have been a factor in the closing of the industry in at least two countries. Despite diminishing manpower needs, the industry is faced with critical manpower shortages. Miners once reared their sons to be miners; now it appears that the opposite is true. This factor alone, however, does not explain an acute labor shortage in the industry. Traditionally, the industry drew much of

Jan 1, 1976

By E. A. Gulbransen, J. W. Hickman

INTRODUCTION DURING the past two decades considerable progress has been made in the art of manufacturing heater alloys. The conventional iron-chromium-nickel alloys have been improved by the addition of small quantities of other elements. Up to the present time, to our knowledge, there has not appeared a systematic study of these alloys where the newer tools of investigation have been brought to bear on the problem. It is not yet clear what roles the additional elements play in increasing life time in usage. As a first approximation one might guess that elements such as manganese, silicon, zirconium, calcium and aluminum would aid in the formation of a protective film on the alloy surface, thus retarding the oxidation rate and increasing lifetime. If these additional elements do form protective oxides in the outer surface of the oxide film, it may be possible to identify them by means of reflection electron diffraction. It is also possible that the additional elements may not diffuse to the surface but may remain at the interface between the oxide and the metal. Then, too, the major elements in the alloys undoubtedly form oxides which are stratified on the surface. If the minor elements concentrate in a layer in contact with the substrate where they undergo oxidation and if this oxide film offers resistance to the diffusion of iron, chromium and nickel ions, then the lifetime of the heater element might be expected to increase. It is also possible that preferential reduction in the diffusion rates of the several ions may occur to such a degree that oxides may form in the body of the film and on the outer surface which are different from those that would normally form if the additional elements were not present. The use of transmisson electron diffraction may aid us in interpreting these phenomena. Up to the present time all of the factors which influence the lifetime of a given heater element are not definitely known. Among these are: (I) The rate of oxidation of the alloy. This may be dependent upon the composition and the physical state of the alloy. (2) The stability of the structure of the coating which forms. Transitions from one structure to another or solid phase reactions resulting in a change of composition may occur. The tendency of the film to adhere to the substrate when heated and cooled successively will be important. (3) The evaporation of various constituents from the alloy such as the removal of carbon by oxygen in a decarburization reaction. With these possibilities in view, an electron diffraction study of the oxides occurring on six different nickel-chromium alloys was undertaken with the hope that the results of this study could be correlated with oxidation rate studies as determined by means of the vacuum microbalance method1 and with

Jan 1, 1948

By J. E. Hilliard

AS is well-known, the length per unit volume, Lv, of any lineal feature (such as grain edges in a polycrys-talline specimen) can be estimated from a count of the number of point intersections with a random plane of polish. Specifically:' Lv = 2NA in which NA is the expected number of intersections per unit area of the plane. As with all other measurements in quantitative metallography, the estimation of Lv is subject to a sampling error, the magnitude of which will depend on the number of observations. The analysis is usually performed by counting the number of intersections falling within a closed test figure of known area applied to a succession of different areas on the plane of polish. The test figure can be drawn directly on the screen of a projection microscope or else superimposed on the image of the structure by means of a reticule in a focusing eyepiece of an ordinary microscope. The use of micrographs is very inefficient unless, as in the present study, these are also needed for some other purpose. Consider an analysis in which n applications are made of a test figure within which the expected number of intersections is N. The expected total number of intersections counted is then given by NT = nN If (N) is the standard deviation in N for one application of the figure and if the latter is applied to non-overlapping regions so that the N's are independent in the statistical sense, then the standard deviation in Nt is given by: a(NT) = a(N)vn Eliminating n from Eqs. [2] and [3] we obtain: Thus, k will be a constant for a given specimen and test figure. From Eqs. [ I] and [4] we find As is to be expected, therefore, the fractional error in the estimation of Lv is inversely proportional to the square root of the total number of intersections counted. It is very desirable to have at least a rough estimate of k before starting an analysis, since it will then be possible to decide in advance by use of Eq. [5J how many counts should be made in order to achieve the desired accuracy in Lv. Without such information the investigator, unless lucky, will either do needless (and tedious) work or else obtain a result with too large an error. It is very easy to calculate k for the limiting case of N — 0, i.e., when the test figure is vanishingly small. In this case there is a negligible probability of two or more intersections falling within the figure. There are therefore only two possible outcomes: a count of one with a probability of, say, p and a zero count with a probability of (I-p). Thus and Therefore: We might expect k to depend on N and therefore on the size of the test figure. Such a dependence was observed2 in the analogous case involving the estimation of grain-boundary area per unit volume by a count of the number of intersections of a test circle with traces of the boundaries on the plane of polish. In this case the theoretical value of k at the limit N — 0 was 1.41. It was also predicted that k would display an initial sharp decrease with increasing N. Experimentally, k was observed to decrease to a value of 0.62 at N - 6 and thereafter remain approximately constant. Furthermore, the value of k for N > 6 was found to be insensitive to the form of the structure provided no pronounced anisotropy or grain-size variation was present. In order to determinewhether k would exhibit a similar dependence on N in the estimation of grain-

Jan 1, 1967

By T. K. Perkins, O. C. Johnston

Because of the influence of dispersion on miscible-displacement processes, diffusion and dispersion phenomena in parous rocks are of current interest in the oil industry. This paper reviews and summarizes a great deal of pertinent information from the literature. Porous media (both unconsolidated packs and consolidated rocks) can be visualized as a network of flow chambers, having random size and flow conductivity, connected together by openings of smaller size. In such a porous medium, the apparent diffusion coefficient D is less than the molecular diffusion coefficient Do, as measured in the absence of a porous medium. For packs of unconsolidated granular material the ratio D/D, is about 0.6 to 0.7. For all porous rocks, both cemented and unconsolidated, the ratio of diffusion coefficients can also be represented as D/Do = 1/FF where F is the for- mation electrical resistivity' factor and 4 is the porosity. If fluids are flowing through the porous medium, dispersion may be greater than that due to diffusion alone. At moderate flow rates the porous medium will create a slightly asymmetrical mix zone (trailing edge stretched out), with the longitudinal dispersion coefficient approximately proportional to the first power of average fluid velocity (if composition is nearly equalized in pore spaces by diffusion). If the velocity in interstices is large enough, there will be insufficient time for diffusion to equalize concentration within pore spaces. In this region, longitudinal dispersion increases more rapidly than fluid velocity. At low velocities in interstices, transverse dispersion is characterized by a region in which transverse diffusion dominates. If the fluid velocity gets high enough, there will be a transition into a region where there is stream splitting with mass transfer but with insufficient residence time to completely damp-out concentration variations within pore spaces. There are several variables that must be con- trolled to get consistent longitudinal and transverse dispersion results, viz., (1) edge effect in packed tubes, (2) particle size distribution, (3) particle shape, (4) packing or permeability heterogeneities, (5) viscosity ratios, (6) gravity forces, (7) amount of turbulence, and (8) effect of an immobile phase. INTRODUCTION Diffusion and dispersion in porous rocks are of current interest to the oil industry. This interest arises because of the influence of dispersion on miscible-displacement processes. In a recovery process utilizing a zone of miscible fluid, there is the possibility of losing miscibility by dissipating the miscible fluid or by channeling or "fingering" through the miscible zone. Diffusion and dispersion are two of the mechanisms that may lead to mixing and dissipation of the slug. On the other hand, dispersion may tend to damp-out viscous fingers which may be channeling through the miscible slug. 58 Hence, dispersion may be detrimental or beneficial (if it prevents fingering through the miscible zone). Therefore, it is doubly important that we understand these processes. In this paper we review, summarize and interpret a great deal of information from the literature. In particular, we will briefly discuss molecular diffusion in miscible fluids. Then we will discuss what differences to expect for diffusion in a porous rock. If there is movement of the fluid through the rock, then there may be an additional mixing or "dispersion". Furthermore, the dispersion longitudinally (in the direction of gross fluid movement) and transverse to the direction of fluid movement will not be equal. We will discuss both types of dispersion as well as several variables which can affect dispersion (viscosity differences, density differences, turbulence, heterogeneity of media, etc.). This group of variables has sometimes led to difficulty when comparing literature data. DIFFUSION OF MISCIBLE FLUIDS If two miscible fluids are in contact, with an initially sharp interface, they will slowly diffuse into one another. As time passes, the sharp interface between the two fluids will become a diffuse

By W. O. Philbrook, R. H. Spitzer, F. S. Manning

A generalized mathematical model has been developed to describe the kinetics of gas-solid reactions with special attention given to the hydrogen reduction oj dense spheres of hematite. This reduction process must pvoceed through a sequence of transport and chemical .reaction steps acting in series. Under typical experimental conditions, none oj the individual transport and reaction resistances may be neglected in the development of a physically significant model. A linear vate of thickening oj the product layer, usually taken as evidence of interface-controlled .reuction, may be observed even though transport resistances play a dominant role in the over-all kinetics. The temperature and pressure dependencies of all terms have been carefully evaluated in order to .make fill use oj arailable expe-inzental data in evaluation oj the model. FOR obvious technological reasons, the kinetics of reduction of iron oxides has become the subject of intensive experimental and theoretical investigation during recent years. Continuing efforts to construct mathematical models to describe the kinetics of reaction between a gas stream and a granular bed of solid particles have demonstrated the necessity of a thorough understanding of the reaction kinetics of a single particle within the system as a prerequisite to the construction of physically significant models of complex, reacting systems. This paper presents a critical examination of the transport and chemical-reaction processes involved in single-particle oxide reduction and develops the mathematical expressions necessary to evaluate their importance. Comparison of theoretical predictions with experimental results contributes important new understanding of the complex nature of this process. The reduction process has been studied under a wide range of experimental variables, and it is not surprising that apparent conflicts in observation and interpretation appear in the literature. The interested reader is referred to the reviews of Themelis and auvin"? and Manning and philbrook3 for a description of much of this work. The course of reaction commonly has been followed by measuring the oxygen weight loss from the particle as a function of time. A number of authors have suc- cessfully correlated their data in terms of a model which assumes that the reduction process is controlled by the rate of reaction at a single, sharply defined, advancing interface. According to this model, the interface will advance linearly with time. A mathematical model for gaseous reduction in a packed bed developed by the present authors in an earlier paper4 recognized that reduction must proceed through the series hematite (Fe203), magnetite (Fe30,), wiistite (Fe,O), and finally metallic iron. The reduction scheme permitted a stepwise topochemical reduction of the individual particles to metal or to the lowest oxide thermodynamically possible for the local gas composition in the bed. The limiting situations of theoretically dense and very porous oxide structures were considered. On the basis of available experimental evidence, the simplifying assumption was made in each case that all product layers would thicken linearly with time. A generalized single-particle model has now been developed to determine the significance of transport resistances in the product layers and in the gas film surrounding the particle. The analysis shows that the interplay of transport and chemical resistances is such that an apparently linearly advancing interface may be observed despite the fact that the reaction may be under significant transport control. Attention thus far has been focused on the development of a model for the topochemical behavior of dense spheres of hematite in atmospheres capable of reducing them completely to metal. The formation of successive product layers of iron, Fe,O, and Fe304 is assumed to follow the mechanism originally described by dstrijm.' All oxygen removal from the core occurs at the iron/Fe,O interface, intermediate oxide layers being propagated by sol id-state diffusion without change in the oxygen density of the core. Since fractional reduction is operationally defined in terms of oxygen weight loss, the kinetics of the over-all reduction of FeZ03 to iron is properly studied in terms of the gas-solid reaction occurring at the iron-wiistite interface. The fractional reduction of a partially reduced oxide sphere is given by: here refers to the radial position of the iron/Fe,O interface. This model is not universally applicable because, as explained in the earlier paper,4 a consideration of porous particles or of dense particles in atmospheres not capable of reducing wiistite must allow for the possibility of gaseous reduction at interfaces other than the one between iron and Fe,O. However, evidence that certain hematite specimens actually do follow the dense-pellet mechanism developed here is provided by the data of cewan' and of Bogdandy and

Jan 1, 1967

By V. M. Karve, K. K. Majundar, K. V. Viswanathan, J. Y. Somnay

The effect of calcium, magnesium, iron (both ferrous and ferric) and aluminum ions, which are commonly encountered in a typical beryl ore, was studied in the flotation of pure beryl, soda-feldspar and quartz. The vacuumatic flotation technique was employed. With sodium oleate as collector and in the absence of any activator, beryl floated in a pH range of 3 to 7.5, whereas feldspar and quartz did not float at any pH up to 11.5. The pH range of flotation increased in the presence of the ions studied. With calcium and magnesium ions beryl floated from 3 to 11.5 pH and beyond, soda-feldspar floated beyond pH 6 and quartz floated beyond pH 8. Ferrous ion activation was found to be similar to that of calcium and magnesium. Activation by ferric and aluminium ions was found to be complex and the lower and upper critical pH for all the three minerals was around 2 and 10 respectively. These studies indicated the possibility of separation of beryl from feldspar and quartz even in the presence of calcium, magnesium and ferrous ions between pH 4 and 6. Flotation tests on a mixed feed of pure minerals in a 10 g cell revealed that beryl can be selectively floated from feldspar and quartz if ferric ion is reduced to ferrous state or if it is complexed. Beryl occurs mostly in pegmatites, and hence is associated with feldspar, quartz and micas and small amounts of other minerals such as apatite and tourmaline. The separation of beryl from these minerals is difficult because all the silicates accompanying beryl have more or less the same physical properties. Specific gravities of beryl, feldspar and quartz are 2.70, 2.56 and 2.66 respectively. Electrostatic separation has been suggested but no work has been reported. ' The adsorption of sodium tri-decylate tagged with Cl4 on beryl, feldspar and quartz reveal similarity in surface properties. Much work has been reported on the flotation of beryl from ores, either directly or indirectly as a by-product, but little is known about the fundamental aspects of beryl flotation. Kennedy and O'Meara3 laid emphasis on prior cleaning of the mineral surfaces with HF. Mica is removed first by flotation of beryl with oleic acid, around neutral pH. Runke4 introduced calcium hypochlorite conditioning in a final separation stage for activating beryl in a mixed beryl-feldspar concentrate, and after washing to remove the hypochlorite, floated beryl with petroleum sulphonate. The Snedden and Gibbs5 procedure is somewhat similar to that of Kennedy and O'Meara. Emulsified oleic acid is used as collector. Recently Fuerstenau and Bhappu6 studied the flotation of beryl, feldspar and quartz with petroleum sulfonate in the presence of activators and stressed the importance of iron in the flotation of beryl. From the studies conducted in this laboratory, it was found that feldspar and quartz as such do not float with sodium oleate, but in practice selective flotation of beryl from feldspar and quartz in an ore is found to be impossible with sodium oleate as collector. A glance at the chemical analysis of typical beryl ore indicates the presence of several ions like Ca ++, Mg++, Al + + + and Fe+++ in abundance and Ti++++ and Mn++ in traces. Hence, in an attempt to explain the behaviour of feldspar in the beryl flotation, the effect of Ca++, Mg++, Al+++ and Fe+++, which are known as gangue mineral activators7'8 has been investigated. Materials and Methods: Lumps of beryl ore (hand picked) were boiled with 10% sodium hydroxide and washed with distilled water. They were further boiled many times with 10% hydrochloric acid till no positive test for iron was obtained with ammonium thio cyanate. This was followed by thorough flushing with double distilled water. The lumps were crushed in a porcelain mortar and pestle under water. The minus 65 + 100 mesh fraction was used for testing and was always stored under distilled water. Pure feldspar and quartz were similarly prepared and the minus 65 + 100 mesh fractions collected. Inorganic ions tried as activators were ca++, Mg++ , Fe++, Fe ++ and A1 +++ . Calcium nitrate, magnesium chloride, ferrous ammonium sulfate, ferric ammonium sulfate and aluminum nitrate of G.R.E. Merck grade were used. B.D.H. technical grade sodium oleate was used as a collector. The vacuumatic flotation technique developed by Schuhmann and Prakash was used for studying the effect of pH on flotability. 7 The indications given by this work were confirmed by using 10 g miniature cell.'

Jan 1, 1965

By Barbara A. Thompson

A previously reported high-resolution method for the location of boron-rich areas in metallurgical and biological specimens was been adapted for general use on a routine basis. The rnetlzod utilizes neutron activation and autoradiograpizy. Alpha-particles emitted by boron nuclei upon neutron capture are recorded on a photographic emulsion. The resulting a-particle tracks show the location of boron-rich areas. Experimental techniques, interferences, and limitations of the method are discussed in detail. The method is most useful where there is marked segregation of boron. In this type of sample, the segregation can be observed when the nominal boron concentration is as low as 0.0006 pct. THE positive identification and location of boron-rich areas in metals is frequently of great interest in metallurgical work. Unequivocal identification is often difficult to make by conventional metallo-graphic methods. Recently, a method has been described which accomplishes this objective by neutron activation and autoradiography.l-3 The method can be described briefly as follows. Upon neutron capture, a -particles are emitted by boron nuclei according to the following reaction: ,Blo + n - ,a4 + 3Li7 + 2.4 mev The energy is dissipated as kinetic energy of the products. By irradiating a boron-containing sample in contact with a photographic emulsion and subsequently developing this emulsion, a-particle tracks are obtained whose location corresponds to the location of boron-rich areas in the sample. Two factors combine to make the reaction extremely specific for boron. The first is the unusually high (755 barns) cross section of boron for thermal neutron capture. The second is the higher neutron energy required to produce (n, a ) reactions in essentially all other nuclei except lithium. These two factors make the method specific for boron by six to seven orders of magnitude when a predominantly thermal neutron source such as the Brookhaven reactor is used. The reported limit of detection of this method is of the order of 0.01 pct B., The present work was originally undertaken to determine whether this limit could be lowered by use of a thinner emulsion. However, initial experiments showed that in order to use the method at all, it was necessary to reestablish the optimum experimental conditions in terms of the available irradiation facilities. It is the purpose of this paper to describe these experimental conditions in detail, to discuss the factors influencing sensitivity, and to evaluate several techniques for increasing sensitivity. EXPERIMENTAL A) Preliminary Experiments—The first measure-ments were made using samples of crystal oriented silicon steel containing various concentrations of boron. In the later experiments, samples of various high-temperature alloys such as M-252, hcoloy 901, Nichrome V, and so forth, were used. Faraggi, et al.,2 reported that the lower limit of sensitivity in this type of sample was about 0.01 pct B using nuclear emulsions of 50- u thickness. but that it should be possible to extend this limit by the use of thinner emulsions. Accordingly, we first used Kodak Auto-radiographic Stripping Film (Permeable Base) which has an emulsion thickness of only 5 µ. This was mounted on the metallographic specimens according to the technique described by Boyd.4 The emulsion remained in contact with the metal surface throughout exposure and development. Since the emulsion is transparent after development, the autoradiograph and metal surface can be viewed simultaneously and any correlation between film blackening and structure of the metal can be made directly with no problems of realignment. Because the silicon steel is readily attacked by moisture alone, it was necessary to apply a protective coating to the metal surfaces before mounting the emulsion. The coating was made extremely thin in order to absorb as few a-particles as possible. Boyd4 and Gomberg5 have discussed various plastics used for this purpose; however, none was sufficiently impermeable to prevent chemical attack of the steel during the developing process. This attack resulted in the production of gross chemical artifacts in the emulsion. It was, therefore, necessary to use the method of Wolfsberg and John6 as follows. A very thin (approximately 1 µ) coating of Plexiglas II was applied by dipping the sample in a 2 pct solution of Plexiglas II in dichloroethylene. Then, because the emulsion will not adhere to Plexiglas 11, a thin coating of Parlodion was applied in a similar manner using 2 pct Parlodion in iso-amyl acetate. No protective coating was necessary with the high-tem-

Jan 1, 1961

By A. Mitchell, T. Bagshaw

A recent paper by Thomas1 has presented new data on the solubility of hydrogen in solid silver at 1 atm pressure in the temperature range 600° to 963°C. However, no data is reported in the literature on hydrogen solubility in liquid silver. The Sieverts technique which has been described previously2,3 was used in the present work. Charges of approximately 160 g were melted in Morgan "purox" recrystallized alumina crucibles and purified helium was used for the determination of the "hot volume" during each experiment. A chemical analysis of the silver indicates that the impurity content (Cu + Al) is less than 0.02 wt pct. Hydrogen solubility in the temperature range 963° to 1200°C was investigated. The results of three experiments are shown in Table I. Fig. 1 shows an Arrhenius plot of the present work together with the solid-state data of Thomas, Steacie, and johnson,4 Eichenauer et al.,5 and Siegelin et al.6 The following expression has been derived from the Arrhenius plot of the present data: log (solubility of hydrogen, cm3 per 100 g) = 2.154-3512.0/ToK The heat of solution derived from Fig. 1 is 31,150 cal per g mole H2 compared with the value of 33,020 cal per g mole H2 obtained by Thomas and 12,000 cal per g mole H2 obtained from the data of Steacie. It was observed that hydrogen evolution took place when the silver melts were solidified under 1 atm of hydrogen, which would not be expected from an extrapolation of the results of Steacie. Schenck and Lange7 have observed that, for several transition metals at their melting points, the ratio of the hydrogen solubility in the liquid to that in the solid lies in the range 2.1 to 3.1. The present results and those of Thomas are in accord in this respect having a ratio of 2.8. 'C. L. Thomas: Trans. TMS-AIME, 1967 vol. 239, pp. 485-96. 2T. Bagshaw and A. Mitchell: I. Iron Steel Inst., 1966, vol. 204, p. 87. 'M. Weinstein and J. F. Elliott: Trans. TWS-AIME, 1963, vol. 227, p. 382. 'E. W. R. Steacie and F. M. G. Johnson: Proc. Roy. Soc. (London), Ser. A, 1928, vol. 117, pp. 662-79. 'W. Eichenauer et al.: Z. Metallk., 1958, vol. 49, pp. 220-25. 6W. Siegelin et al.: Z. Elektrochem., 1957, vol. 61, pp. 359-66. 'H. Schenck and K. W. Lange: Arch Eisenhuettenw., 1966, vol. 37, no. 9, pp. 739-48.

Jan 1, 1969

By C. G. Dunn

NUCLEI that are formed during the recrystallization of a grain following plastic deformation generally have orientations that differ from the original. This aspect of recrystallization may be described in terms of orientation changes. It was shown previously, in an investigation on recrystallization in silicon ferrite,1 that the observed orientation changes were highly improbable on a chance basis, and that some mechanism must be involved. Analysis showed that the data could be satisfactorily classified into the smaller of two subclassesf of the 36 third- order twin transformations. No attempt was made at that time to classify the data within the special class of 12 third-order twin transformations, although results did indicate a greater probability for some of them to occur. A classification of this type would be more valuable, of course, with more data on orientation changes per old deformed grain. The present work fulfills this condition to some degree and also extends the scope of the investigation to include the effects of original orientation and the amount of plastic deformation. The effect of original orientation is of considerable interest because of the known effects of orientation on plastic deformation, particularly with regard to degree of fragmentation and the formation of de- formation bands, and because the orientations produced by deformation should influence the orientations obtained through recrystallization. Barrett and Levenson2 reported that single crystals of iron deformed in the range 82 to 97 per cent could be put into three general classes; namely, crystals in class I maintained a reasonably sharp single orientation, those in class 2 transformed into two distinct orientations, and those in class 3 changed into a large number of major and minor orientations. Something similar would be expected for silicon ferrite crystals, and verification of this for a few cases of types class I and class 2 deformation has been reported elsewhere3 for single crystals of silicon ferrite cold-rolled in the range 10 to 20 per cent. As an example of class 2 deformation, it was shown that a crystal of silicon ferrite cold-rolled in a {110} plane in a < 100> direction developed two layers, or deformation bands differing in orientation. When this happens it is possible to etch away one band and leave a single structure for use in studying the orientation changes that occur during recrystallization. when preferred crystal orientations are obtained in recrystallization, it is notparticularly necessary to evaluate groups of common orientation, as was done previously (ref. I, Table 6); but an

Jan 1, 1946

By R. P. Rothwell

THE first difficulty mentioned is that in some instances two or more beds of coal separated by sandstone or slate rocks of considerable thickness in one part of a basin, are found running together in another part. Of course, we may happen to strike first the part of the basin where there is but a single seam, and in this case the bed would appear to divide into two or more branches within a short distance. Such cases are not rare in the anthracite coal-fields. I would suggest as an explanation of this phenomenon the gradual sinking of the peat-marsh-the embryo coal-bed-on one side, and the moving forward of the marsh, so that on one part of the bed the formation of peat would still be progressing, while another part, being under water, would be covered with mud and sand. Thus we have different portions of the same bed of different ages. Now if the sinking of the marsh be stopped for a time, the bed will become thicker in the portions left exposed, and if the sinking now changes in direction, so that the part that had previously gone down com¬mences to rise, we should have the phenomenon of a bed, continuous throughout, with one portion overlying another, and separated from it by rock strata. These are exactly the conditions observed in splitting beds. While one side of the lake is sinking, and the peat-marsh moving on in that direction, the other side may be rising,

Jan 1, 1873

By R. S. Sandhu, L. E. Baker, W. Y. Shieh

The finite element method of analysis was introduced by Clough.1 Within a short period, it has developed into a powerful solution technique in structural and continuum mechanics. It has been used to solve boundary value problems in two and three-dimensional elasticity.2-5 Anisotropy and heterogeneity of materials were allowed for at the earliest stages. 1,4 Its application has been extended to allow for cracks,5 creep and viscoelasticity, 6,7 incremental construction,6-8 nonlinear elasticity3,9 effect of joints in rock,10 and to materials with different behavior in tension and compression.7 Because of its versatility, the finite element method has found increasing application in the field of rock mechanics. In fact, several of the more significant developments have been motivated by problems in this field. Elasto-plastic material behavior based on the incremental or rate-type theory of plasticity rather than the deformation theory was considered by Reyes and Deere11 A material law based on a generalization 12 of the Mohr-Coulomb criterion was used. In this chapter, the formulation of material laws developed by Reyes and Deere 11 is used. An efficient analysis procedure, incorporating recent developments in finite element analysis, is developed for plane-strain conditions. To demonstrate its effectiveness, the procedure is applied to three cases, one for which an exact solution is available, another for which field observations had been made, and a third one for which a parallel study was made, using an accepted limit-equilibrium method.

Jan 1, 1970

By Thomas M. Brown

The method usually employed in accurate determinations of sulphur in pig-iron and steel is to treat a weighed sample of borings in a flask with muriatic acid, and to pass the gaseous products through an alkaline solution of lead or silver, which precipitates all the solphur of the sulphuretted hydrogen in the form of sulphide of lead or silver. The sulphide thus formed is subsequently oxidized by aqua regia, bromine, or other oxidizing agent, and the sulphuric acid formed precipitated in the usual way by chloride of barium. I have substituted for the alkaline metallic solution, a solution of permanganate of potash in the strength of one gramme of permanganate to 200 cubic centimetres of water, and find that it gives results quite as accurate as those obtained by using an ammoniacal solution of silver. By the employment of the permanganate it will be readily seen that there is considerable saving of time and work. In order to test the accuracy of the method, six samples of pig-iron borings were weighed out (about six grammes each) and treated identically

By Richard Akerman, Frederick Prime Jr

[THE attention now being paid both in this country and Europe the greatest economy in the working of the blast furnace, and the eagerness with which all thoughtful men in the iron business look for any new information which will tend to throw light on this subject, is a quite sufficient excuse for presenting this paper to the American Institute of Mining Engineers.] I. It must be borne in mind that when two bodies unite to form a chemical compound, heat is almost always evolved. In order to

By C. H. Wilson, J. J. Jakosky

In recent years geophysical prospecting methods have become well established as important steps in economically initiating new mining ventures in the field of base-metal exploration, placer mining and water-supply problems. The value of these methods as applied to these problems has been greatly increased by new and improved instruments, and a greater degree of skill in laboratory and interpretative technique. Considerable success has been attained, with subsequent drilling checking the predicted depths within 1 to 5 per cent, on problems requiring information on thickness of fill material, depth to and contour of bedrock, extent and yardage of gravels to be mined, and location of hydrostatic water table. In these applications the geophysical work gives data comparable to drilling, and at a cost of about one-fiftieth that of drilling. Discussion of several surveys with accompanying illustrations showing geophysical methods applicable to both simple and complicated placer problems are contained in the paper. The electrical instruments for measuring electromagnetic field strength and surface potentials are described, and their use, coupled with that of other geophysical instruments in modern field procedure, is noted.:

Jan 1, 1934

By William F. Haddon, Phillip J. Maddex

Marco Polo brought the first borax to Europe late in the 13th century. It was especially treasured then for one of its many qualities-that of working with gold as a soldering flux. Georgius Agricola in 1556 gave it the name chrysocolla (which the Moors called borax)-literally, "gold glue." Deposits of borax have been elusive and widely scattered-first found only in Tibet and Italy, and, in 1836, at Iquiqui, Chile. Dr. John Veatch made the first California discovery in 1856 while examining a mineral spring east of Red Bluff. This "Borax Lake" soon supplied 90% of U.S. demand, but flooding and other production problems caused the scene to shift from Borax Lake to Little Borax Lake and then to Nevada in 1871. Early transportation was by "Twenty-Mule Teams."

Jan 1, 1971

By R. E. Robbins, H. R. Brager

THIS note describes an unusual result obtained in an electron microscope investigation of cavities produced in commercial type 304 stainless steel irradiated in a thermal reactor (ETR) at 290°C to a high neutron flu-ence, 6 x loz1 n per sq cm. The analysis of the steel used is given in Table I. The unusual result is that the calculated quantity of helium gas produced by transmutation during the irradiation, 12 ppm, is less than one-tenth the amount of gas necessary to balance the surface tension of the observed cavities produced in the steel during ETR irradiation. Therefore, the cavities would be expected to behave like voids; however, they behave like "gas filled" bubbles. The maximum quantity of helium produced in the steel by B" transmutation was 8 ppm. In addition, the amount of helium formed by (n, (1) fast neutron reactions with the major alloy constituents and nitrogen was calculated to be 4 ppm based on the tabulated differential or effective fission-averaged cross sections of elements in type 304 stainless steel irradiated in typical thermal reactors.&apos;, In previous investigations concerning commercial austenitic stainless steel irradiated in a thermal reactor, the amount of helium gas calculated to be produced by transmutation has always been significantly greater than the amount calculated on the basis that the bubbles were gas filled, PPs= 2y/R. The balance of the gas was assumed to be in bubbles smaller than could be detected on the electron micrographs. Accordingly, the bubbles were attributed to helium produced from transmutation of impurity boron by thermal neutrons. These bubbles were not uniformly dispersed in the matrix but were located principally at grain boundaries, or were radially positioned around a few precipitates located in the matrix and at the grain bundaries., 4 Voids have also been observed in austenitic stainless steel irradiated at high temperature to high neutron fluences in the EBR-I1 and Dounreay Fast Reactors. The voids were uniformly distributed throughout the matrix. The amounts of helium gas produced by transmutation during these irradiations were less than one-tenth the amounts needed to balance the surface tension of the voids formed by the fast reactor irradiation. The fast reactor results are quite analogous to those reported here for the ETR irradiated steel. Electron microscope examination of the fast reactor irradiated material after a 1 hr postirradiation annealing at 900°C disclosed that essentially all the voids had been eliminated. The authors stated that the voids had developed due to the high concentration of vacancies produced during irradiatin., 6, &apos; The microstructure of the ETR irradiated material as-tested at 75O°C, Fig. 1, contained about 2 X lot5 cavities per cm3 with an average diameter of 110A. With the Van der Waals b correction and y = 1500 ergs per cm2, 300 ppm He would balance the surface tension of the observed cavities. Stereoscopic examination of the electron micrographs showed that the cavities were neither preferentially located near the grain boundaries nor highly concentrated at specific regions or precipitates. The cavities were nearly uniformly distributed throughout the matrix, on dislocations and at grain boundaries. These observations imply that the cavities were not the sole results of B&apos;O

Jan 1, 1969

By R. M. Jorda

The mechanism of parafin deposition and prevention has been studied in the laboratory using an apparatus which provides a quantitative means of studying parafin deposition on metal and plastic surfaces. The amount, hardness, adhesion, per cent wax and mean molecular weight of parafin deposits appear to be governed by surface roughness alone, all other conditions being constant. Tests of various plastic coatings indicate that most smooth, nonparafinic plastics are capable of reducing parafin deposits in oil wells, but flexible, highly polar, nonparafinic plastics are more suitable for providing long term resistance to parafin deposition in oil wells if the flow stream contains abrasive materials. INTRODUCTION The problem of paraffin deposition is one of long standing in the oil industry.&apos; Crude oils often contain paraffins which precipitate and adhere to the liner, tubing, sucker rods and surface equipment as the temperature of the producing stream decreases in the normal course of flowing, gas lifting or pumping. Heavy paraffin deposits are undesirable because they reduce the effective size of the flow conduits and restrict the production rate from the well. Where severe paraffin deposition occurs, removal of the deposits by mechanical, thermal or other means is required, resulting in costly down time and increased operating costs. The troublesome paraffins are normal hydrocarbons ranging from approximately C15H38 to C38H78 mixed with small amounts of branched paraffins, monocyclic paraffins, polycyclic paraffins and aromatics.&apos; The amount of paraffins found in crude oils varies from less than 1 to more than 30 per cent. Many publications are available which deal with this problem, and perhaps the most significant findings in recent literature are contained in a publication by Hunt3 ho developed the "cold spot tester", a really useful means of investigating paraffin deposition. Hunt&apos;s observations led to many generalized conclusions concerning the effect of surface roughness on paraffin deposits. He ascertained that there was an observable qualitative correlation between the severity of paraffin deposition and the roughness of the surfaces which he tested (cold rolled steel, stainless steel and several plastics). Because of the number of meaningful observations made by Hunt, his cold spot tester was modified somewhat and extensive tests were per- formed to study the quantitative relationship between surface roughness and the physical and chemical nature of paraffin deposits. LABORATORY TEST PROCEDURES The cold spot test apparatus consists of a flat circular plate mounted on a curved tube and positioned in a vessel containing a wax-oil solution (Fig. 1). The apparatus is arranged so that the temperature of the central portion of the circular plate can be varied by means of a circulating liquid stream; the test equipment includes provisions for maintaining a constant wax-oil solution temperature and stirring speed. In the paraffin deposition studies, the modified cold spot tester was used as follows. The cold spot probe consisted of a flat circular plat 2 in. in diameter and 1/8-in. thick positioned in the wax-oil solution kept at constant temperature. As in Hunt&apos;s earlier experiments," a cold liquid was circulated through a tube connected to the circular plate so that the liquid impinged on one side of the plate cooling the plate from the center outward, causing paraffin to deposit on the side of the plate exposed to the wax-oil solution.

Jan 1, 1967