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By P. G. Shewmon

A novel technique for determining the surface energy (?) and its derivative with respect to orientation, (?') is described. Essentially it involves the 'floating" of a wedge on the substrate, said wedge being made of a material which is not wet or only slightly wet by the substrate, i. e., as a greased needle "floats" on water. A thermodynamic analysis of a system in which the wedge is supported entirely by surface energy is given. If the original suyface is not at a cusp orientation, the surface tension is directly measurable from the groove angle formed. If the original surface is at a cusp orientation, there may or may not be a groove depending on the relative value of ?' and the weight of the wedge. Experiments primarily on copper and silver showed that sapphire, quartz and refractory metal wedges were wet while graphite wedges were not. The technique was demonstrated to work using graphite wedges, but the results obtained were not as eccurate as those obtained by other workers using the wire-creep experiments. It is concluded that the technique might prove most useful with non-metals where ?' is large and filament creep experiments would be quite difficult. If an absolute value of the surface free energy (?) of a metal is to be determined, the most reliable methods used to date measure an average over the various orientations exposed on a polycrystalline sample. For example, ? for silver, gold, and copper have been measured by determining the force required to just keep a thin wire,' or foil,' specimen from contracting under the influence of ?. Herring 3 has predicted and experiment confirms, that the sensitivity of this method is inversely proportional to the grain size.' Thus it cannot be used to measure ? for a particular orientation by using a foil single crystal or a very coarse-grained specimen. An accurate value if ? for tungsten averaged over a range of orientations has been determined using a field emission technique. The same techniques cannot or have not been used to measure ? for non-metallic solids, and as a result the values available are much less accurate.4 This Paper resents a means of making an absolute determination of ? for a particular surface orientation on any solid, as long as the given surface orientation does not break up into other orientations during an anneal. Experimentally ? is found to vary with orientation and at a few low index orientations it is found to have a cusped minimum, i.e., the derivative of ? with respect to the orientation of the surface changes discontinuously at the low index orientation, see Fig. 1. The slope of a plot of ? vs orientation (herein designated ?') is called the torque on the surface, since it tends to rotate the exposed surface toward the low index orientation, or if the surface is at the cusp orientation it opposes any force tending to rotate the surface out of the low index orientation. The ratio ?'/? has been determined for a few metals, but in cases where this ratio is high there is presently no means of determining either ?'/? or the absolute value of ?' for the orientations present on an annealed surface. The technique discussed herein also provides a means of determining an absolute value of ?' for those orientations which deviate only infinitesimally from a cusp orientation. It should work best on surfaces where ?'/? is large; that is, for cases where no other technique is available for measuring ?'. Aside from trying to learn more about surfaces through measuring ? and ?', the primary reason for wanting values of ? or ?' is to study adsorption. From measurements of the variation of ? for a particular orientation with the concentration of an impurity, one can obtain the number of impurity atoms adsorbed per unit area (Ti) on that orientation using the Gibbs adsorption equation.' where µi is the chemical potential of the adsorbed impurity. Thus, if absolute values of ? could be obtained for the free surface of a given surface orientation as a function of µi, ri could be determined for the given orientation. Furthermore, by equilibrating a grain boundary with the given surface at various values of ki, one could also determine ri for the grain boundary. Similarly Robertson 6 has pointed out that if y is taken to be a continuous function of and µi, then a2 ?/a @a µ2 = a2 ?/a pi a +. Thus, at all orientations away from cusps the following equation holds From a measurement of ?' vs ki, it is thus possible

Jan 1, 1963

By A. H. Heim

A method and apparatus for measuring gas porosities of rocks are described. The apparatus can be assembled from commercially available components. In principle, measurements are made by volume substitution at constant pressure. The maximum error is not more than 0.3 porosity per cent. Typical results are given. INTRODUCTION Determining the porosity of rock samples is one of the most important and yet most varied types of measurement in core analysis. Among the many techniques devised are the so-called "gas porosity" methods. An old and well known example is the Washburn-Bunting method.' The U. S. Bureau of Mines2-' described and later improved the apparatus for a now widely used method generally known as the "Boyle's law" method. In the present form of the Washburn-Bunting method,' the volume of air in the pores of a rock sample at atmospheric pressure is extracted and then collected in a graduated burette at atmospheric pressure. The volume of air is read directly as the pore volume of the sample. The absolute error in reading the collected volume of gas is independent of the total volume; thus, the relative error is larger when the volume is small, as it is for rocks of low porosity. In addition, the sample after measurement contains mercury, which limits its use for other analyses. The Bureau of Mines (or Boyle's law) method measures directly the solids volume of a sample from which the pore volume and porosity are derived, using a separate measurement of the bulk volume. Gas at a few atmospheres pressure is introduced into a sample chamber of known volume containing the rock sample. The pressure is accurately measured. Following, the gas is expanded into a burette at 1 atm, and the gas volume is read directly. From the initial pressure p, and the final pressure p2 and volume v,, the initial gas volume v1 is calculated using Boyle's law; that is, p1v1 = p2v2. Volume v, minus the volume of the empty sample chamber is the solids volume of the sample. The accuracy of the method is limited, unless corrections are made, by deviations of the gas from the "ideal" gas-law behavior assumed in the simple form of Boyle's law. The purpose of the present paper is to describe a method for measuring the gas porosity of a rock which avoids many of these difficulties. Gas volumes are measured directly with the same accuracy as the bulk volumes. Pressures of at least an order of magnitude larger than those of previous methods are employed to insure rapid penetration of the gas into the sample. While special equipment may be built to apply the method, the porosimeter may be constructed as well from commercially available components. For simplicity, the apparatus described will be referred to as the "Constant-Pressure gas porosimeter". THE CONSTANT-PRESSURE METHOD Fig. 1 shows schematically the arrangement of components comprising the present Constant-Pressure porosimeter. Briefly, the method is one of volume substitution and may be considered a null measurement. Omitting (for the present) some of the operational details, the method of measurement consists of the following three steps. 1. After evacuation, the volume of the measuring system (a ballast chamber, a manifold, two gauges and their connections) up to the sample chamber is filled with gas to a high pressure (- 1,000 psi). A sample of the gas at this pressure is trapped in one side of a sensitive differential pressure gauge to serve as the reference pressure for subsequent steps. 2. The evacuated sample chamber containing the rock sample is opened to the measuring system. As the gas expands into the chamber, the resulting decrease in pressure unbalances the differential pressure gauge. 3. The pressure is restored by means of a mercury volumetric pump. The volume of mercury injected exactly equals the free or void volume of the sample chamber (volume of empty chamber minus the solids volume of the rock within). From the injected volume and the known empty chamber volume, the solids volume is obtained and the porosity calculated. The pressure and the volume occupied by the gas are the same before and after opening the sample chamber. Expansion and compression of the gas are incidental operations and do not enter into the calculation of porosity. By the pressure balancing or nulling, the free volume of the sample chamber is merely substituted by an equal and measured volume of mercury. Since the measurements are at constant pressure, there are no compressibility corrections necessary for the sample chamber.

By G. H. Bishop

The kinetics of the inter granular penetration and embrittlement of [100] tilt boundaries in 99.998 pct pure nickel upon exposure to bismuth-rich Ni-Bi liquids have been determined in the temperature range from 700° to 900°C. The kinetics of penetration are parabolic in time at constant temperature over most of the temperature range. In a series of 43-deg bicrystals the rate of penetration is anisotropic with respect to the direction of penetration into the grain boundaries. In lower-angle bicrystals the penetration rate is isotropic. The rate of penetration decreases with tilt angle at 700°C. The activation energy for penetration in the 43-deg bicrystals is 42 kcal per g-atom independent of direction. It is concluded that the intergranular penetration and embrittlement in the presence of the liquid proceeds by a grain boundary diffusion process and not by the intrusion of a liquid film. This was confirmed by a determination that the kinetics of penetration and embrittlement were the same in the 43-deg bicrystals upon exposure to bismuth vapor under conditions such that no bulk liquid phase would be thermodynamically stable. WhEN solid metals are exposed to a corrosive liquid-metal environment, the grain boundaries are sites of preferential attack. Depending on the temperature, the composition of the liquid, and the composition, structure, and state of stress of the solid, a number of modes of attack are possible. This paper reports a study of the kinetics of intergranular penetration and embrittlement of high-purity nickel bicrystals upon exposure to bismuth which, together with an earlier study by Cheney, Hochgraf, and Spencer,&apos; demonstrates that there are at least two modes of intergranular attack possible in the Ni-Bi system. In the study by Cheney et al., columnar-grain specimens of 99.5 pct pure nickel were exposed to liquid bismuth presaturated with nickel in the temperature range 670" to 1050°C. They found that the majority of the boundaries, which were predominantely high-angle boundaries, were penetrated by capillary liquid films, the attack proceeding by a process which will be termed grain boundary wetting. This process occurs in a stress-free solid when twice the liquid-solid surface tension is less than the surface tension of the grain boundary,* i.e., when 2yLs < YGB In this case the penetration of the grain boundary by the liquid occurs at a relatively rapid rate, resulting in the severe embrittlement of a polycrystalline solid. Grain boundary wetting is a common mode of intergranular attack in systems in which the lower melting component is relatively insoluble in the solid, but the solid has an appreciable solubility in the liquid, for example, the Ni-Bi system, Fig. 1. In systems of this type at temperatures above the range of stability of any intermetallic phases, once the liquid is saturated with respect to the solid so that no gross solution occurs, chemical gradients are small, and surface tensions become major driving forces for attack, provided the solid is stress-free. The results of Cheney et al. appear to be typical of those encountered when grain boundary wetting occurs.&apos; Capillary films were observed in the boundaries after quenching from the exposure temperature. The mean depth of penetration increased linearly with time, and the activation energy for the process was found to be 22 kcal per g-atom. In a study of the Cu-Bi system Yukawa and sinott4 found that the depth of penetration of bismuth into high-purity copper bicrystals of orientations from 22 to 63 deg of tilt about (100) at 649°C ranged from 0.05 to 0.25 in. after a 12-hr anneal. This corresponds to a linear rate of 6 to 15 X 10~6 cm per sec. At the same reduced temperature of 0.68 the rate for the Ni-Bi system&apos; was 7 x lo-&apos; cm per sec. In another study of the Cu-Bi system, Scheil and schess15 determined the kinetics of grain boundary wetting in hot-worked commercial rod. While there were several complicating factors present in this study, there is general agreement with the above results. The kinetics of penetration were linear, the activation energy was 20 kcal per g-atom, and at 650°C the rate of wetting was 2 to 5 x 10-6 cm per sec. The rate of wetting in the A1-Ga system6 is somewhat

Jan 1, 1969

By R. O. Williams

Analytical representation of the thermodynamics of solutions is highly desirable from the standpoint of accuracy, compactness, and numerical manipulations. In particular, computer calculations are greatly implemented. Mathematical considerations show that previous expressions have one or more serious defects. This investigation shows a Fourier series to be satisfactory but that it is also possible to derive a new series which fits certain additional conditions. Included examples show the value of analytical expressions in giving a simple characterization of each system using some two to five parameters, the elimination of the Gibbs-Duhem integration, and the es timation of the error for the experimental function as well as derived functions. It is further shown that the present characterization provides easy comparison between systems. IN the past, thermodynamic calculations have depended to a considerable extent on tabular and graphical methods. As the volume and precision of such data increase such methods become less satisfactory. Specifically, the selection of the optimum representation and the estimation of errors require statistical methods which in turn require analytical representation. The utilization of such data require further manipulations which are best done analytically for maximum precision. For example, phase equilibria are determined by common tangents to free-energy curves: a graphical determination is normally of low accuracy. As computers are increasingly used analytical representations become almost mandatory. Insufficient mathematical consideration has been given previously to the selection of empirical expressions. Those expressions having some theoretical justification are generally too inflexible and mathematically unattractive. We consider the problem in some detail and show that a Fourier series can be effectively used. Also a new series is defined which has certain advantages. ANALYSIS We wish to consider the analytical representation of the heat of mixing, AH, the excess free energy, ?Gxs, and the excess entropy, ?sXS, as a function of composition, X, for binary solutions relative to the pure components in the same state. When a distinction is not required, we use W to denote any one of the above functions. One may use a Taylor expansion around X = 0 to generate a power series. As the derivatives are un- known we represent the series as W = A + BX + CX2 + DX3 + EX4 + ... [l] where the constants A , B, C , ..- are to be selected to provide some optimum fit. For the extremes of composition W is necessarily zero so it follows that A = 0 [2a] B +C + D + E +••• = 0 [2b] Nonelectrolytes, which we are considering, appear to satisfy the condition that d3W/dx3 = 0 [3] in the terminal regions. This is the basis of the a, ß, and Q functions used by Hultgren et al.&apos; and others. While this condition does not have a strong theoretical basis it does appear desirable that any analytical relation should satisfy this condition. Darken2 and Turk-dogan and Darken3 have shown that many systems exhibit this behavior over an extended range from each terminal region, departure being restricted to a limited intermediate region. Since we have no a priori knowledge as to where this transition occurs we can require that this condition be satisfied only as a limit at the extreme compositions as a general condition. We will show later how more restricted conditions can be included in specific solutions. Darken2 has called this behavior the quadratic formalism; we call our application the limiting quadratic formalism, LQF. This condition applied to the above power series requires that D = 0 [4a] 4-3-2E +5-4-3_F + 6 • 5 . 4G + ••• =0 [4b] The form of the power series normally used, due to Margules,4 is W=X(1-X)(A + BX + CX2 + DX3 + EX4 + •••) [5] where A, B, C, --. are a new set of constants. (Guggenheim5 has given a variation of this expression in a more desirable form. Since, however, it is contained in the above expression it does not require separate consideration.) This form is precisely what results by incorporating the conditions in Eq. [2] into the power series and regrouping the constants. The LQF requires that B =C [6a] and 4.3.2(D-C) +5-4-3(E-D) + ••• =0 [6b] Thus, the correct form of the Margules expression with two adjustable parameters is w =X(1-X)[A + B +X2-2/3x3)] 171 and the EX4 term must be included before three adjustable parameters are permitted.

Jan 1, 1970

By M. D. Arnold, P. B. Crawford, P. C. Hall

An experimental study has been made to determine the optimum flooding pressures for four different oils. The oil formation volume factors ranged from 1.08 to 2.13, and solution gas-oil ratios ranged from about 200 cu ft/bbl to 2,250 cu ft/bbl. Viscosities ranged from 0.38 to 0.95 cp at the respective bubble points of the fluids and from 0.7 to 20 cp at atmospheric pressure. Water floods were conducted at various pressure levels from run to run. The recovery as a function of flooding pressure was found to be different for each fluid, with optimum gas saturations ranging from 7 up to 35 per cent. The data indicate that substantially higher recoveries may be obtained if water floods are conducted at an optimum pressure and that this optimum pressure is a function of fluid properties. The same core was used for all tests, and the reproduction of saturations for various runs indicates that wettability in the predominantly water-wet core did not change. INTRODUCTION A paper was presented by Bass and Crawford&apos; which described an experimental study of the effects of flooding pressure and rate on oil recovery by water flooding. This work was conducted using high-pressure models operated in a manner similar to that of an actual reservoir, with gas saturations being obtained by a solution-gas-drive mechanism. They found that the greatest oil recovery was obtained for the system studied by flooding in the presence of a 5 to 7 per cent gas saturation. Another experimental study simulating field conditions was presented by Richardson and Perkins.&apos; They used an unconsolidated sand pack containing kerosene-natural gas fluid and interstitial water. They flooded at various pressures and flooding rates. For their system it was found that the recovery was independent of the pressure level at which the water flood was performed. Kyte, et al," found that oil recovery by water flooding was increased as the free gas saturation at waterflood initiation was increased. However, after the initial gas saturation was increased above 15 per cent, the increase in oil recovery tended to level off. All of their runs were made at the same pressure using a light oil saturated with helium. The desired gas saturation was obtained by injecting helium into the core. Dyes&apos; made calculations which showed that an optimum gas saturation of 12 to 14 per cent may result in an increase in oil recovery of 7 to 12 per cent over that obtained by flooding at the bubble-point pressure. Others have also found that the presence of a free gas saturation may increase the waterflood oil recovery. In each case shrinkage was small and changes in fluid properties with respect to pressure were small. A careful review of the literature reveals that at the present time there is a wide difference of opinion on the factors affecting waterflood recoveries. This diversity of opinion is probably due to the fact that very little research has been done which has taken into account the many variables existing in an actual field being water flooded. Since the literature contains little information on high-pressure waterflooding studies using various types of reservoir fluids, it was believed appropriate that such a study should be made. EQUIPMENT AND PROCEDURE All tests were made using the same consolidated sandstone core. Torpedo sandstone was used to turn a cylindrical core 13.5-in. long and with a 2.92-in. average diameter. The core had a porosity of 28 per cent and a permeability to brine of 146 md. This brine was made up by adding 20,000-ppm sodium chloride and 30,000-ppm sodium nitrite to distilled water. This was used as connate water and flooding water. No fresh water was ever brought in contact with the core, as tests showed the sandstone contained argillaceous material which swelled in the presence of fresh water and plugged the stone. The core was sealed in a section of 6-in. N-80 tubing with Woods metal filling the annulus. The core was mounted horizontally; an injection well was placed in the center of one end and a production well in the center of the other. Pressure control was maintained by placing a back-pressure regulator (upstream control) on the producing well. The "live" oil was stored in a separate bottle and water was injected into this bottle to displace the oil for saturating the core using a two-cylinder standard-proportioning pump. This same pump was used for water flooding the core at a constant rate. This system was enclosed in water jackets and the temperature was automatically main-

By Irving Cadoff, Kurt Komarek, Edward Miller

Barium can be purified by equilibration with titanium. The melting point of barium was found to be 726.2° i 0.5 °C. The room-temperature lattice parameters of BaTe and Bask are 7.004 * 0.002A and 6.600 * 0.002A. Melting points for BaTe and Base were found to be 1510° * 30°C and 1830° ± 50°C, respectively. HIGH-purity barium and its compounds are difficult to prepare because of the reactivity of barium with the atmosphere and the large heats of formation of the compounds. Purification of barium by vacuum distillation,&apos; and the preparation and properties of barium oxide2 and barium sulfide3 have been reported. However, little has been done on the homologous compounds barium selenide and telluride. PURIFICATION OF BARIUM Distilled barium obtained from King Laboratories was used as the starting material. The analysis supplied with the metal showed the presence of: 0.4 wt pct Sr, 0.001 pct Mg, 0.02 pct F, 0.003 pct Cu, 0.005 pct Na and less than 5 x 10-3 wt pct of any other metallic impurity. Analyses for oxygen and nitrogen were not available. Since there is evidence4 that any barium nitride present in the starting material may decompose on distillation producing nitrogen which can contaminate the distillate, further purification was performed. At elevated temperatures, any nitrogen and oxygen present in barium should be removed by reaction with titanium. Assuming that the solubility of oxygen in liquid barium is negligible near the melting point of barium, any oxygen present will be in the form of BaO. Removal of oxygen from molten barium is expressed by the equation: BaO(S)+ TixOy(S) = Ba(l)+ TixO(y+1)(s) where Ti,Oy and TixO(y+1) are solid solutions of oxygen in titanium. At 1000°C, the change in free energy for this reaction is negative for (y+1)/x +y+1) x (100) 17.5 at. pct O.5 Since reaction with commercially pure titanium (containing 0.07 wt pct oxygen) results in a free energy change for the reaction of -19 kcal per g-atom, slight solubility of oxygen in barium would not hinder the oxygen removal. Since comparable thermodynamic data are not available to permit calculation of the partition of nitrogen between liquid barium and titanium, a similar quantitative relationship cannot be obtained. However, on the basis of work by Kubaschewski and Dench,5 complete removal of nitrogen from liquid barium can be expected. Since the melting point of barium is depressed markedly by small additions of nitrogen,&apos; the change in melting point during reaction of barium with titanium was used to follow the purification reaction. MELTING POINT OF BARIUM A 50-g sample of barium was sealed by arc welding under argon into an all titanium crucible provided with a thermocouple well. The melting point of the sample was determined by thermal analysis, using a Pt/Pt-10 pct Rh thermocouple which was calibrated according to National Bureau of Standards specification6. The crucible was then heated for 48 hr at 950°C in vacuum and the melting point redetermined. This procedure was repeated until three successive thermal analyses agreed within ±0.5oC, the limits of error of the analysis. The melting point increased from an initial value of 720.0°C to a final value of 726.2°C. Analysis on samples quenched from 950°C gave a solubility value of 0.004 wt. pct Ti. Assuming that the titanium-barium phase diagram is similar to those of titanium-magnesium7 and titanium-calcium,8 the solubility of titanium in liquid barium decreases with decreasing temperature. Therefore, the solubility of titanium in liquid barium should be less than 0.004 wt. pctat the melting point (726oC), and the effect of dissolved titanium on the melting point would be negligible. Addition of up to 3 wt pct Sr does not significantly change the melting point of barium,7 so that the effect of the 0.4 wt pct Sr in the starting material will also be negligible. The value of 726.2" ± 0.5C obtained for the melting point of barium can be compared .with a determination carried out by Keller and coworkers in low-carbon steel crucibles,&apos; who obtained a value of 725± 1C, using barium purified by fractional distillation. The higher value obtained in the present investigation is indicative of the effectiveness of titanium in removing traces of nitrogen. PREPARATION OF BaTe AND Base The compounds were prepared by direct reaction

Jan 1, 1961

By Lawrence A. Shepard, Richard H. Krock

A series of ductile, two phase W-Ni-Fe composites, sintered in the presence of a liquid phase, were tested in tension. Identical room temperature stress-strain curves were obtained for specimens containing from 80 to 92 wt pct W (58 to 75 vol pct W particles). The composites exhibited a maximum elongation of 29pct at room temperature, and 10.7 pct at 77 °K. The tungsten particles in the composite elongated by the same amount at these temperatures. Single-phase alloy specimens matching the composition of the composite matrix showed about one half the flow stress of the composites. The test results demonstrated that the mechanical properties of W-Ni-Fe composites are determined by the tungsten particles alone and are independent of matrix volume fraction or mean free path over the composition range studied. A general prediction of the plastic behavior of two-phase alloys or composites from a knowledge of the properties, size, shape, and dispersion of the individual components is not, at present, possible. The excellent theoretical and experimental exposition of the dispersion-strengthening problem applies only to cases where the stronger phase is present as fine particles and in volume fractions of a few percent. Materials in which the stronger phase constitutes a significant fraction of the volume, although of broad engineering interest, have received comparatively little analytical attention. This important group of materials is the concern of the present study. The degree of deformation of each phase during the plastic working of a ductile two-phase alloy has been established by Boas and Honeycombe,1 Clare-brough,2 and Clarebrough and berger.3 These workers empirically correlated the recrystallization temperature of the individual phases with the degree of cold work sustained by each. It was shown that the deformations of both phases are equal and therefore the same as that sustained by the composite whole when the volume fraction of the stronger phase exceeds 35 pct. At yielding, however, deformation begins in the weaker phase. A direct correlation of composite strength, as a function of deformation, with the strength of the individual components cannot be made. In the presence of stronger phase particles, the flow stress of the weaker matrix phase is enhanced by an additional hydrostatic component. The development and potential magnitude of matrix strength promotion upon straining has not even been experimentally established. Quantitative work in this field has been confined to ceramic-metal composites. These materials fracture at strains considerably below 1 pct by cracking of the ceramic particles.4-6 An indication of the potential constrained matrix strength capacity is given by the observation by Nishimatsu and Gur-land4 that the maximum tensile strength of a WC-Co composite is almost double the bulk strength of the cobalt matrix. The relationship between composite strength and geometry is ordinarily expressed in terms of the mean-free matrix path (referred to subsequently as MFP) between the stronger particles.* This factor takes into account both the volume fraction of matrix phase and the average size of the particles. unke17 concluded that composite strength varied directly with the decreasing log MFP, following the Gen-samer8 relationship. However, Gurland and ~radzil~ reported a strength maximum at an MFP of the order of 1 p in WC-Co composites. A ductile two phase metallic composite was chosen for the present investigation of composite mechanical properties with the view of avoiding the difficulties and ambiguities noted above. The W-Ni-Fe heavy alloy of Green, Jones, and pitkin9 contains 80 to 94 wt pct W, and nickel and iron in a weight ratio

Jan 1, 1963

By J. F. Smith, J. R. Ogren, N. J. Magnani

The uapor pressrcres of magnesium over binary alloys of magnesium with twelve of the yare-earth eletnetzts have been measured by the Knudsen effuion method in the temperature range 675° to 910°K. These vapor-pressure measurments were combined with data concerning the tevtrlitzul magnesium solubility and the vapor pressure of pure magnesinm to evaluale the standuvd free energies of pluase jormation. These free-etzergy values indicate that the CsCl structures of the heacy rave earths tend to be somewhat less stable than those of the light rare earths. This dif-]eying- behaviov covrelates with differences which have been obsevz~ed in other alloy systetns wherein a phuse appeurs, disappeavs, or changes crystal stvucture as the atomic number of the rare-earth com-ponent is changed. This behauior also appears to correlate with the struclurul rariations within the rare-earth elements themselves, and it is speculated that cariations in the spatial extent of the 4f orbitals are responsihle. STUDIES of the phase relationships and crystal structures in the binary systems between rare-earth metals (lanthanons) and magnesium are extensive but far from complete. However, the currently available information1-10 does produce a rather interesting pattern. This is illustrated in Table I. If one excludes europium and ytterbium from consideration because of their generally atypical behavior, it can be seen from the table that the phase relationships in the magnesium-rich regions show a distinctly different pattern for the lighter lanthanons as compared to the heavier lanthanons. For the lighter lanthanons, LnMg2 phases occur from lanthanum to gadolinium with the cubic MgCu2 structure, LnMg3 phases occur from lanthanum to terbium with the BiLi3 structure, and magnesium-rich phases occur from lanthanum to gadolinium with stoi-chiometries between Ln5Mg42 and LnMg12. In contrast, for the heavier lanthanons, those LnMg2 structures which have been examined have the hexagonal MgZn2 structure, LnMg3 phases have not been observed beyond terbium, and the magnesium-rich phases occur with the a manganese structure near a stoichiometry of Ln5MgZ4. The heavy lanthanon-magnesium systems thus appear to be analogous to the Y-Mg system""2 wherein YMg has the CsCl structure, YMg2 has the MgZn2 structure, and the region Y4Mgz5-Y5Mg24 has the a manganese structure, and no other intermediate phases are observed. Similarity in alloying behavior between yttrium and the heavy lanthanons occurs commonly, and on this basis it seems likely that LnMg2 phases will be found with the MgZn2 structure in the binary systems of dysprosium, thulium, and lutetium with magnesium when the appropriate investigations are made. In the case of the magnesium-rich phases of the lighter lanthanons, only the Ce-Mg phase relationships have been investigated thoroughly and in detail, and until similar investigations are made for the other systems there will remain questions as to which magnesium-rich stoichiometries represent equilibrium phases and what systematic variations occur in the sequence from lanthanum to gadolinium. Thus the data in Table I show that only the LnMg phases occur with the same crystallographic structure throughout the sequence from lanthanum to lutetium. It was speculated that the relative stability of these LnMg phases might vary from one lanthanon to the next in such a way as to presage the differences which occur among the more magnesium-rich lanthanon-magnesium phases. On this basis the present investigation of the thermodynamics of phase formation was Gndertaken for the LnMg phases. PROCEDURE AND RESULTS A generalized phase diagram for the lanthanon-rich portion of a lanthanon-magnesium alloy system is shown in Fig. 1 where ß represents a high-temperature bcc

Jan 1, 1968

In early March 2011, a 6.2 m (20.3 ft) diameter Rob-bins Double Shield tunnel boring machine (TBM) crossed the finish line in Sochi, Russia. The machine completed a 4.5-km- (2.8-mile-) long section of tunnel that will ultimately become part of the transportation infrastructure for the 2014 Winter Olympic Games. The TBM advanced through difficult ground at aver-age rates of 100 to 120 m/week (330 to 390 ftpw) for contractor OJSC Bamtonnelstroy, a division of the SK Most Company. The section of tunnel will ultimately become a service tunnel for Complex #3 - a section of Sochi?s transportation infrastructure under construction, which includes road and rail tunnels. A second, 10 m (32.8 ft) diameter Robbins Double Shield TBM is currently excavating the parallel 4.6-km- (2.9-mile-) long main railway tunnel using a continuous conveyor system for efficient muck removal. A 13.2 m (43.3 ft) diameter highway tunnel is also under construction. The 6.2 m (20.3 ft) Robbins TBM achieved high rates despite difficult conditions. The tunnels run through mixed ground including massive to completely fractured limestone with clay seams. Some sedimentary rock including sandstone and siltstone is present, along with fault zones consisting of breccias and conglomerates. In May 2010, the machine was stopped after encountering a significant fault zone consisting of broken rock and running soft ground. Field service personnel and crew successfully freed the machine by excavating a bypass tunnel around the TBM, freeing the cutterhead. Following the restart, a combination of continuous probe drilling and ground treatment with cement silicate and foam kept the machine moving forward.

Jan 1, 2011

By Staff

"INTRODUCTION Sheet mica is one of the most important minerals in modern industry. It is used in many kinds of electrical devices, and up to the present time no satisfactory substitute for it has been developed. It is necessary for the successful operation of airplanes, ships, motor vehicles radios, and radar equipment. Early in World y r II, the Array and Navy, foreseeing the need for conserving the stock of sheet mica on hand and realizing that imports from India and Brazil were falling off, had strategic mica placed on the critical war-materials list.Examination and exploration by the Bureau of nines indicated that there probably are large undeveloped deposits of mica in Alabama, some of which are near the surface and others at greater depth. The quality of most of this mica is high.During World War I, Alabama mica producers added materially to domestic production, but after 1920 virtually all of the mines closed end miners scattered. During World War II, when imports from India, Madagascar,Brazil,,other foreign sources were reduced, sometime was required for Alabama to act into production. Operators began to produce small quantities in 1942.The Colonial Mica Corporation was created by the Government during 1942 to buy Mica for the Metals Reserve Company, end later Colonial was made sole buying accent for strategic mica. About this time the Bureau of Mines estab¬lished the graphite field laboratory at Ashland, Ala. Samples of mica wore submitted for examination, and advice was requested by property owners and mine operators. This continued during 1943, when as many as 400 visitors a month called at the Bureau's Ashland field laboratory."

Aug 1, 1946

By Dupuy. Leon W., R. T. C. Rasmussen, W. A. Calhoun

"INTRODUCTION For many years it has been known that low-grade manganese deposits occur in the bluffs along the Missouri River Valley. Frequent attempts have been made to develop the ore and to produce a marketalble commodity but they have had little success. Under pressure of the war emergency and the shortage of manganese, the attention of the Federal Bureau of Mines was directedtoward the deposits.Manganese-bearing shale occurs from a point near Pierre, S. Dak., down the river to the Rosebud bridge near the Nebraska line (1).5/ The Bureau of,confined its work to the more accessible central portion of the deposits near Chamberlain, S. Dak. The ore occurs principally as concretionary nodules in the form of iron and manganese carbonates (manganosiarite and perhaps some manganocalcite; rhodochrosite has not been identified). At the surface the carbonate is often broken down so that the oxide of manganese gives the nodules a black The matrix or host rock is generally known as Pierre shale, composed of ""interbedded layers of bentonite, an altered volcanic ash, and dissemi¬nated bentonite particles,"" (2) and montmorillonite-beidellite clay minerals (3). The shale weathers to the very sticky gumbo characteristic of South Dakota and well-known to hunters and travelers in the area.The area selected for the experimental mining and pilot-plant work discussed in this report lies about 8 miles westerly from Chamberlain and is a few hundred feet north of U. S. Highway,16, on land owned or controlled,by M. Q. Sharpe of Kennebec, S. Dak., and the General Manganese Corp."

Feb 1, 1946

The STATE MINERAL SUMMARIES publication provides estimated data and summaries of mineral activities at the State level for 1989. Most of the estimates are based on nine months data. These summaries have been prepared in cooperation with State geological surveys or related agencies. Individual State summaries are published separately as State Mineral Industry Surveys and copies can be obtained from the appropriate State Activities field office.

Jan 1, 1990

By E. S. Chalpin

On 25 August 1971, the U.S. Bureau of Mines contracted with the Aerojet Liquid Rocket Company to perform an engineering research program to be completed on 25 May 1972. The program objective was to evaluate the advantages and disadvantages of the underground use of several power sources including but not limited to a closed cycle diesel, electric cable/motor, rechargeable battery/ motor and exhausting diesel for mine shuttle cars, with emphasis on health and safety. This report, Research in Advanced Power Systems for Mining Health and Safety consists of four (4) main parts: (1) Hazards and Safety Analysis of Mine Power Systems, (2) Evaluation of Closed Cycle Diesel Power System for Mine Applications, (3) Closed Cycle Diesel Power System Consumables Compatibility, and (4) Concluding Remarks and Recommendations. The hazards introduced to a mine by shuttle car power system failure modes were evaluated and reported. A "fault tree" analysis was generated for each power system and the probability of death or injury during an eight (8) hour shift and for a week of operation (105 hours) were estimated. Advantages and disadvantages were also reported for each system studied. Aerojet&apos;s assessment, based on a "forced decisions analysis," of the four shuttle car power systems as to their relative health and safety is that the exhausting or open cycle diesel is preferred, followed by the closed cycle diesel, the electric cable/motor and the rechargeable battery/motor. The assessment was based on ten parameters pertinent to the health and safety aspects of shuttle cars. Drawing layouts of two typical mine shuttle cars incorporating closed cycle diesel powerplant concepts are included in this report. The performance parameters established for the two concepts are tabulated. A study was made of the logistics involved in transporting and replenishing the consumables needed to operate a shuttle car equipped with a closed cycle diesel. The closed cycle diesel powerplant consumables -oxygen, potassium hydroxide, and diesel fuel - were analyzed as to their compatibility with materials found normally in a gassy coal mine. Spill tests simulating inadvertent leakage of liquid oxygen in a coal mine were performed. A critical evaluation of existing oxygen sensitivity data and the relationship to the use of oxygen on a shuttle car in a coal mine environment is presented.

Jan 1, 1972

By John F. Wiss

A series of controlled experiments was conducted at four surface coal mines to study the effects of certain blast parameters upon the ground and air vibration. Preliminary scale-model blasts were conducted at a quarry to provide basic data. It was found that the amplitudes of the ground and air vibration were controlled by the maximum explosive weight per delay. Either cube root or square root scaling could be used for the seismic amplitudes, and cube root scaling could be used for the overpressure amplitudes. Both amplitudes were not significantly affected by the total charge weight per blast, the attitude of the boreholes, or the charge length or diameter. The overpressure amplitudes were affected by the charge depth, the use of cover over surface detonating cord, and the use of adequate stemming. The length of the delay intervals and the spacing of holes were important in determining the potential for reinforcement of the amplitudes in certain directions from the blasts. In downwind directions from the blast, the attenuation of the overpressure with distance decreases. Surface terrain did not significantly affect the overpressure amplitudes within the range investigated. The type of overburden affects the generation of both amplitudes and the propagation of the seismic amplitudes. Spectral analysis of the ground and air vibration is reported. A bibliography of pertinent literature is included as an appendix. A scaled distance of 300 ft/lb1/3 should produce a peak particle velocity of less than 1 ips and an overpressure of less than 128 dB linear peak. For square root scaling, a scaled distance of 75 ft/lbl/2 should limit the ground vibration to less than 1 ips.

Jan 1, 1978

By David Bendersky

The principal objectives of this study are to: (1) survey electrical practices in metal and non-metal mines, (2) survey electrical practices in metal and non-metal mills, (3) clarify the federal regulations governing electrical practices in metal and non-metal mines/mills, (4) analyze electrical accidents, and (5) make recommendations aimed at improvement of the safety of electrical practices in metal and non-metal mines. Information was obtained from literature searches, accident reports, visits to 27 mines and 12 mills, and discussions with knowledgeable industry and government people. The various electrical power systems and practices at the mines and mills visited are described. Similarities and differences based on the type of mining and the minerals being mined or milled are presented. The federal regulations governing metal/non-metal mine/mill electrical practices (Code of Federal Regulations, Title 30, Sections 55.12, 56.12, and 57.12) are presented and discussed. Explanations of each regulation are provided in an appendix. The attitudes of mine/mill operators towards the federal regulations are described. An analysis of the electrical accidents in metal/non-metal mines and mills during the period 1972-1978 is presented. Recommendations, including specific research and development activities, aimed at improvement of electrical safety in metal/non-metal mines are submitted.

Jan 1, 1980

By W. E. Johnston

At last year&apos;s Annual Meeting a paper by Haultain and Johnston was presented entitled Is the Gold in Tellttrides Soluble in Cyanide? Since then the writer has continued the study of various phases of this problem. Samples and specimens of ore from some of the Kirkland Lake mines have been studied and non gold-bearing tellurides have been found in these that are not soluble in ordinary mill solutions. Samples of tailings, both old and recent, from this district have been examined with apparatus and methods that have proved very successful in detecting the presence of extremely minute quantities of tellurides. Tellurides, both base-metal and gold-bearing, have been discovered in these tailings, but only in such minute quantities that their presence would not affect the ordinary assay results. More free gold particles have been found in the tailings than gold-bearing tellurides. Much experimental work has been done on tellurides, concentrated from high-grade material and from ordinary run-of-mine ore. The gold-bearing tellurides behave very much as does gold itself. Finely divided particles are dissolved fairly rapidly, coarser particles more slowly. All the tellurides are soft and brittle and also have a high specific gravity, with the result that they are extremely finely divided in ordinary mill practice. The ordinary high-lime solution of Kirkland Lake practice is suitable for the dissolving of the gold tellurides. Oxygen is necessary, but apparently not more so than in dissolving gold. Some particles have been found that appear under the microscope to be ordinary metallic gold particles, but on heating they show a small telluride content. These appear to dissolve more slowly than gold. There is considerable variation in the ratio of tellurides to gold from different points in the mines. So far the writer has failed to find any connection between this ratio and the richness of the ore. Generally speaking, the base-metal tellurides predominate. Some of these contain gold but this may be due to a mixture of tellurides in the one particle.

Jan 1, 1933

By Mark Samonds

"Manufacturing processes which involve liquid to solid and solid state transformations in metals encompass a wide variety of physical phenomena. The past twenty years have seen a steady evolution in the complexity and scope of numerical models of these processes, beginning with thermal analyses without phase change. Recently, a few software packages have become available which have true multi-physics capabilities. This permits the treatment of thermal, fluids, stress, electromagnetic, chemical reaction and microstructure development aspects altogether in a fully coupled simulation. This paper will consider various aspects of these types of models.Coupled thermal and fluid flow analyses of continuous castings have been around for fifteen years. Coupled thermal and free surface fluid flow simulations of shape castings have been available for ten years, including view factor radiation models for investment castings. Only recently, however, have fully coupled thermal, fluid, and stress analyses become practical. This implies the reverse coupling of the mechanical deformations to the solution of the energy and momentum equations through modification to the interface heat transfer coefficients and the fluid domain geometry. This has been implemented with a combined eulerian-lagrangian finite element method. Appropriate mechanical constitutive models will also be discussed.Many types of defects need to be predicted in casting processes. Those related to stress include hot tearing, hot cracking, part distortion, and thermal fatigue in dies. Macroporosity, microporosity, and microsegregation are determined by the solidification behavior and microstructure development in a casting. In particular, microporosity is influenced by dissolved gases, the morphology of the mushy zone, the liquid to solid density change, and the local pressure conditions. Macrosegregation is caused by the partitioning of solutes during. solidification and subsequent thermo-solutal convection. An additional transport equation is required for each solute that is being tracked. Computational thermodynamics is being incorporated into these types of analyses to determine transformation temperatures, partition coefficients, densities, and enthalpies. In combination, the microstructure and microporosity models can frequently predict a variety of mechanical models, such as yield strength, tensile strength, and elongation."

Jan 1, 2001

By Raj Thamburaj

"Over the last few decades, the emphasis on affordability and reduced cost of ownership has necessitated the development of innovative processes to carry out repairs in aero engine components. Conventional weld and braze repairs have evolved into advanced, sophisticated processes using state of the art knowledge in lasers, robotics and materials technology. This paper illustrates past and present scenarios in an attempt to illustrate progress that has been made in this area. The problems encountered in the past have been detailed along with the solutions that have been developed and commercially implemented to address these issues. Apart from technical progress, this presentation also addresses the progress made in business approaches and in Certification/Regulatory issues surrounding aero engine repair. Progress in Technology Repair technologies have also been the embryo from which new and revolutionary manufacturing technologies have evolved as well. Electron Beam Free Forming and LENS are examples of how a completely new manufacturing concept can evolve what was originally only a process to join metals. The current and future potential of these spin offs is discussed providing examples of application. While several problems have been solved over time with the implementation of advanced repair technologies, the demands of the industry have created new challenges. The paper describes these issues, outlines potential solutions and discusses the future of repair technologies in terms of the far reaching influence it is sure to have in design, manufacturing, maintenance management and life extension. Progress in Business Trends.Business approaches to repair and maintenance have also gone through considerable change with the introduction of ""Power by the Hour"" and other similar arrangements between the companies responsible for engine overhaul and the end-users. Program Based Logistics (PBL) is yet another innovation to provide a win-win situation for the repair service provider and the end user. This paper traces the development of these business initiatives and highlights successful applications. Progress in Repair Certification, Regulatory Issues.Understanding of the issues surrounding certification of repairs has also evolved with time and regulatory issues have been clarified considerably. Procedures for analysis and testing are much clearer and ""Check Lists"" are being drafted for certifying repairs on various engine components. The PMA phenomenon has added yet another dimension to the issues regarding certification and these are discussed as well."

Jan 1, 2010

Energy is central to respond to critical stakes on human and industrial development requirements as well as on climate change. The increase of the share of carbon-free energy sources in the global supply mix will help to reduce significantly greenhouse gas emissions (GHG) as power generation accounts currently for 41 per cent of these emissions from the energy sector. In this energetic mix, nuclear and renewable energies are complementary, the first more focused in the baseload power generation whilst the second is well suited for decentralised power generation. In this context, AREVA&apos;s goal is to enable everyone to have access to a cleaner, safer and more economical energy. Regarding nuclear energy, AREVA&apos;s strategy is to capitalise on its integrated operation model, which groups together fuel cycle and nuclear power plant construction, aiming at building one third of the new nuclear capacities and securing the fuel cycle supply chain for its existing and future customers. Therefore, the front end of the uranium fuel cycle, from mining to the fabrication of fuel assemblies, has a key role in the sustainability of the nuclear industry. The replacement of the current capacity and the entrance of new countries on the nuclear power generation might lead to a significant rise of uranium demand by 2020. In order to be prepared in time, AREVA defined an ambitious industrial program to expand mineral reserves, increase the production of uranium concentrates, replace the conversion capacity, build two new uranium enrichment plants, one in France and one in the United States and upgrade its fuel manufacturing plants. To support the front-end industrial activities in the short and long term, AREVA invests on a portfolio of R&amp;D projects to find out solutions to meet customers&apos; needs, to improve its competitiveness and to develop new concepts and solutions to anticipate future market evolutions. In particular, some important technological challenges in mining must be surmounted to develop cost-effective methods to explore and exploit low grade deposits while creating sustainable solutions for reducing reagent, water and energy consumptions. In this lecture, an overview of the industrial investments of AREVA in the front end of the uranium fuel cycle and some highlights on its R&amp;D major axis will be presented. This is an abstract only. No full paper was prepared for this abstract. &nbsp;

Sep 13, 2010

By B. B. Rath, Hsun Hu

In wedge-shaped bicrystals of zone-refined aluminum it is observed that (111) pure tilt boundaries migrate under the driving force of their own inter-facial free energy. The boundary velocity is a power function of the driving force. The driving force exponent decreases with decreasing angle of misorien-tation. For example, at 64O°C, the exponent decreased from 4.0 for a 40 deg to 3.2 for a 16 deg tilt boundary. An evaluation of the driving force acting on the boundaries during their motion indicates that for low driv-forces, up to about 2 x l03 ergs per cu cm, the velocity is relatively independent of misorientation, whereas at higher driving forces a 40 deg tilt boundary exhibits the highest velocity. The measured activation energy for boundary migration approaches that for bulk self-diffusion at low driving forces, decreasing from 33 to 27 kcal per mole as the driving force is increased from 1 x l0 to 5 x l03 ergs per cu cm. These results are compared with current theories of grain-boundary migration. In previous experimental studies of grain boundary migration the driving force has been limited to a difference in stored energy across the boundary. This stored energy has been introduced into the crystal either by prior deformation1-3 or by grown-in lineage structure. A part of the energy stored in the deformed crystal is released by recovery either prior to or concurrently with grain boundary migration, thus introducing an uncertainty as to the magnitude of the driving force responsible for grain boundary migration. The grown-in lineage structure, though thermally stable during annealing, neither provides conditions under which different levels of energy may be stored in the imperfect crystal nor provides a control of orientation difference across the migrating boundary of a growing grain. Furthermore, because of variation in the lineage structure, it is difficult to determine accurately the energy stored in the imperfect crystal. Several investigations of grain boundary migration during normal grain growth have also suffered from difficulties in estimating the driving force because of uncertainties in the principal radii of curvature.~ In the present investigation the velocity of pure tilt boundaries in zone-refined aluminum bicrystals of selected orientation (40, 30, and 16 deg around the [Ill] tilt axis) has been measured in the absence of a dislocation density difference across the moving boundary, thus eliminating the previous experimental difficulties. The driving force for boundary migration is derived from a gradient of the total interfacial free energy of the migrating boundary in wedge-shaped bicrystals. A similar method was attempted by Bron and Machlin in a study of grain boundary migration in silver. However, they found that one of the crystals was deformed and consequently the motion of the boundary was partly due to a difference of stored energy across the boundary. The observed behavior of boundary velocities as affected by the driving force is examined in the light of the predictions of the current theories of grain boundary migration.7"10 The effect of boundary misorientation on velocity is compared with the theory of " which is based on a dislocation core model for high-angle boundaries. EXPERIMENTAL METHOD Seed-oriented bicrystals of zone-refined aluminum, 2.5 cm wide, 0.5 cm thick, and 12 cm long, containing tilt boundaries with a common (111) axis, were grown from the melt in the direction of this axis. Spectro-graphic analysis, reported earlier,&apos;&apos; indicated the purity of the crystals to be 99.999+pct. Three such bicrystals containing 16, 30, and 40 deg tilt boundaries were used. Wedge-shaped specimens were prepared from these bicrystals by spark cutting followed by electrolytic polishing. The angle of the wedge was usually 40 deg and the specimens were usually 0.25 cm thick. The intercrystalline boundary was located within 0.2 to 0.5 cm from the tip of the wedge. Fig. 1 shows a section of an oriented bicrystal containing an outline of a wedge-shaped specimen. The crystallographic directions shown in Fig. 1 represent the orientation of one of the crystals (the larger section of the bicrys-tal); the orientation of the other crystal differs only by rotation around the common [lil] axis. The parallel faces of the wedge always corresponded to the common (171) planes in both crystals, whereas the orientation of the side faces varied, depending on the misorientation angle. The bicrystal orientations were determined

Jan 1, 1970