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By J. W. Evans

ONE of the most important and frequent calculations that the extractive metallurgist is called upon to make is that of the standard free energy change of a reaction (?F°). For many reactions of metallurgical interest, the lengthy arithmetical calculations have been eliminated by the use of free energy-temperature diagrams which have been constructed by Ellingham,1 Richardson and Jeffes,2 Kellogg,3 and Osborn4 (e.g., for oxides, sulphides, halides) from critical surveys of existing data. The speed and simplicity of making calculations with these graphs make them of great practical value and, this should be stressed, in the majority of cases no greater accuracy is obtained by the individual calculations from specific heat data, entropies, and heats of reaction. With the increasing industrial application of vacuum methods to the winning of metals, notably at present magnesium and the alkaline earth metals, it is necessary to calculate low metal vapor pressures above reaction mixtures. The existing free energy diagrams usually give values where the solid and liquid metals are at unit activity. To obtain the free energy change associated with the reaction Metal (solid or liquid) = Metal (gas) it is customary to calculate this from either vapor pressure equations or from the appropriate free energy functions. This paper presents graphically the free energies of vaporization of a number of metals of economic importance which can be used in conjunction with other free energy diagrams. Certain metals have been excluded on the following grounds: titanium, tungsten, molybdenum, and platinum have very high heats of vaporization and boiling points and the uncertainty of these values arising from difficulties of high temperature measurements makes free energy values of doubtful accuracy; the data for cobalt, vanadium, and zirconium are uncertain; finally, arsenic, antimony, and bismuth could not be conveniently included. because of the presence of mixtures of polyatomic and mona-tomic vapors in the temperature range considered. Free Energy Diagram In Fig. 1, the standard free energies of vaporization per mol (?F°T) have been plotted for the temperature range 0" to 2000°C for the reaction M (solid or liquid) = M (gas) The data have been obtained from the free energy functions — (F-H298)/T for the solid, liquid, and gaseous elements and the heats of vaporization at 298°K, i.e., ?H298 (vapor). The values of these functions have been taken without change from the recent critical survey by Brewer;' the bulk of this data is from Kelley7 with adjustments in the light of more recent work. Values of the function — (F-H298) /T at T = 298°, 500°, 1000°, 1500°, and 2000°K were employed. Where possible, a further independent value was obtained by using the boiling point, i.e., where ?F°T = 0. All calculations are based on the assumption that the metal vapors are monatomic and that the boiling points refer to those temperatures at which the partial pressure of the monatomic vapor above the metal is 760 mm. For the alkali metals, e.g., sodium, potassium, and lithium, diatomic gas molecules are present as minor species; details of these are discussed by Brewer." On the basis of the above values and allowing for the change in slope at the melting point, straight line graphs were constructed and extrapolated to 2000°C. The deviation from a straight line did not exceed ±500 cal, which in all cases appears less than the probable error in the ?F°T values.

Jan 1, 1954

By Spencer S. Shannon

The lanthanide elements from lanthanum (atomic number 57) to lutetium (71) plus yttrium (39) are called the rare-earth elements; scandium (21) is chemically similar to yttrium and the lanthanides, but differs in occurrence. The rare-earth metals were divided into three categories by the chemist, Berzelius, in the early 1800s; however, modern usage defines only two groups. The cerium group is named after the most abundant -element and comprises lanthanum (57), cerium (58), praseodymium (59), neodymium (60), promethium (61), samarium (62), europium (63), and gadolinium (64). Traces of natural promethium were discovered in apatite in Finland (Erametsa, 1965). The yttrium group, also named after its most abundant representative, comprises terbium (65), dysprosium (66), holmium (67), erbium (68), thulium (69), ytterbium (70), and lutetium (71). Yttrium most closely resembles holmium in chemical properties, and occurs most commonly with the heavy lanthanides. The rare-earth minerals may be divided into cerium-group, yttrium-group, or mixed-group classes. A number of rare-earth minerals contain thorium and uranium, but these are variable in content and are not essential to the composition of the minerals. In monazite, a mineral that is a principal source of rare earths, the worldwide average content of thorium oxide is 7.2 % ; however, varieties of monazite contain as little as 0.001% and as much as 31.5% thoria. Monazite is the chief ore of thorium and, until recently, thorium has been the main product; the rare-earth metals were in fact byproducts. However, because of the great demand for rare-earth metals by the petroleum refining and the iron and steel industries since the early 1970s, the roles have been reversed so that thorium is now the byproduct. Uses A 9 to 1 mixture of yttrium and thorium oxides is used for high-intensity incandescent lamps and for high-temperature-resistant windows and lenses. Yttrium oxysulfide and orthovanadate, doped with europium oxide, are used in color television tube phosphors. Yttrium, as well as cerium, praseodymium, and samarium, is alloyed with cobalt to form strong permanent magnets. It hardens magnesium alloys and retards the oxidation of iron-chromium alloys. Yttrium-iron garnets are used for transmitting low microwave frequencies. Yttrium-aluminum garnets are used as host crystals for lasers and as artificial gems. Yttria also forms strong, stable, high-temperature refractories. Gadolinium-gallium garnets are used in substrate wafers on which bubble-memory films are deposited. Rare-earth chlorides, particularly of lanthanum, neodymium, and praseodymium, are used as catalysts for petroleum cracking. Mischmetal is used for lighter flints and to improve the ductility and impact strength of iron and steel alloys. Mischmetal also reduces the fatigue resistance of magnesium and aluminum alloys. Rare-earth oxides are used for polishing glasses and lenses. Individual or specific combinations of high-purity oxides are used as additives in glass to maintain or change its color, dispersion, or refractive index. High-purity oxide combinations are also used to color tile and to opacify porcelain enamel. Rare-earth fluorides and oxides are used in carbon-arc electrodes to provide incandescent white light. Lanthanum or gadolinium oxysulfide phosphors, activated with terbium, are used as x-ray screen intensifiers. Hydrogen can be stored by sorption on lanthanum-nickel alloys (Anon., 1979). Thorium232 is bombarded with slow neutrons in breeder reactors to create fissionable thorium233 for nuclear fuel cells. The 330-MW, high-temperature gas-cooled reactor at Fort St.

Jan 1, 1983

By Pol Duwez, Paul Pietrokowsky

Titanium and vanadium form a complete series of solid solutions at temperatures above 885°C. Below 885°C, vanadium is slightly soluble in a titanium (about 1.5 pct V at 650°C) and a two-phase a plus ß region extends to 18.5 pct V at 650°C. The alloys up to 15.0 pct V transform into a supersaturated a solid solution upon rapid cooling from the ß phase. Above 15 pct V the ß phase may be retained. The temperature at which the ß to a' martensite-type transformation takes place decreases steadily from 850°C for 0.5 pct V to 325°C for 12.7 pct V. IN the transition series of the periodic table, the six elements that have a body-centered cubic structure at all temperatures, namely chromium, vanadium, molybdenum, columbium, tungsten, and tantalum, fulfill the conditions required for the existence of complete series of solid solutions with the high temperature (ß) form of titanium. Up to the present time, complete solubility at temperatures above the a to ß transformation of titanium has been observed in the systems Ti-MO,1,2 Ti-Cb,2 Ti-W,³ and Ti-Ta.³ The two remaining elements, vanadium and chromium, have atomic diameters which are not as near that of titanium as the atomic diameters of the four other elements. Both are smaller than titanium and the difference, expressed in percentage of the titanium atomic diameter, is 12.3 pct for chromium and 8.2 pct for vanadium. On this basis, the least favorable conditions for solid-solution formation are therefore encountered in the Ti-Cr system. The early work on the Ti-Cr system4 revealed that up to about 1100°C the solubility of chromium in ß titanium is limited, and an intermetallic phase exists near the stoichiometric composition TiCr2. It was found later' that a continuous series of solid solutions extends across the diagram at higher temperatures, and TiCr2 forms by solid state reaction. It became apparent therefore that complete solubility would also be present in the Ti-V system. The present investigation confirms this possibility. The iodide-refined titanium used in this investigation was purchased from the New Jersey Zinc Co., New York. According to the manufacturer, a typical analysis of this product is 0.0065 pct Mn, 0.0022 pct Fe, 0.0015 pct Cu, and 0.0042 pct Pb. The Vickers hardness number (10 kg load) of the crystalline bar varies between 55 and 80. The vanadium metal was purchased from the Westinghouse Electric Corp., Lamp Div., Bloomfield, N. J. The purity of this metal is probably above 99 pct V. The oxygen content must have been quite low, since a bar about 1/4 in. square could be cold rolled into a ribbon 0.020 in. thick. To prepare the various alloys on the titanium-rich side of the diagram, the titanium rod was machined into cups 1 cm in diam and about 1.5 cm high. Pieces of vanadium, of the proper weight, were cut from the square bars and placed within the cups prior to melting. On the vanadium-rich end of the diagram, single pieces of the metals, in the proper weight pro-

Jan 1, 1953

By M. A. Dayananda

Based on the Kirkendall frame of reference, a method is proposed for the determination of atomic mobilities of all the diffusing species in a multicorn-ponent system with a single diffusion couple. The method is based on an atomic mobility model developed on the concept of negligible interactions among the intrinsic fluxes. It is shown in the model that mobilities can be obtained directly from the cumulative intrinsic fluxes past the Kirkendall interface. The proposed method replaces the need for a prior determination of interdiffusion coefficients far the calculation of mobilities. Relations between intrinsic diffusion coefficients and mobilities are derived and the mobility calculations are illustrated with diffusion data in Cu-Zn-Mn alloys at 850°C. ThE concept of "intrinsic flux" with respect to a fixed lattice was introduced "i Darken1 to explain toa Kirkendall effect2 demonstrated by the motion of inert markers during isothermal diffusion in single-phase binary solid solutions. Based on this concept, intrinsic diffusion studies have been made in various binary metallic systems3,4 employing such a lattice frame of reference, commonly referred to as the Kirkendall interface. Similar approaches, both theoretical and experimental, have been presented5"10 to study intrinsic diffusion in multicomponent systems. Based on the direct integration of Fick's law extended to multicomponent diffusion, Philibert and Guy8 proposed a method for the determination of intrinsic diffusion coefficients. For an n-component system, this procedure requires an experimental study with (n — 1) diffusion couples, all having their Kirkendall interfaces at the same compositio;, where n(n — 1) intrinsic diffusion coefficients are defined. This technique has been employed for ternary diffusion studies by Dayananda and Grace" and Guy and Leroy.11 A different approach is recommended by Ziebold and Cooper,12 who have derived relations between interdiffusion coefficients and atomic mobilities employing fluxes referred to the local center of volume. Their analysis is based on the simplifying assumption of negligible interactions among intrinsic fluxes. This assumption has been considered satisfactory for dilute solutions.5"7 The use of this analysis for the calculation of mobilities requires an initial determination of interdiffusion coefficients with a set of diffusion couples having intersecting diffusion paths. It is the purpose of this paper to propose a method that would permit a direct determination of mobilities of all components of a multicomponent system from a single diffusion couple. This method is based on a mo- bility model developed with diffusion fluxes referred directly to the Kirkendall interface, generally identified by inert markers. gen erall, like that of Ziebold and Cooper,12 employs the simplifying assumption that the flux of each component relative to a fixed lattice is caused only by the driving force of its own chemical potential gradient. THE KIRKENDALL INTERFACE Inert markers are employed in diffusion couples to locate experimentally the position of the Kirkendall interface. They are initially placed at the weld interface for "sandwich" couples, or at the original vapor-solid interface for vapor-solid couples. Studies of marker motion in binary systems3'4 with both types of couples indicate that markers remain in a plane of constant composition and move with this plane para-bolically with time. Parabolic marker movements were also observed in ternary Cu-Zn-Mn couples by Dayananda and Grace.10 It is reasonable to expect a similar marker behavior even for diffusion couples with a higher number of components.

Jan 1, 1969

By H. Warlimont

Precipitation of cementite plates from carbon-rich austenite gives rise to localized formation of martensite in the matrix next to the precipitate upon quenching. The growth of this martensite is urmsually restricted. A distinct lattice relationship is found between this martensite and the cementite phase. It is concluded that the martensite is nacleated in the region of lowest carbon concentration at the austenite-cementite integace, with low-energy matching to the cementite lattice. The restriction of the growth of the martensite phase to the vicinity of the cementite plates can be explained by misfit in the austenite -martensite glissile interface and the uphill carbon gradient in the austenite. The investigation was carried out by light- and electron-microscopy and by electron-diffraction of thin foils. THE precipitation of cementite from carbon-rich austenite gives rise to a localized formation of martensite in the matrix next to the precipitate upon quenching. This behavior has been described previously by A. B. Greninger and A. R. Troiano1 for a 1.78 pct C steel ("pseudomorphic martensite"), and by A. Hultgren2 for a Fe-0.99 pct C—5.20 pct Mn steel. By measuring the axial ratio of the martensite phase,' it was found that the carbon content of this martensite was lower than that of the martensite which formed without prior partial transformation to cementite. Therefore, it was concluded that lowering of the carbon concentration in the matrix next to the precipitate raised the M, temperature locally and thus led to nucleation of martensite at the ce-mentite-austenite interface. However, the restriction of the growth of the martensite phase to the vicinity of the cementite plates cannot be explained by localized carbon impoverishment alone. Under ordinary conditions a martensite plate which has been nucleated in a favorable site can continue to grow until it encounters a physical barrier, or until it encounters a compositional barrier in the matrix, where the total free-energy change for the reaction is not negative, since it has been shown by numerous experiments that the activation energy for growth of ordinary martensite is virtually zero.' An investigation was conducted by transmission electron microscopy and electron diffraction to study this extraordinary martensite. It was expected that crystallographic in addition to compo- sitional conditions caused this abnormal mode of martensite formation. MATERIAL AND PROCEDURE An Fe-C-Mn alloy containing 1.15 pct C and 5.1 pct Mn was used for most of the experiments. For metallographic work, specimens 15 by 15 by 3 mm were used. For preparation of thin films, the initial specimen size was 15 by 15 by 0.7 mm. The heat treatment of each specimen consisted of austenitizing for 1/2hr at 1100'~ in an argon atmosphere, subsequent isothermal holding in a lead bath at one of a series of different temperatures, and, finally, quenching into brine at room temperature. For metallographic examination, the specimens were mounted in bakelite (slight tempering effects resulted from the heat in the mounting press) ground, polished, and etched in nital. Thin films for transmission electron microscopy and electron diffraction were obtained by grinding the specimens to approximately 0.2 mm thickness and subsequent electrolytical thinning. The orientation relationships were evaluated from sets of electron micrographs and selected-area electron diffraction patterns of single units of the transformation products and the adjacent matrix. RESULTS In the alloy which was used for the experiments, proeutectoid carbide precipitates over a wide tem-

Jan 1, 1962

By Albert S. Trube

Increasing emphasis is being placed on the necessity for obtaining reasonably accurate estimates of the physical properties of reservoir fluids well in advance of more accurate laboratory data. One such factor is the isothermal coefficient of expansion of an undersaturated hydrocarbon liquid which may be contained in a particular reservoir. This coefficient, or liquid "compressibility", has often been assumed to be relatively insensitive and nearly constant. Although this assumption may be nearly correct in the case of high specific gravity liquids, it cannot apply in the case of medium to low specific gravity liquids. Any treatment of the nature of liquid compressibilities must give consideration to the variable nature of the isothermal expansion coefficient and the fact that it can be both pressure sensitive and temperature sensitive. The isothermal coefficient of expansion, or compressibility, of a substance is defined as -c = 1/V (?V/?p)T......(1) The value of Eq. 1 may be approximated for a finite pressure change by using the well-known relation, c = V1 - V1/Ve (p2-p1), ........(2) in which p1 > p1 and V2 > V2 and V1 + V2/2. The instantaneous compressibility may also be estimated from the slope of a curve on which log V is plotted vs pa. In this instance, it has been shown that c = In V1/V2/p2-p1 ...........(3) Eq. 3 may be used for variable compressibilities by plot-ting V vs p on semi-log paper. In this case, the instan-taneous or point compressibility is c = 2.303 m.......... . (4) in which m is the slope of the curve at a point in log cycles per psi. ISOTHERMAL COMPRESSIBILITY OF UNDERSATURATED LIQUID In the case of gases, the compressibility has been defined by Muskat' and others as Co = 1/p - ?z/z?p ..........(5) This was later generalized through application of the theorem of corresponding states' to co = 1/pr - (?z/z?pr) T8 ........(6) in which c, is defined as the pseudo-reduced compres-sibility and is numerically equal to (c.p,) and the sign is arbitrarily changed for mathematical convenience. Eq. 6 is general and applies to gases and liquids. In the case of liquids, c. = c1,pe, but if Eq. 6 is used, values of z and ?z/?p, must be determined for the liquid in question. The difficulty of obtaining accurate values of ?z/?p,, particularly in the region where T, is approaching 1.00, was pointed out in the previous paper'. This method of approach is unreliable for extension into computations of liquid compressibilities. On the other hand, c, can also be defined as follows: - Cr = 1/Vr (?Vr/?pr) Tr ......(7) and from which, Cr = 1/pr (?pr/?pr) Tr .....(8) In accordance with the theorem of corresponding states, Vr = V/Vr, p, = p/pr and pr = p/pr. Ref. 2 pro-vides an excellent source of reduced density, reduced pressure and reduced temperature data for a wide variety of fluids. For the purpose of this investigation, the set of fluids2 having ze = 0.27 was chosen because it in-cludes most of the heavier hydrocarbons usually found in those complex mixtures loosely defined as "reservoir oils". Data on undersaturated liquids in Ref. 2 were rearranged to conform with Eq. 8. To simplify the computation of cr, the isothermal p, data were plotted vs the log of pr, in which case for any straight line or tangent cr = 1/M pr pr .....(9)

Jan 1, 1958

By James T. Waber, Allen C. Larson, Karl Gschneidner, Margaret Y. Prince

The original graphical method proposed by Darken and Gurry for predicting which elements are soluble in a given element was slightly modified and was used to predict terminal solubilities in 1455 known binary combinations. it was found that the modified Darken and Gurry method had a reliability of 61.7 pct in predicting extensive solid solubility (greater than 5 at. pct) and of 84.8pct in predicting limited solid solubility (less than 5 at. pct), an over-all reliability percentage of 76.6. Using the same experimental data, it was found that using only the simple Hume-Rothery size-effect criterion was 50.1 pct reliable in predicting extensive solid solubility, only slightly better than a purely random choice. and 90.3 pct reliable for predicting limited solid solubility, an over-all reliability percentage of 67.6. THE first rational rules for determining a priori whether two metals are not freely soluble in the solid state were announced by Hume-Rothery and coworkers.1,2 These well-known rules have been accorded a special place in metallurgical literature. Since the "electronegative" and "relative valence effect" rules of Hume-Rothery were only qualitative in nature it was difficult to use them in a quantitative analysis. The next major step was made by Darken and gurry3 and apparently went unexplored for a number of years. They prepared graphs illustrating the influence of both electronegativity and size difference on the solubility of elements in silver, magnesium, and aluminum, and they drew elliptical figures, whose maximum width was ±15 pct of the solvent radius and the maximum height was ±0.4 electronegativity units. The purpose of the present paper is to assess and compare the effectiveness of using the simple size-factor and the Darken-Gurry criteria to predict which elements will be soluble and insoluble in a given solute. In 1957, waber4 prepared Darken-Gurry plots for determining the solutes that were likely to be soluble in 6 and plutonium and introduced an inner ellipse as an aid to determining which elements should be soluble to a considerable extent. As illustrated in Fig. 1, the major axis of the outer ellipse corresponded to ±0.4 electronegativity units (OD) while the minor axis corresponded to ±15 pct of the radius of the solvent phase (OB). This simultaneous "action" of the two Hume-Rothery criteria was used to indicate which elements would have little or no solubility in the host lattice, namely those elements whose points lay outside this ellipse. An inner ellipse, "centered" over the same point of the solvent was drawn with ±0.2 electronegativity units (OC) and ±8 pct (OA) as the major and minor axes. Solutes with points lying within the inner ellipse were expected to be capable of forming extensive solid solutions with the host element. Use of this method of applying the earlier Hume-Rothery criteria was moderately successful for plutonium. For 6-phase plutonium, only one element out of the eight predicted to be extensively soluble was known to be almost insoluble, and of the sixteen elements predicted to have more restricted solubility, five were known to be essentially insoluble. The success of discerning solubility in the E phase by this method was comparable. One prediction made on the basis of this analysis was that the heavier rare earth metals, such as holmium, erbium, and thulium, should be soluble in the 6 phase, whereas the lighter rare earth elements, such as lanthanum or

Jan 1, 1963

By A. Rosenzweig, M. M. Karnowsky

The generalized binary diagram of the Au-Sn-Pb system is presented. The chief characteristic is the pseudobinary between lead and AuSn. On the high-gold side of the pseudobinary, four reaction isotherms were found at 363°, 274°, 225°, and 204°C. On the low-gold side of the pseudobinary, three reaction isotherms at 277°, 205°, and 176°C were found. A vertical section from the eutectic solder composition to gold was developed from the isothermal sections generated. METALLURGICAL problems arising from the intentional or accidental formation of Au-Sn-Pb alloys in soldering applications have indicated a need for information on the phase equilibria in this ternary system. The literature indicates that a complete diagram presenting this information has not been prepared. Even the recent excellent work by prince' entitled "The Au-Pb-Sn Ternary System" actually extends only to the AuSn or 50 at. pct Au range. There are more events in the 50 to 100 at. pct Au than in the less than 50 at. pct range. This article by Prince furnished much guidance in preparing this report. Initial efforts with the isopleth from the eutectic solder composition 61.9 wt pct Sn-38.1 wt pct Pb and 0 to 90 wt pct Au indicated that extensions of the work to the whole of the diagram (even if in less detail) were necessary to understand this system. In undertaking the construction of such a diagram, this study used differential thermal analyses (DTA) and metallography with verification and identification of phases by electron microprobe analyses. EXPERIMENTAL PROCEDURE The procedure began with the development of a cell which would be unreactive with lead, tin, and gold, retain its strength to 1100°C, exclude oxygen, and also furnish a suitable well for insertion and protection of a thermocouple to monitor temperature changes in the material. Such a cell would make it possible to reuse the sample should a repetition of determination be desired. Fig. 1 is a photograph of two such quartz cells as finally developed. The specimens have been run many times. The cell is made up of an inner sample bucket and an outer capsule with a thermocouple well which the sample surrounds. The DTA unit was an assembly devised from available instrumentation. The sample holder was a 3-in.-long cylinder of nickel, 2 1/2 in. in diam, fitted securely in a vertical tube furnace. Two holes 7/8 in. in diam were symmetrically located to receive the quartz cells. A dummy cell with nickel powder was used as the reference. The absolute temperature was recorded with a Pt/Pt 10-pct Rh thermocouple with an automatic Kaye ice bath compensator. (Calibration indicated the compensator to be accurate to better than ±0.5° over the 100° to 1000°C range.) The absolute temperature was measured in the sample and recorded on an L&N mul-tirange recorder with a full-scale display of 1 mv and automatic ranging of 99 mv. The differential signal between the sample temperature and the reference temperature was amplified with an L&N microvolt amplifier and recorded on an L&N Speedomax G recorder. Since two charts were obtained, the chart speeds were equalized and each event was noted on the differential chart, and the temperature at that time was obtained from the temperature record.

Jan 1, 1969

By J. F. Evers, S. Sadiq, F. W. Preston, G. W. Swift

Proper scaling of unsteady-state flow in laboratory gas reservoir models can be achieved if the permeability/fractional porosity ratio is less than 0.5 md. Porous media meeting this specification can be obtained from mixtures of sand and Portland cement provided (1) the water/cement ratio is in the range of 0.35 to 0.40, (2) the sand/cement ratio is in the range of 1/1 to 2/1, (3) the sand grain size is in the range of 48-100 to 18-28 mesh, (4) the mortar curing time is 7 days or more and (5) the cured mortar is dried under vacuum to reduce the temperature level employed during the drying process. The areal homogeneity of the mortars tested is reasonably good, although significant trends in vertical permeability were noted. The Klinkenberg and non-Darcy coefficients of mortar are such that proper scaling of these effects in the laboratory model could be expected. INTRODUCTION A long term deliverability prediction for a gas well is generally based on data determined from flow tests that are of short duration relative to the producing life of the well. These data, together with an estimate of gas reserves in place, form the basis for establishing the parameters of the mathematical model used to predict performance at future times. Results obtained from a mathematical model represent only an interpretation of the physical process being modeled. Experimental verification of the production process from discovery to abandonment is needed where production occurs under carefully controlled conditions. Ideally, one might consider such an experiment to be conducted in the field. Even if the cost of such an experiment could be justified, the time required would make it impractical to consider. However, if the time scaling problem could be handled properly, an experimental model of the gas reservoir production process could provide the necessary data to study the mechanisms of the production process in a reasonable time period. An experimental model has been designed and constructed using the data of this study as a basis. The model reservoir system consists of one producing well located at the center of a right-circular cylinder of porous material. Ten to 15 observation wells are located at strategic offset positions from the producing well. These wells, and the producing well, are fitted with pressure transducers so that the pressure-time history can be recorded at various radial and azimuthal positions in the drainage area during the entire production life of the system. Time is scaled in the model so that the time required to produce gas from discovery pressure to abandonment pressure is about 2 hours. This compares with a 20-year producing life in the model's field counterpart and gives a time scale factor of approximately 1:100,000. DESIGN CRITERIA To establish design criteria for the experimental model, the reservoir is considered to be a finite right-circular cylinder of radius rr, and height h with a producing well of radius rw located at the center and completed through the producing formation. This reservoir consists of a porous medium which has a uniform permeability k and gas porosity and the gas contained in the reservoir has density p, viscosity µ and molecular weight M. Initially, the pressure at all points within the reservoir is uniform at po. and the reservoir temperature is T. Since the reservoir production process has been demonstrated to occur in two distinct transient modes for either Darcy or non-Darcy flow,l it is

By S. A. Falconer

This paper deals with the practical application of the Dutch State Mines cyclone separator for fine-coal cleaning. The more important operating variables are discussed, and results of a number of continuous-scale tests on various fine coals with a 6-in. cyclone separator are given. Descriptions of the Cyanamid Pilot Plant and the 50 tph Cyclone Separator Plant at the Emma Washery in Holland are included. TODAY, as never before, the coal producers of this country are faced with the necessity for obtaining maximum yield of marketable coal of all sizes down to and including the finest. Particular interest is being displayed in a more effective means of recovering the finer sizes which in the past so often have been discarded to waste or treated by inadequate equipment. The reasons for this interest are easily understood. Rising mining costs have resulted in the increased use of mechanized equipment underground for full seam mining. This, in turn, means more refuse in the run-of-mine and also more fines in the feed going to the cleaning plant. Stringent antistream pollution laws now make it necessary at least to impound the fines, and usually it is a paying proposition to recover the coal from these fines before sending them to the storage area. Finally, the market and price of the finer sizes has increased, but at the same time specifications have tightened and the demand is for higher grade products. During the past four years a great deal of publicity has been given to this new process and apparatus for treating fine sizes of ores as well as coal. Excellent discussions of the apparatus itself and the theoretical aspects of the basic operating principles involved in its operation have been presented by M. G. Driessen,1-3 M. R. Geer and H. F. Yancey,4,5 J. W. Hyer6 and more recently by D. A. Dahlstrom8 as well as others.7,9-11 In view of this, it has been decided to include in the present paper only a brief description of the cyclone separator and its operating principles. This paper deals primarily with some of the more practical commercial aspects of the process and equipment required for its operation; the variables in the operation of the cyclone, their effect and means for control; and the results obtained with a 6-in. semicommercial size separator on a variety of fine coals, bituminous and anthracite, using finely ground magnetite for the separating medium solids. A description is included of the commercial-size cyclone separator pilot plant installed by the Dutch State Mines at its Emma mine in Holland, where finely ground slate is utilized as medium solids. Field of Application: The Dutch State Mines cyclone separator operates most efficiently on ores and coal in the size range of % in. to about 48 mesh. On some types of feed, effective separation can be made on sizes as small as 100 mesh, but up to the present, this may be considered exceptional. Depending upon the type of medium used, the specific gravities of separation can be varied within wide limits, up to as high as 2.70, if magnetite is used as medium. Early Development: The development of the Dutch State Mines cyclone as a separator, or cleaner, was the outgrowth of early experimental work by Dries-sen' and others in Holland, just prior to World War 11, in the course of which was discovered the effectiveness of the cyclone in reclaiming and thickening the dense medium used in the "Loess" process of

Jan 1, 1951

By S. A. Falconer

This paper deals with the practical application of the Dutch State Mines cyclone separator for fine-coal cleaning. The more important operating variables are discussed, and results of a number of continuous-scale tests on various fine coals with a 6-in. cyclone separator are given. Descriptions of the Cyanamid Pilot Plant and the 50 tph Cyclone Separator Plant at the Emma Washery in Holland are included. TODAY, as never before, the coal producers of this country are faced with the necessity for obtaining maximum yield of marketable coal of all sizes down to and including the finest. Particular interest is being displayed in a more effective means of recovering the finer sizes which in the past so often have been discarded to waste or treated by inadequate equipment. The reasons for this interest are easily understood. Rising mining costs have resulted in the increased use of mechanized equipment underground for full seam mining. This, in turn, means more refuse in the run-of-mine and also more fines in the feed going to the cleaning plant. Stringent antistream pollution laws now make it necessary at least to impound the fines, and usually it is a paying proposition to recover the coal from these fines before sending them to the storage area. Finally, the market and price of the finer sizes has increased, but at the same time specifications have tightened and the demand is for higher grade products. During the past four years a great deal of publicity has been given to this new process and apparatus for treating fine sizes of ores as well as coal. Excellent discussions of the apparatus itself and the theoretical aspects of the basic operating principles involved in its operation have been presented by M. G. Driessen,1-3 M. R. Geer and H. F. Yancey,4,5 J. W. Hyer6 and more recently by D. A. Dahlstrom8 as well as others.7,9-11 In view of this, it has been decided to include in the present paper only a brief description of the cyclone separator and its operating principles. This paper deals primarily with some of the more practical commercial aspects of the process and equipment required for its operation; the variables in the operation of the cyclone, their effect and means for control; and the results obtained with a 6-in. semicommercial size separator on a variety of fine coals, bituminous and anthracite, using finely ground magnetite for the separating medium solids. A description is included of the commercial-size cyclone separator pilot plant installed by the Dutch State Mines at its Emma mine in Holland, where finely ground slate is utilized as medium solids. Field of Application: The Dutch State Mines cyclone separator operates most efficiently on ores and coal in the size range of % in. to about 48 mesh. On some types of feed, effective separation can be made on sizes as small as 100 mesh, but up to the present, this may be considered exceptional. Depending upon the type of medium used, the specific gravities of separation can be varied within wide limits, up to as high as 2.70, if magnetite is used as medium. Early Development: The development of the Dutch State Mines cyclone as a separator, or cleaner, was the outgrowth of early experimental work by Dries-sen' and others in Holland, just prior to World War 11, in the course of which was discovered the effectiveness of the cyclone in reclaiming and thickening the dense medium used in the "Loess" process of

Jan 1, 1951

By W. R. Foster, J. M. McMillen, A. S. Odeh

The complete equations of average linear momentum balance for a single-phase fluid in an incompreisible, homogeneous, porous medium are derived. The derivation begins with Euler's equation of motion for a continuum and uses an integral transform recently developed by Slattery. 7 For steady flow of a compressible, Newtonian fluid, the usual equations of motion result. For transient flow, the space-time description of the pressure is determined in the lowest approximation by the telegrapher's equation. From the analysis a new phenomenological coefficient results which connects the viscous traction to the deriv ative of the linear momentum density. The magnitude of this coefficient determines the velocity of sound through the pore structure in this approximation to the pressure field. INTRODUCTION The modification of Darcy's law of momentum balance for steady, single-phase flow through porous media has been discussed for many years. The first modification was suggested by Forcheimerl who added terms of higher order in the velocity. These can be expected to appear because the underlying microscopic equations of momentum balance are themselves nonlinear in the point velocity field. The Reynolds tensor pvv, which represents the convective flux of momentum density, appears in the momentum balance equation. Only in rectilinear flow (parallel stream lines) does the divergence of this tensor vanish. Since the steady flow stream lines in most porous media are not parallel, nonlinear dependence of the pressure gradient on the velocity should naturally appear. This nonlinearity has nothing to do with turbulence in the ordinary sense of random fluctuations in the pressure and velocity fields. It arises simply because the stream lines converge and diverge, even for steady flows. Klinkenberg2 demonstrated that the permeability coefficient in Darcy's law depends on the absolute pressure or, alternatively, on the density field. However, because he neglected inertial terms of the Forcheimer type, his correction coefficient could not be represented by a constant but tended toward a constant as the velocity decreased. Forcheimer's and Klinkenberg's modifications can be combined in a rigorous way to account for both inertia and slip during steady flow. This will be shown in a future paper. The transient change of pressure in porous media has been described by the diffusion equation.3 This form results from eliminating the velocity and density fields from a combination of the equations of motion in the form of Darcy's law, the continuity equation and an equation of state. Fatt4 suggested that the cause of deviations from the prediction of the diffusion equation for pressure transients lies not in the choice of Darcy's law as the equation of motion but on the existence of dead-end pores which might invalidate the averaged equation of continuity. On the other hand, Oroveanu and Pascal5 noted chat the time derivative of the momentum density must be included in the equations of motion since this measures the local rate of change of momentum density. Their differential equation for pressure is the telegrapher's equation (neglecting gravity). However, their form of this equation predicts that the speed of pressure propagation through the pore structure is the same as that through the bulk fluid. M. K. Hubbert6 attempted a derivation of Darcy's law by volume averaging the Navier-Stokes equations. Since these equations represent momentum balance at a point within an open set of points containing the fluid itself, Hubbert's volume averaging cannot lead to tenns involving transfer of momentum between the fluid and the walls of the pores. Once these viscous tractions are lost by choosing a control volume containing only fluid, they cannot

By C. F. Weinaug

In recent years, several methods have been proposed for correlation of physical properties and behavior of hydrocarbon systems. These correlations were found to be unsatis. factory for predicting differential gas liberation and shrinkage data now obtained experimentally. To achieve the desired accuracy, methods were developed to adjust the correlations with two experimental pieces of data. The required data are the saturation pressure at reservoir temperature and the specific volume or density at these conditions. The saturation pressure is used to adjust the vapor-liquid equilibrium-ratio correlations. The density measurement is used to determine the apparent density of liquid methane. With these adjustments, differential gas liberation and shrinkage are predicted within the experimental error. EQUILIBRIUM RATIOS Equilibrium ratios published by the National Gas Assn. of America' were used as a basis for the calculation. The convergence pressure for the sample was determined by using a hypothetical binary system, with methane as one component and the remainder of the system lumped together to form the other component. For the critical temperature of the heavy constituent, the weight average of the critical temperatures of the ethane and heavier components was used. The correlation of pseudo-critical temperature, density and molecular weight of Matthews, Roland and Katzl was used in this calculation for the hexane and heavier fractions. Points for the critical properties of methane and the hypothetical heavy constituent were placed on a chart of the critical loci of hydrocarbon systems. A critical loci for the hypothetical binary system was drawn, and the critical pressure of this system was determined at the reservoir temperature. This critical pressure became the convergence pressure for which equilibrium ratios were read from the NGAA4 charts. The NGAA equilibrium constants for C, through C, were used for the C,; through C, fractions since they were separated on the bases of normal paraffin boiling points. The correlation of Hoffman, Crump and Hocott5 as used to estimate the equilibrium constant for the C fraction. The NGAA eauilibrium-ratio charts are based primarily on paraffin systems and have to be corrected for the presence of naphthenes and aromatics. The correlations in the literature proved too unsatisfactory for determining these corrections. EXperimental data, the saturation pressure, is used with the correlation of Soloman2 to make this adjustment. The correction factors of Soloman were cross-plotted so that the factors for ethane and heavier components were made a function of the factor for methane. a2 = 0.7927 at + 0.1646 .........(1) where a, = correction coefficient for for methane NGAA equilibrium ratio, and a2t = correction coefficient for ethane and heavier NGAA equilibrium ratios. This equation and the equation for the bubble point are solved simultaneously for the correction coefficients. The bubble-point equation is anKnXn = 1.0 . . . . (2) The equilibrium constant for the saturation pressure at reservoir temperature is used. This procedure not only corrects for the relative volatility between components, but also assures that the results will be directly related to the experimental saturation pressure. METHANE DENSITY After determining a set of equilibrium ratios, the apparent density of condensed methane at 60°F and 14.7 psia was estimated. This was found to be necessary because the correlations of Standing3 ere found to be unsatisfactory. The law of additive volumes was employed to make this calculation.

By Paul A. Flinn, Jean-Marie Robert Genin

The MCssbauer effect was used to study the distribution of carbon in Fe-C alloys of high carbon content during room-temperature aging. In freshly formed rnartensite the carbon distribution is approximately random; carbon clustering occurs dun'ng aging. In the retained austete the carbon atoms are isolated, suggesting an efiective repulsion; and no rearrangement during room-temperature aging is evident. The kinetics of the carbon clustering in martensite has been studied in detail at 0" . 10". and 20°C. The time and temperature dependence observed is sinzilar to that reported for a variety of other aging effects, such as resistance change, hardness increase, and recovery of internal friction. The stabilization of the martensite kransformation also appears to be related to the clustering effect. DESPITE extensive efforts since the early days of Reaumur, the mechanism which provides the strengthening of steel remains controversial in many cases for several reasons: 1) The structure of as-quenched martensite is not well-determined. 2) Experimental methods capable of distinguishing between various hardening mechanisms are not well-developed. 3) The temperature of formation of many low-alloy martensites is so high that the martensite formed during quenching may be already tempered to some extent before any observation. Among all the hardening phenomena, the most puzzling one occurs at room temperature, where no structural changes have been detected by the usual methods of X-ray diffraction or electron microscopy. However, a new and more sensitive technique became available with the discovery of the MBssbauer effect. This effect makes possible the detection of changes in the local environment of iron atoms in solid solution. It has been extensively used in the study of substitutional alloy systems, for example, Fe-Al,1 Fe-Si,2,3 Fe-Rh,4 and Fe-Ni.5 Making use of the possibility of obtaining new structural information, we undertook an investigation of the aging of high-carbon Fe-C martensite to follow the structural changes involved in the aging at room temperature. Preliminary results6 showed that a clustering of the carbon atoms occurs with time. A systematic study of the kinetics of the process showed a striking similarity to the kinetics of stabilization of the marten-sitic transformation, thus suggesting further investigation of the relationship. EXPERIMENTAL TECHNIQUE To eliminate difficulties with the aging of martensite prior to the first experimental measurements, we needed an alloy with an M, temperature not above room temperature. Other investigators7 were misled by results obtained on alloys which transformed above room temperature and underwent structural changes prior to the first Mossbauer measurements. Winchell and cohen8 dealt with this difficulty by using a third element, nickel, to depress the MS below room temperature. The presence of nickel did not seriously interfere with hardness or resistivity measurements, but it would complicate the interpretation of the Mossbauer data by increasing the variety of iron environments. We chose, therefore, to obtain the necessary lowering of the M, simply by increasing the carbon content. After the first quench to room temperature, our specimens are retained austenite, which we later quench into liquid nitrogen. The martensitic transformation takes place suddenly, so that the as-quenched condition of the samples is retained, since the temperature is low enough to prevent any carbon diffusion. A Massbauer spectrum at 77°K can be taken and analyzed; after an appropriate up-quenching to the aging temperature, a new Mossbauer measurement at 77°K can be made. Fig. 1 shows a typical cycle of experiments. The samples were foils 25 p thick of high-purity

Jan 1, 1969

By L. H. Sjodahl, J. B. Conway

of each particle on grain boundary movement is proportional to the area it occupies on the grain boundary and this increases with the square of the particle radius. In contrast to the impression gained by Tiwari the effectiveness of a particle, as a grain boundary obstacle, increases rapidly as the particle size increases. The counterbalancing factor in a dispersion of constant volume (e.g., those considered by Zener) is of course the rapidly diminishing number of particles, a situation which does not exist in thoria dispersed materials where the volume fraction of thoria remains constant. Although it has been assumed that the Zener approach is valid for the sake of the above argument, it is open to the following objections: 1) It assumes that the effect of many small particles along a grain boundary is cumulative and does not take into account the possibility of each small particle being overcome separately. In this case the boundary will not be able to move forward until the largest particle on the boundary has been overcome. This means that the rate controlling factor will be the rate at which a few relatively large particles are overcome with the remaining small particles playing a negligible role. 2) When the dispersion consists of very small particles the interparticle spacing is usually small compared to the grain size and most particles are located away from grain boundaries where they can play no part. The most efficient dispersion, from a purely geometrical viewpoint, is one where the particle spacing is equal to the grain size so that all the particles are on grain boundaries. Tiwari's second point that voids cannot prevent re-crystallization seems to be unfounded as several workes20-23 have shown that voids alone can retard grain boundary movement and recrystallization. To further convince Tiwari, Fig. 17 shows a void in deformed TD Nichrome holding back a recrystallization interface. Tiwari's explanation for the effect of voids on recrystallization, i.e., they reduce local strain energy and hence lower the driving force for recrystallization may be valid in itself but is irrelevant to the present case where even complete recrystallization after ONE of the more recently proposed expressions for describing stress-strain behavior is that due to Voce.1,2 This equation is usually written: s =s8 ?(s8?so)e??/?c [l] where s is the true stress, ? is true strain, cC is a constant called the characteristic strain, s8 is the asymptotic stress approached at high strain values, and so is the threshold stress at which the plastic deformation begins. While this expression has not been universally accepted as yet it does contain certain features which are consistent with experimental stress-strain behavior. In a more recent publication Hsu, Davies, and Royles3 employed the concept of generalized strain proposed by seth4 and identified a method for linearizing the stress-strain plot. In this approach the generalized strain was given by: where 7 is the generalized strain, 1 is the instantaneous length, 1, the datum length, and n is a constant called the "coefficient of strain measure". A value of n was said to exist which would yield the linearity: s —s+ S[.-(tf] [3] In recent studies of both these approaches, it has been found that while the Voce equation and the gen-

Jan 1, 1970

By Joseph E. Worthington

The present-day Northumberland gold mine is one of the deposits generally characterized as a Carlin-type occurrence. It lies at the crest of the Toquima Range in Nye County near the center of Nevada. Gold mineralization occurs in two modes, in argillaceous and in silicified limestones, and is generally very fine-grained or micron gold. The Northumberland district has had a history that is typical of many western gold districts: minor production prior to World War II and intermittent exploration thereafter until a combination of geological insight, improved economics, and the advent of heap leach technology created the Northumberland gold mine. Nye County, Nevada, was sparsely populated and little explored in the early years of the settlement of the west; the Northumberland district was not established until 1866. Initial interest was in silver and the district operated as a very small producer for the next seventy years. The disseminated gold occurrences in silicified limestones were recognized and Northumberland Mining Co. was organized to develop the property in the late 1930s. Northumberland Mining Co. actually conducted drilling operations (over 200 drill holes) and mined from small open pits in the silicified limestones. They ultimately produced almost 936 kg (33,000 oz) gold before being shut down by War Production Board Order L-208 in 1942. After World War II gold mining activities were essentially nil for over a decade due to the poor economics of gold production. The property was, however, a known gold producer and attracted recurrent exploration attention. About 45 holes were drilled under the direction of Peter Joralemon for private interests between 1959 and 1963. Next Kerr McGee drilled about 25 holes during 1963 and 1964. Some- what later, in 1968, Homestake drilled 20 holes. The property was then acquired by Idaho Mining Co. which drilled about 30 more holes between 1972 and 1974. By this time the Northumberland mine was becoming somewhat shopworn with over 300 holes drilled. Interest in gold prospects was increasing substantially in Nevada, how- ever, due to rising gold prices in late 1974, and several companies were interested in continuing exploration at Northumberland. In 1975 Cyprus Mines Corp. was successful in obtaining a joint venture arrangement with Idaho Mining Co. for further exploration and development of the property. The overall Cyprus exploration program was under the direction of James G. Hansen, Vice President Exploration. The geologist recommending acquisition of Northumberland was Peter E. Chapman who reported to Joseph E. Worthington, Manager of U.S. Exploration for Cyprus. The basis for selection of the Northumberland mine as an exploration target for Cyprus by Chapman was essentially prior knowledge of regional and 16cal geology and of the mine. Exploration for the next few years was directed by Chapman under the supervision of Worthington. During 1975 and 1976 rotary and check core drilling were conducted that indicated that a substantial Carlin-type or disseminated, low-grade gold deposit occurred in two separate bodies. Drilling was based on geologic mapping and rock chip geochemical sampling. Both ore zones were reflected at the surface as gold and arsenic anomalies in rock chips. Heap leach tests attempted in 1977 were aborted by a flash flood, but were completed in 1978. Engineering studies occupied the next couple of years until the property achieved production in the fall of 1981. It is now producing by open-pit mining with gold recovery by heap leaching and cyanide extraction at a rated capacity of approximately 2722 t/d (3000 stpd) ore. Metal recovery has been projected (probably conservatively) at 5 10 kg/a (18,000 oz per year) gold and 1.6 Mg/a (59,000 oz per year) silver. Reserves are reported to be adequate for ten to fifteen years of production. REFERENCES Anon., 1981, "Gold in Nevada," Span Magazine, Vol. 21, No. 3, Standard Oil Co., pp. 6-9. Koschman, A.H. and Bergendahl, M.H., 1968, "Principal Gold- producing Districts of the United States, Professional Paper 610, US Geological Survey, p. 193. Kral, V.E., 195 1, "Minerals Resources of Nye County, Nevada, Bulletin, Vol. 45, No. 3, Geology and Mining Series 50, Nevada University.

Jan 1, 1985

By H. L. Teichman, E. M. Sipprelle

ENACTMENT' of Public Law 290 by the 78th Congress authorized the U. S. Department of the Interior, Bureau of Mines, to conduct an experimental program to develop the technology for obtaining oil from oil shale. In adopting and later extending this legislation, the Congress recognized the impending necessity of supplementing ground petroleum reserves with synthetic fuels. Under the provisions of this legislation, the Bureau of Mines, among other things, was charged with the responsibility of developing mining techniques, methods, and equipment for mining the oil shales of the Green River formation of Colorado, Utah, and Wyoming. The oil shales of western Colorado are apparently richer, more accessible, and more amenable to exploitation than elsewhere in the Rocky Mountain region. The site chosen for the Bureau's Experimental mine is about 10 miles west of Rifle in northwestern Colorado. It is within a 1000-sq-mile area from which, it has been estimated, 300 billion barrels of shale oil could be produced from a 500-ft measure near the top of the formation. One hundred billion barrels of this amount could be produced from the Mahogany ledge, a 60 to 100-ft section near the bottom of the 500-ft measure. This ledge is considered to have economic importance at present. The Green River formation was laid down as sediment in the bottom of vast, shallow inland lakes during Eocene time. The deposit is flat-lying, and there are no faults, fissures, or local rolls. Oil shale is actually a strong, tough magnesium marlstone, which will stand unsupported over relatively wide spans. These and other natural physical characteristics favor mechanized, low-cost mining, which is essential for establishment of an oil-shale industry. It was realized from the outset that an extensive research program would be necessary to develop mining methods, equipment, and techniques for a mechanized, low-cost operation. The program was designed to include research. into all the productive phases of mining, such as drilling, blasting, loading, transportation, and maintenance of the mine structure. The methods, equipment, and techniques developed as a result of this research have established a production of 116 tons per man-shift total labor at a direct cost of $0,292 per ton. Another important phase of the research program that has received little publicity because of its theoretical nature is study of the roofstone behavior and determination of mine structure stresses. This paper purposes to discuss this phase of the research program. Preliminary studies of the physical properties of the Green River oil-shale formation were made in the Barodyramics Laboratory at Columbia University during the latter part of 1945 and the early part of 1946.* The purpose of these studies was to determine the maximum size of unsupported underground openings that would be commensurate with safety and still permit the use of large, efficient mining equipment. Also to be determined were the pillar support to extraction ratio and the shape, size, and spacing of supporting pillars. Selected samples of possible roofstones near the top of the Mahogany ledge, as well as representative samples of different rock types found within the ledge, were obtained from the Bureau's oil-shale mine for these studies. The maximum safe unsupported roof span calculated from this work was 200 ft. Using a safety factor of four, it was theoretically determined that openings 60 ft wide could be advanced under a roofstone at the top of the Mahogany ledge. To support the overburden, 60-ft-sq pillars would be left in a checkerboard pattern. From visual observations made of core samples through the selected roofstone at the oil-shale mine, it was determined that the roofstone was actually a plate 6 to 8 ft thick. Because the calculations were theoretical and allowance had to be made for unknown cracks and fractures in the formation, openings 50 ft wide and pillars 60 ft sq were originally contemplated in the Bureau's Experimental mine. This would be the minimum allowable width that would permit use of large underground mining equipment. For lower mining costs and greater efficiency larger openings were desirable. Different but analogous approaches were made to the problem at the Bureau of Mines Applied Physics

Jan 1, 1951

By H. L. Teichman, E. M. Sipprelle

ENACTMENT' of Public Law 290 by the 78th Congress authorized the U. S. Department of the Interior, Bureau of Mines, to conduct an experimental program to develop the technology for obtaining oil from oil shale. In adopting and later extending this legislation, the Congress recognized the impending necessity of supplementing ground petroleum reserves with synthetic fuels. Under the provisions of this legislation, the Bureau of Mines, among other things, was charged with the responsibility of developing mining techniques, methods, and equipment for mining the oil shales of the Green River formation of Colorado, Utah, and Wyoming. The oil shales of western Colorado are apparently richer, more accessible, and more amenable to exploitation than elsewhere in the Rocky Mountain region. The site chosen for the Bureau's Experimental mine is about 10 miles west of Rifle in northwestern Colorado. It is within a 1000-sq-mile area from which, it has been estimated, 300 billion barrels of shale oil could be produced from a 500-ft measure near the top of the formation. One hundred billion barrels of this amount could be produced from the Mahogany ledge, a 60 to 100-ft section near the bottom of the 500-ft measure. This ledge is considered to have economic importance at present. The Green River formation was laid down as sediment in the bottom of vast, shallow inland lakes during Eocene time. The deposit is flat-lying, and there are no faults, fissures, or local rolls. Oil shale is actually a strong, tough magnesium marlstone, which will stand unsupported over relatively wide spans. These and other natural physical characteristics favor mechanized, low-cost mining, which is essential for establishment of an oil-shale industry. It was realized from the outset that an extensive research program would be necessary to develop mining methods, equipment, and techniques for a mechanized, low-cost operation. The program was designed to include research. into all the productive phases of mining, such as drilling, blasting, loading, transportation, and maintenance of the mine structure. The methods, equipment, and techniques developed as a result of this research have established a production of 116 tons per man-shift total labor at a direct cost of $0,292 per ton. Another important phase of the research program that has received little publicity because of its theoretical nature is study of the roofstone behavior and determination of mine structure stresses. This paper purposes to discuss this phase of the research program. Preliminary studies of the physical properties of the Green River oil-shale formation were made in the Barodyramics Laboratory at Columbia University during the latter part of 1945 and the early part of 1946.* The purpose of these studies was to determine the maximum size of unsupported underground openings that would be commensurate with safety and still permit the use of large, efficient mining equipment. Also to be determined were the pillar support to extraction ratio and the shape, size, and spacing of supporting pillars. Selected samples of possible roofstones near the top of the Mahogany ledge, as well as representative samples of different rock types found within the ledge, were obtained from the Bureau's oil-shale mine for these studies. The maximum safe unsupported roof span calculated from this work was 200 ft. Using a safety factor of four, it was theoretically determined that openings 60 ft wide could be advanced under a roofstone at the top of the Mahogany ledge. To support the overburden, 60-ft-sq pillars would be left in a checkerboard pattern. From visual observations made of core samples through the selected roofstone at the oil-shale mine, it was determined that the roofstone was actually a plate 6 to 8 ft thick. Because the calculations were theoretical and allowance had to be made for unknown cracks and fractures in the formation, openings 50 ft wide and pillars 60 ft sq were originally contemplated in the Bureau's Experimental mine. This would be the minimum allowable width that would permit use of large underground mining equipment. For lower mining costs and greater efficiency larger openings were desirable. Different but analogous approaches were made to the problem at the Bureau of Mines Applied Physics

Jan 1, 1951

By T. B. Massalski, Horace Pops

The occurrence and the temperature dependence of the athermal martensitic transformation in bcc Cu-Zn ß-phase alloys have been studied by cold-state microscopy, differential thermal analysis, and electrical -resistivity measurements. CinenzatograpJzic studies have shown that in the majority of alloys the transformation occurs in two stages. A thermoelastic phase, having a 'needlelike" uppearance, forms initially at the MS temperature and grows relatively slowly, chiefly in the edge (lengthwise) direction. With further cooling, an additional martensitic phase forms in rapid bursts at a lower temperature, MB, Both martensitic phases appear to have the same cry stallographic habit hut their modes of formation and growth are different. For the composition range studied, between 38.55 and 41.49 wt pct Zn, the habit planes determined are close to the (2.17 ,12) plane of the matrix, in general agreement with the prediction of the phenomenological theory of martensite formation. Thermal cycling through the MB temperature produces permanent plastic deformation in the 0 matrix and gradutally eliminates the typical burst phenomena. Thermal cycling only through the MS temperature produces no noticeable deformation effects. THE bcc Cu-Zn ß-phase alloys tend to become unstable at low temperatures and undergo a martensitic transformation,'-3 but the details of the transformation have not been completely determined. Following earlier metal log raphic and X-ray work1 Tichener and ever' determined by means of electrical-resistivity measurements the temperature range of the martensite transformation during continuous cooling. The transformation temperature was found to decrease with increasing zinc content, becoming about -130°C for an alloy containing 40.04 wt pct Zn. Hull and Garwood3 made a metallo-graphic study of Cu-Zn 0 brasses at temperatures down to -160°C, and determined the habit plane of the transformation product for an alloy containing 38.88 wt pct Zn. No metallographic studies below liquid-nitrogen temperatures have been reported. The martensitic transformation in ß-brass alloys can also be induced by deformation.1,4 The MD temperature corresponding to the appearance of the strain-induced martensite is some 300°C higher than that observed without strain, and hence the transformation can be strain-induced in alloys containing a higher percentage of zinc. Massalski and Barrett4 found that alloys containing as much as 51.89 wt pct Zn could be transformed into a faulted hcp structure by cold working at liquid-helium temperature. Because the details of the MS temperature and morphology reported in the literature are somewhat incomplete, a further study has been made of some of the above features. A design of a cryogenic stage for optical metallography5 has permitted the examination of specimens at temperatures down to 4.2oK, and the use of a cinecamera has permitted a study of the morphology on cooling and heating. The particular aim of the present work was to examine the transformation temperatures, the habit planes, and the growth morphology over a wide composition range in the ß-phase field. The effect of thermal cycling upon the subsequent transformation was also examined.

Jan 1, 1964

By G. Meyrick, H. W. Paxton

Observations on the tensile deformation of single crystals of austenitic stainless steels as a function of composition, orientation, and temperature are described and compared with relevant data for other alloys. Crystals free from second phases show sharp yield points followed by Lüders' extensions of up to 20 pct. The critical resolved shear stress is strongly temperature-dependent increasing fourfold between 423O and 77°K. A temperature-independent low rate of hardening follows the Luders' extension and is frequently associated with overshoot. Unlike pure metals where Proficse cross slip usually occurs at the end of linear hardening, this stage is terminated either by cross slip or by slip on the conjugate system, the particular node apparently depending upon initial orientation and composition. The presence of 6 ferrite or martensite has a profound effect upon the magnitude of the yield stress and the shape of the stress-strain curve. In experiments on transgranular-stress corrosion cracking of austenitic stainless steels in boiling magnesium chloride, several workers1'2 have shown that increasing amounts of nickel tend to reduce the probability of specimen failure. Reed and paxton3 have observed in single crystals that the macroscopic crack plane changes as the nickel content is increased. For 18 pct Cr-8 pct Ni, the crack plane is sensibly perpendicular to the applied tensile stress; for 20 pct Cr-20 pct Ni the crack plane is (100). The average crack-propagation speed is much lower in the 20 pct Ni crystals. Furthermore, the possible importance of stack-ing-fault energy in nucleation and growth of cracks has been suggested by a number of workers. While the general effect of variations in stack ing-fault energy appears to be quite well-correlated with observed variations in cracking characteristics, each of the theories assigns rather different detailed reasons for these effects. Because the stack ing-fault energy of austenitic steels is believed to be increased with increasing nickel content, and because some theories of trans-granular cracking postulate a mechanical stage in the crack propagation (rather than relying entirely on electrochemical solution), it appeared to be of some interest to investigate the mechanical properties of a series of different compositions of aus-tenite single crystals. These experiments were considered of intrinsic value in view of the relative scarcity of such data on fcc alloys. This paper gives the results of some experiments carried out with this aim in mind, and suggests various 'other experiments which may be helpful in future studies. The experiments are also of interest in view of the recent interest in obtaining higher-strength steels by control of the imperfection content of austenite; although the compositions are not directly comparable, the results are still probably valuable. Comparisons with experiments on other fcc alloy crystals are made where possible to see how well the general pattern of behavior is understood. EXPERIMENTAL PROCEDURE The alloys used in this investigation were vacuum-melted heats of nominally 20 pet Cr-20 pet Ni-60 pet Fe, 20pctCr-16 pct Ni-64 pct Fe, and 20 pctCr-12 pet Ni-68 pet Fe.* Analyses of the material are

Jan 1, 1964