Search Documents

By J. H. Reynolds

The possibility of using a semiconductor, metal, semiconductor structure as a light detector is discussed. A brief theoretical argument is presented which predicts that this structure should have pho-toresponse characteristics similur to those of a metal-semiconductor diode, but with the magnitude of the current increased by a transistor gain factor. Measurements made at low frequencies on a particulur S-M-S device agree u~th this prediction aizd shoul that significant gain factors are attainable. The current gain is substantially higher than that predicted for the metal base transistor. It is proposed that the operation of these units is more closely approxinzated by the metal-gate model which predicts higher current gains. A qualitative discussion of its high-frequency performance indicates that detection of light modulated at microwave frequencies by a S-M-S deuice is possible. ADVANCES in the technology of chemical vapor deposition'-4 have made it possible to form a S-M-S structure consisting of a thin metallic layer sandwiched between layers of single-crystal semiconductor. It has been proposed5-7 that, if the metal layer is made sufficiently thin, this structure could be used in an amplifier having several advantages over presently available transistors including higher-frequency performance. Calculations8 predict that the maximum gain-bandwidth product is nearly an order of magnitude higher than that of a bipolar transistor having the same geometry. Maximum oscillating frequencies in the microwave range are predicted. Electrical measurements made on S-M-S devices have shown that, although the theoretical frequency characteristics are not presently attainable, current and power gain is obtained. Another possible application of the S-M-S structure is its use in a light detector. This structure is a three-layer relative of the metal-semiconductor diode. Light detection using M-S diodes is the subject of considerable present interest. They are known to have a short response time and the ability to detect light having a photon energy below the semiconductor bandgap. In this paper, the mechanism by which S-M-S photocurrent is generated is discussed. An expression is derived which shows that the response characteristics are similar to those of a M-S diode, but that the magnitude of the current is increased due to the transistorlike behavior of the device. The results of low-frequency response measurements on a particular S-M-S structure are presented. These agree with the theoretical predictions and show that significant gain factors are attainable. A qualitative discussion of the high-frequency characteristics is presented which predicts that detection of light at microwave frequencies by a S-M-S device is possible. THEORY In this discussion, the photocurrent, iT, measured across terminals attached to the semiconductor emitter and collector layers is related to the current pho-toemitted from the metal base layer. The latter will be referred to as the primary photocurrent. The behavior of the primary photocurrent is determined by the characteristics of the two metal-semiconductor diodes. The diode photoemission is illustrated in Fig. 1, which shows the emitter and collector potential barriers. The metal thickness has been greatly exaggerated. As will be discussed later, the actual barrier shape can be much more complex, but this diagram illustrates the essential features of the photoemission process. An absorbed photon having an energy greater than the barrier height can emit an electron into the emitter or collector. Since this process is discussed

Jan 1, 1968

By E. J. Harris

Mathematical solutions to complex mine ventilation problems are possible, but often the airway network is so complex that the mathematical solution becomes tedious and impractical. A fluid network analyzer, designed and built for analyzing mine ventilation problems has been in service at the Bureau of Mines' Pittsburgh station for approximately nine years. Using this analogue as a model, the mine ventilation network is simulated electrically by a combination of series and parallel circruits laid out to conform with actual mine airways. A tungsten filament lamp, referred to as a Fluistor, is used to simulate mine airway resistance. With the analogue ventilation model established, voltages of the proper amplitude to represent ventilating pressures are impressed across the circuit at points where mine fans and airshafts are located. Comparison of mathematical solutions of complex systems against analogue results showed a maximum variance of 3% for pressures and 2% for quantities. An electrical fluid network analyzer, designed and built especially for analyzing mine ventilation distribution problems, has been in service at the Bureau of Mines, Pittsburgh, for approximately nine years. It is a nonlinear, low voltage, fluid network analyzer of the type developed by the late Malcolm S. McIlroy, Professor of Electrical Engineering, Cornell University, who cooperated with G. E. McElroy, of the Bureau of Mines, in adapting the instrument to mine ventilation systems. Several modifications have been made since the original installation, but a considerable part of this paper is drawn from G. E. McElroy's original description of the analogue.' The analysis of water or gas distribution systems2,3 led to the development of this type of network analyzer. Several similar units are now employed by utility companies for this purpose; however, the Bureau of Mines unit is the only one designed specifically for mine airflow problems. Other airflow analogues employing a similar principle have been used at the Central Research Station of the Netherlands State Mines,4 in England,5 and in South Africa.6 Information on these devices indicated they were somewhat inflexible because commercial lamps with a sufficient range of resistance are difficult to obtain. Computers for mine ventilation analysis have been developed in Germany which instead of lamps use a variable resistance to adjust for turbulent flow laws. These units are expensive, but excellent results have been reported in their application. THE ANALYZER Theory of Application: As airflow generally follows the law of turbulent fluid flow, resistance to flow is nonlinear; consequently, the problem has been to find a nonlinear resistance element of suitable range that can be used for electrically simulated airflow. Tungsten filament lamps operated on alternating or direct current approximate the square-law resistance characteristics of mine airflow over a large range below maximum or rated voltage; that is, the voltage drop varies approximately as the square of the current. Consequently, the heart of the network analyzer is a nonlinear resistor known as a Fluistor, which is simply a custom-made low voltage, tungsten filament lamp that is available in a progressive series of relative resistance values ranging from 0.05 to 500 in nominal 5% steps. However, variations in manufacturing large groups result in differences of 1 to 3%, but series arrangements required for high-loss branches can be matched within about 1%. Utilizing a combination of Fluistors and load circuits, the mine ventilation system is duplicated electrically. Intake load circuits are connected from power intake to primary points of the circuit network; segments of unregulated flow along intakes and returns are represented by Fluistors, regulated splits and leakage paths are represented by load circuits and Fluistors of proper capacity; and mine exhausts are connected to ground from the last point of the network to complete the circuit. For the special purpose of representing booster fans or natural draft conditions, boosters or separate source circuits are provided that can be inserted between any two points of a network to increase voltage to the required value. Physical Layout: The analyzer consists of three 42

Jan 1, 1963

By B. K. Miller, R. S. Bradley

THE principal producing areas of fire clay in Missouri are: (I) the east central district, which includes Audrain, Callaway, Montgomery, Warren, and Boone Counties [ ] (Fig. I); (2) the St. Louis district, which includes St. Louis and St. Louis County; (3) the north central Ozark district, which includes Franklin, Gasconade, Osage, Maries, Phelps, and Crawford Counties. [ ] Most of the semiplastict fire clay is found in Audrain, Callaway, Montgomery and St. Louis Counties, and in St. Louis. Flint fire clay is found in Callaway, Audrain, and Montgomery Counties and in most of the north central Ozark district. High-alumina [ ] diaspore clay is found only in the north central Ozark district, except a few deposits found in Montgomery County. This paper is concerned with the semiplastic fire clay that occurs in the east central Missouri district near Mexico, Audrain County, Missouri, which is mined by the open-pit method as practiced by the A. P. Green Fire Brick Co. About one-fourth of the semiplastic fire clay in that district is mined in shaft mines, and three-fourths in open pits.

Jan 1, 1941

By Earl Oliver

This paper is based on the formula that the petroleum industry is sick—find the cause, eliminate it, and the industry will get well. There is perhaps no difference of opinion that the cause is overproduction, actual or potential. But that, again, is a result rather than a cause. The problem is to study the influences that serve to keep production and consumption out of balance. Production control is a popular theme and a natural one at this time when the whole world is unstable; but production control in its popular sense means little more than the application of emergency measures while danger threatens. Economists differ as to the effectiveness of these, most of which are designed to alleviate and not to cure, but we assume there are none who question the wisdom of promoting conditions under which economic forces are permitted to operate freely in bringing about stable conditions. The petroleum industry suffers from two classes of economic ills that serve to promote overproduction; namely, those which are common to all industries and those which are peculiar to this industry. It is of the latter I wish to speak. Strange to say, government is responsible in large part for this latter class of ills that affect the petroleum industry and we are coming to recognize that only through the assistance of government can they be corrected. Instability of the petroleunl industry, in so far as human agency was involved, had its inception in 1875 when a Pennsylvania jurist, called upon to make a decision for which there was no precedent and fancying he noted some resemblance between the so-called fugitive nature of oil and gas and that of wild game, made mention of that resemblance. Other courts being impressed by the analogy enlarged upon it, and gradually fixed upon oil and gas a legal status in certain important respects similar to that of wild game. Although later the courts abandoned this analogy, certain practices that developed out of that early concept have continued to this day and are largely responsible for the industry's present plight. Thus, instead of ownership in place that is characteristic of private property generally, the law of capture was applied to oil and gas. Now, the rapid and wasteful depletion of game

Jan 1, 1932

By L. D. Jaffe, M. R. Norton, J. H. Hollomon

IN the practical heat-treatment of steel the decomposition of austenite usually occurs during cooling rather than at constant temperature. Nevertheless, the course of this decomposition has generally been studied only isothermally. Isothermal studies are not only simpler experimentally, but have the great theoretical advantage that one of the variables, temperature, is constant. It is the purpose of this paper to outline the principles that govern the relations between isothermal and anisothermal? decomposition of austenite, to present and systematize the available experimental information, and to indicate the gaps in the existing knowledge. Some of the experimental information is the result of new work. § Most of it is derived from scattered data in the literature. Many of these data were obtained incidentally in the course of research on other subjects and their significance has not been pointed out and perhaps not understood. It is hoped that this paper will aid future planning of more extensive research on anisothermal decomposition. METHOD In order to study the relations between isothermal and anisothermal decomposition, it appears fruitful to view anisothermal decomposition as taking place at a series of constant temperatures1 (except for the martensite reaction, which does not occur isothermally to an appreciable extent). When the time the steel is at each temperature is finite, the over-all amount of the reaction is considered to be the sum of the amounts occurring at each of the successive temperatures. During continuous cooling or heating, the time the steel is at each temperature and the difference between successive temperatures can be considered to approach zero. The over-all amount of transformation will then be given by integration over the range of temperatures involved. This point of view is advantageous in that it considers anisothermal transformation to be a series of isothermal transformations. The problem thus becomes one of determining the effect of partial decomposition at any given temperature upon subsequent decomposition at another temperature. Single Anisothermal Reaction Consider a phase brought to a temperature at which it is unstable, held there until it has partially transformed, and then brought to another temperature at

Jan 1, 1946

By M. Sagheer

This paper gives a report of the laboratory work investigating the fundamental flotation characteristics of chromite and its commonly associated mineral, serpentine. Floatability curves, showing floatability of chromite at different concentrations of sodium oleate and pH, were obtained by pick-up method. One of the difficulties encountered in flotation of chromite in presence of serpentine has been attributed to dissolved metal ions. The influence of metal ions, dissolved in pulp filtrate, on floatability of pure chromite and serpentine has been studied and it has been shown that Mg, Ca and Fe ions depress chromite. A considerable amount of work applying bubble pick-up method was carried out to counteract the depressing action of metal ions. Various methods and reagents were applied in this connection. Validity of each method and reagent has been discussed. Probably due to the abundance of high-grade chrome ores, very little has been published concerning the flotation of chromite. As improvements in mineral beneficiation are realized, more attention is being directed to low-grade ores previously considered unusable. Currently, gravity concentration is the principal process applied to upgrade chrome ores, but this cannot be used for finely disseminated ore because of the substantial losses in the fines,1,2,3 To avoid these losses, flotation can be applied to material which is too fine for satisfactory gravity concent ration, and it is probable that a combination

Jan 1, 1967

By P. Somasundaran

Processing of fine particles in suspension is markedly affected by their state of dispersion/aggregation. In addition, tendency for a given component of the system to undergo selective aggregation or selective dispersion is an important property which may be put to use for processing. In this paper, principles governing flocculation, dispersion, and selective flocculation of mineral fines are discussed and then the role of major solution properties such as pH, ionic strength, etc. is examined.

Jan 1, 1980

By Frank R. Milliken

This paper is a running commentary on metallurgical problems and developments, stressing ilmenite flotation, since the start of operations five years ago, at the mill of National Lead Company, Titanium Division, MacIntyre Development, Tahawus, New York. In early 1941, when world conditions threatened to cut off the supply of ilmenite (obtained largely from India) to this country, the National Lead Company started to develop and bring into production their MacIntyre Development. This operation supplied the bulk of the ilmenite used during the war period for the manufacture of the much needed titanium pigments. MacIntyre Development is at Tahawus, New York, on the headwaters of the Hud- son River in the center of the scenic Adirondack Mountains. A general description of the operation was given in the Adirondack Issue of Mining and Metallurgy for November 1943. Operating tonnages and production have increased since 1943, however. Nearly 10,000 tons of.ore and waste is broken and loaded daily in the open-pit mine. About half of this tonnage is ore, from which is produced nearly 800 tons of ilmenite concentrate and 1600 tons of magnetite concentrate daily. Ore—types From an ore-dressing standpoint, there are five rather distinct ore types and two waste-rock types in the mine. The ore types are shown in Table I. The anorthosite waste is a coarse-grained white rock, largely labradorite feldspar. The gabbro waste is generally finer grained, and contains, in addition to feldspar, 35 to 75 pct iron silicates such as hornblende, in garnet and biotite. A minor mineral mineralogically, but important metallurgically, is apatite. A few calcite

Jan 1, 1949

By P. T. Gallagher, W. A. Oates

THE partial excess entropy of interstitial solutes in metals, SXS , has usually been interpreted as being principally vibrational ever since the initial statistical treatment of hydrogen in metals by Fowler and Smith-ells. The vibrational entropy is considered being due to the optical modes of the light interstitial atom. Little attention has been given to the magnitudes of the values of SXS'. Leiser and Witte2 and Ebisuzaki and O'Keeffe3 have noted that for hydrogen in metals Si is approximately constant for different metals. On the other hand if it is assumed that the interstitial solute is an isotopic defect then, as shown by McLellan, SXS should vary from metal to metal as follows: where S is the standard entropy of the solvent and Mi, M, are the masses of the interstitial and solvent atoms. respectively. Fair agreement with this equation was found for oxygen in silver and nitrogen in iron4 and for carbon in iron.= Ln a subsequent analysis of metal- hdrogen systems McLellan' found a variation of $' from metal to metal but not in a manner expected from the isotopic impurity equation. However, a possible correlation between the energy of solution, Ei, and sf was noted. Similar correlations have been noted for certain dilute substitutional solid Solutions 7, 8 and recently Kubaschewski 9 has demonstrated a correlation between integral heats and ex-

Jan 1, 1970

By F. M. Yans, A. D. Donaldson, A. R. Kaufmann

Beryllium was mixed by powder. metallurgical techniques with copper, nickel, iron, and chromium, respectively, to form beryllium -rich binary alloys which Mere then extyuded and rolled transtverse to the extrusion direction. The effect of each alloying element was determined by tensile testing. In solid solution, small amounts of iron and nickel had an embrittling effect, while copper in solution increased the strength but had no effect on ductility. The effect of chromium was complicated and not readily explainable. Observations concerning the planes and modes of fracture were made. BERYLLIUM possesses some very attractive properties for general design applications, especially its strength to weight ratio which is approximately twice that of aluminum and three times that of stainless steel. Equally significant, however, is its combination of high moduli , high strength (approximately 70,000 psi tension and 40,000 psi shear), and low density (0.0658 Ib per in.3), which has made it a potentially important structural material for use in high-speed aircraft and missiles. The main attractions of beryllium are most marked when compared to other constructional alloys now in use. For example, while its density is approximateiy that of magnesium, its modulus of elasticity is approximately seven times that of magnesium, three times that of titanium, four times that of aluminum, and 1 1/3 times that of steel. Furthermore, its relatively high strength and high melting temperature permit design for service temperatures to about 1100°F. It is felt by the aircraft industry in general,' that the high cost of beryllium can easily be amortized by the savings in fuel costs, and increases in aircraft payload and range. The only factor which has prevented the use of the metal in structural applications is its lack of sufficient ductility. It is this property that has retarded the development and utilization of beryllium. Beryllium's modes of deformation, Fig. 1 indicate that the main fracture planes at room temperature in a randomly oriented sample are the (0001) basal planes; the (1150) prism planes are the planes of secondary fracture.' Klein, Macres, Woodard, and Greenspan3 obtained elongations of up to 40 pct in beryllium sheet rolled above 700°C when the (0001) basal planes were oriented parallel to the plane of the sheet (see Fig. 2).

Jan 1, 1962

By V. W. Aubel

Among the iron-bearing ores of the world, the titaniferous iron sands of New Zealand are probably the least known to American engineers. This is not surprising in view of the fact that American ironmasters look with disfavor on any, even domestic, ores containing over 1 per cent. titanium. The possibilities of smelting titanium-bearing ores in the blast furnace are still undetermined, but the problem of their efficient reduction is becoming more important each year. There seems to be little inclination on the part of American furnace operators to tackle this problem, and they will no doubt continue to utilize the non-titanium ores at their command, leaving research and experiment to those countries not so fortunately endowed. New Zealand has, however, been intensely interested in her deposits of titanium-bearing iron sand, and during the last 50 years considerable English and New Zealand capital has been expended on this problem. The extent of the New Zealand iron-sand deposits is almost beyond measure. From Patea north to Manuka Heads, along almost the entire west coast of the North Island, these deposits exist. Wherever there is beach sand along this 300 mi. of coast line, the sand is iron bearing. It varies considerably in grade; but wherever the contour of the coast affords small bays and inlets, large dunes are found that are remarkably uniform in quality. Several of these large deposits, especially those at New Plymouth and Patea, are noted for their high iron content. The dune at New Plymouth runs between 55 and 60 per cent. of metallic iron; the panning action of the prevailing westerly winds and northwesterly currents has no doubt resulted in this concentration. Whatever the origin of this material may be, there is no doubt that deposition is going on continuously. At New Plymouth, a small artificial harbor, protected from the drifting sand by a large breakwall, has been dredged. Here sailing vessels have for years been loaded with iron sand for ballast by means of a crane and grab bucket operated from the wall of the breakwater. Thousands of tons of sand have been removed from this spot yet each succeeding storm renews the supply. The sand dune shown in Fig. 1 has been tested to a depth of 50 ft. (15 m.) without losing its

Jan 1, 1920

By A. McLean, D. W. Gomersall, R. G. Ward

An experimental study has been made of the solubility of nitrogen in liquid iron and liquid Fe-C alloys using levitation melting and a rapid quenching device. Iron alloy droplets were equilibrated with nitrogen gas at 1 atm pressure, quenched, and analyzed. Previous techniques for studying the Fe-C-N system have produced data which me in marked disagreement. This disagreement is due largely to errors caused by reaction between the molten alloy and the crucible material. With the levitation procedure, errors from this source have been eliminated and precise solubility data obtained for temperatures between 1450° and 1750°C. C-N interactions in molten iron have been expressed in terms of first- and second-order free energy, enthalpy, and entropy parameters. ALTHOUGH the solubility of nitrogen in iron base alloys is in general small, the effects of nitrogen on the properties of steel may be quite profound. For most purposes nitrogen in finished steels is undesirable, particularly in the low-carbon grades, since on cooling to room temperature the solubility limit of nitrogen in the steel may be exceeded and this can lead to embrittlement and loss of ductility on aging. On the other hand, nitrogen can improve the work-hardening properties and machinability of steels while in certain stainless grades nitrogen is important in order to stabilize the austenite phase. It is, therefore, desirable that one should be able to predict the solubility of nitrogen in liquid iron alloys. To do this, information is required concerning the interactions between nitrogen and the various alloying elements which may be present in liquid iron. There have been several investigations of these effects in recent years1"7 and the interactions between nitrogen and many elements dissolved in liquid iron are now known to a high degree of precision at steel-making temperatures. Unfortunately, a number of iron alloy systems which are of interest in steelmaking have been difficult to deal with by the experimental techniques generally used for this type of investigation. Among the most important of these are the Fe-C alloys. In the past, two methods have been widely used for determining nitrogen solubilities: the Sieverts' technique, in which the amount of nitrogen required to saturate a given mass of liquid metal at a particular temperature and pressure is measured volumetrically, and the sampled-bath technique in which liquid metal held in a crucible is equilibrated with a gas phase containing a known partial pressure of nitrogen, and samples drawn from the melt are quenched and analyzed. These two methods have been discussed in detail elsewhere.5,8 With the Sieverts' technique, errors may be introduced from the following sources: i) Gas adsorption on metal films which have condensed on the cooler parts of the reaction chamber. ii) Uncertainty in the determination of "hot volume" calibrations. iii) Crucible-melt interaction, particularly if a gaseous reaction product is formed or if the melt becomes contaminated with material from the crucible walls. The sampled-bath method may also suffer from errors due to reaction between the melt and the crucible material. In addition, there is the possibility that gas may be lost from the sample during solidification and cooling. In the present investigation, the solubility of nitrogen in liquid iron alloys has been studied by means of a new technique based on the use of levitation melting equipment and a rapid quenching device. In addition to the fact that problems of the type outlined above are avoided, this particular approach has the following advantages: i) The high-frequency current induces vigorous stirring within the levitated droplet so that gas-metal equilibration is rapidly attained. ii) The gas phase surrounding the melt can be changed very quickly and is easily controlled. For example, a droplet may be levitated in helium, deoxidized in hydrogen, equilibrated with nitrogen, and quenched, within a period of 15 min. ii) Melts can be readily under cooled or superheated, thus extending the effective temperature range of an investigation and allowing temperature-dependent data to be determined with a high degree of precision. Excellent reviews of levitation melting techniques and their application to physical-chemistry studies at high temperature have been published recently by Jenkins et al.,9 Peifer,10 and Rostron.11 In the present investigation a levitation melting technique has been used to obtain data for the solubility of nitrogen in pure liquid iron and liquid Fe-C alloys at temperatures between 1450° and 1750°C. The solution of nitrogen in liquid iron can be described by the reaction:

Jan 1, 1969

By Sales, Reno

Since leaving school my efforts have been geared to the task of making geology useful to the mining industry. The responsibility of the economic geologist or mining geologist of today has grown to be more, than that of merely finding a faulted segment of a vein. The very life of our mining industry is at stake. The tremendous progress in every branch of our modern civilization has been made possible through the developments in the use of metals. Many of our great industries, including that amazing field of aircraft production live and thrive only because of metals.

Jan 1, 1942

By Reno H. Sales

Since leaving school my efforts have been geared to the task of making geology useful to the mining industry. The responsibility of the economic geologist or mining geologist of today has grown to be more, than that of merely finding a faulted segment of a vein. The very life of our mining industry is at stake. The tremendous progress in every branch of our modern civilization has been made possible through the developments in the use of metals. Many of our great industries, including that amazing field of aircraft production live and thrive only because of metals.

Jan 1, 1942

By C. R. McEwen

The displacement equations of Buckley and Lever-ett' have been successfully applied to the prediction of oil recovery in frontal drives for a number of years. Commonly, the capillary pressure term is omitted from Leverett's fractional flow formula. The resulting satura-tion-vs-distance curves become multi-valued, however. Buckley and Leverett, recognizing that the neglect of capillarity was most likely the cause, proposed that this part of the solution he ignored. An ingenious method of propagating a discontinuity in place of the multi-valued portlon of the curve was devised by Cardwell using "non-capillary displacement theory". However, it would seem that a completc description of the displacement pracess would require the inclusion of capillary forces. Three publications on displacement theory have appeared in which capillary pressure was included. Ter-williger. et al', calculated saturation profiles which matched those which they observed when gas displaced water vertically downward. Based on their study, Jones-Parra and Calhoun5 roposed a method of computing saturation distributions sufficiently removed in time from the initial conditions so that all saturations in the flood front region were assumed to move with the same velocity. This latter assumption corresponds to the tangent construction on the flowing fraction-vs-satura-tion curve proposed by Welge." A numerical solution to the problem of water displacing oil from a water-wet porous medium was recently presented by Blair, ef at'. The initial conditions included a uniform saturation slightly above interstitial water saturation. that is, the permeability to water ahead of the front was not zero. This appeared to result in a region of slowly rising water saturation ahead of the front, at least for the particular set of relative permeability and capillary pressure data used to illustrate the computation. The authors also postulated an "end-effect" at the outflow face of the system, whereby no water could pass out of the system until the water saturation had built up to a high value. The saturation profiles computed under these assumptions show water accumulating at the downstream end of the system while the flood front proper is still traveling toward the outlet. The purpose of this paper is to present the results of a numerical solution to the one-dimensional water-flooding equation in which no outlet end-effect is considered and where there is no flow of water ahead of the flood front. It should be noted that the contemporary paper of Fayers and Sheldon8 deals with the problem under discussion. For a thorough treatment including both capillarity and gravity the reader is referred to their paper.

By E. W. Johnson, M. L. Hill

Equilibrium concentrations of hydrogen in iron were measured at H2 pressures up to 136 atm and temperatures down to 145°C. Residual hydrogen was prominent near 600°C in air-melted but not in vacuum-melted iron. The diffusible hydrogen solubility is abnormally high below 390°C, confirming the hypothesis of hydrogen trapping.' It appears that the traps for hydrogen in iron form suddenly on cooling. The estimated H2 pressure in equilibrium with 5 ppm hydrogen in steel at room temperature is less than 1000 atm. It was shown previously1 that the diffusivity of hydrogen in a-Fe below 200°C is anomalously low, a behavior attributed to the presence in the metal structure of hydrogen "traps." The energy of the trapped hydrogen was computed as 4.8 kcal Per g-atom below that of the interstitially dissolved hydrogen. The strongest confirmation of the trap hypothesis should be obtainable from measurements of the hydrogen solubility at low temperatures. such measurements have been performed and are reported in this paper. The "residual hydrogen" effect1'' must be carefully controlled if valid measurements of the solubility are to be obtained, and such an effort was made in the present work. Previous data for the solubility of hydrogen in iron have been summarized by Geller and Sun.3 Their equation for the most probable solubility at 1 atm in a-Fe above 400°C is

Jan 1, 1962

By John C. Sawyer

A brief review is given to show that catastrophic oxidation of stainless steel in the presence of lead oxide is similar in many respects to catastrophic oxidation as caused by MoO3 and V2O5, Experimental data are presented to show that lead oxide accelerates the normal oxidation process of stainless steel by chemically altering the normally protective oxide film formed on the base metal. Data are given to show that similar reactions occur during oxidation of stainless steel in the presence of MOO3,and V2O5. THE mechanism by which pure metals oxidize at high temperatures has been the subject of intensive research for many years and much has been accomplished towards understanding the processes involved. The mechanisms by which alloys oxidize have also been investigated, but due partly to the fewer number of investigations and partly to the complexity of the oxide systems present, available knowledge is not as extensive as with pure metals. When oxidation processes are further complicated by atmospheres contaminated with sulfide, halide, or oxide vapors, the knowledge of fundamentals becomes meager or altogether lacking. Thus, it is not surprising to find that the catastrophic oxidation of stainless steels in metal oxide vapors of MOO, and V2O5 is not a well understood phenomenon despite the fact that a number of investigations have been undertaken. The literature in dealing with the subject of catastrophic oxidation is primarily concerned with the effects of MOO3 and V2O5, but does mention that other metal oxide vapors, one of which is lead oxide, appear to promote a similar type of accelerated oxidation. While this latter effect is virtually unknown, the deleterious effect of lead oxide is of considerable commercial importance, as it is believed to be one of the fundamental reasons for exhaust-valve failure in gasoline engines. For this reason studies have been in progress for many years attempting to better understand the mechanism involved. Modern exhaust-valve alloys"2containing 20 to 25 pct Cr plus nickel and/or manganese are in effect high-grade austenitic stainless steels exhibiting ex- cellent oxidation resistance in air at exhaust valve operating temperatures of 1100° to 1700°F; yet these same alloys are prone to corrode during engine service because of the conditions attending their operation. These conditions are such that the valves become coated with deposits of complex lead compounds mainly derived from gasoline additives of tetraethyllead, ethylene dibromide, and ethylene dichloride. Literature searches3-7 and discussions with various investigators show that considerable difference of opinion exists as to the nature of the lead-bearing deposits found on the surface of exhaust valves and the atmospheres to which they are subjected; yet, all seem to generally agree that corrosion, a gradual transformation of alloy to nonmetallic products of corrosion, is a consequence of the presence of lead compounds. This majority opinion seems to be substantiated by laboratory engine tests which show that corrosion does not occur to any appreciable extent when lead-free fuels are used. The first observations of catastrophic oxidation reported in the literature were probably made by pfeil,8 but it was Leslie and Fontana9 who undertook the first detailed study of the phenomenon. Their work was chiefly centered on the acceleration of oxidation which took place when stainless steels containing more than 3 pct Mo were heated in air with restricted circulation. These investigators reported that the presence of other oxides near the surface would further accelerate the rapid oxidation which occurred. While they recognized that the effect was attributable to the presence of molybdenum, it was Rathenau and Meijering" who emphasized the fact that the presence of molybdenum in the alloy was incidental to the presence of MOO3 vapor in the atmosphere surrounding the specimens. Evans,11 as well as Cunningham and Brasunas 12 studied similar

Jan 1, 1962

By K. H. Coats

This paper describes an approximate technique for handling the problem of percolation of evolved gas upwards through the oil column in computer simulation of natural depletion. This technique has been incorporated into a general model for simulating three-phase flow in one, two or three dimensions. The mathematical model for perfonning these calculations is described in detail in a separate article. 1 While vertical gas percolation occurs during natural depletion in a reservoir of any configuration, it is especially pronounced in the pinnacle reel or bioherm. The reel may have an areal extent less than one section with a thickness of up to 800 It. The upward percolation of evolved gas often limits the time step in calculations as little as one day. Using this small time step, computer expense for a single 30- to 40-year simulation on even a one-dimensional basis has exceeded 92,000. The method described here for handling the percolation allows time steps of 60 days or more (depending on reservoir size and production rate), resulting in a considerable reduction in computing expense. The method also allows calculations in which secondary gas caps build up in tight zones of the oil column below the main gas cap. The validity of the method is indicated in connection with an example pinnacle reef field. Calculated results using a 2-day time step (where the method in question is not needed and not invoked) are compared with results using the method and a 60-day time step. The comparison shows good agreement. Results from one- and two-dimensional simulations of the reef are presented along with the corresponding computing times on the CDC 6600 computer. A three-dimensional simulation was also performed and the required computing time is given. INTRODUCTION A general analysis for simulating three-dimensional, three-phase flow in reservoirs has been developed. 1 In applying this model to reservoirs undergoing natural depletion, a time-step restriction was encountered due to the flow of evolved gas upwards through the oil column and toward the gas cap. A remedy for this problem has been incorporated in the analysis and is described here. The time-step restriction is encountered only in calculations which include flow in the vertical or near vertical direction. The restriction occurs to some extent in reservoirs of any geometrical configuration, but it is especially pronounced in the pinnacle reef or bioherm where the ratio of thickness to areal extent is unusually large. This paper describes the problem, a method of handling it, incorporation of the method in the three-dimensional, three-phase model, and, finally, a test of the method's validity in an application to an example pinnacle reef reservoir. THE PROBLEM During the early stages of reservoir depletion, pressure falls below bubble point in progressively lower regions of the oil column. Continuing production results in evolution of dissoived gas throughout the oil column. This gas then percolates upwards toward the top of the reservoir. If the gas encounters a sufficiently low permeability zone in its travel upward, then it can accumulate and form a secondary gas cap. If no zones are encountered which are tight enough to hold gas against the gravity forces, then the gas travels on until it reaches the top of the sand or the main gas cap. Numerical simulation of multiphase flow in reservoirs is generally performed with time steps such that the flow of a fluid into or out of a block in one time step is a fraction (considerably less than one) of the total amount of that fluid present in the block. Use of a time step where the time step's

Jan 1, 1969

By D. W. Brunton

The maps of our large mines are usually prepared with the greatest care; and it is somewhat singular that, in compari~on with the great amount of time and money spent in surveying and platting, 80 little actual use is made of them. Almost the only purpose for which a completed survey-map is afterwards consulted, is the determination of the relative position of the different workings to each other, and to the boundary-lines of the property. After the completion of such a map, it should be made the beginning of another, and in most cases a far more important undertaking, namely, its utilization as a starting-point for a complete inventory of the company's underground possessions. The ordinary mine-survey map, being nothing but a record of what has been done, is, in one sense, only ancient history. To increase its value, such additions should be made as will render it a complete statement of the amount and value of ore in sight at any particular time, and a guide for future development. Comparatively little extra labor is involved in this undertaking, since the larger and most expensive part of the work has already been completed when the mine has been surveyed and mapped. The necessary additions consist in working out and platting on the maps, the geology of the mine as exposed in the workings, in such a manner that the geological survey may be of daily use in the development and operation of the mine. The first step towards the production of a geological map consists in tracing individual level-sheets from the general or composite map. The area to be included, outside of the property in question, will depend very much on local conditions; but, for geological, legal and commercial reasons, it should be extended as far as reasonably practicable. The scale to be

Jan 1, 1906

By J. W. Downey, M. V. Nevitt

The phase boundaries for the 950" isothermal sections in the ternary systems Zr-Co-0 and `Zr-Ni-0 have been determined for the composition range from 50 to 100 at. pct Zr. The two systems show very similar phase relations, having no extensive solid solution phase fields. Each contains a ternary phase. These phases are apparently isostructural, but their structure has not been determined. Some aspects of the phase relations are discussed in terms of the alloying behavior of transition metals. THE work described in this paper is the outgrowth of a recent study of the occurrence of phases having the Ti2Ni-type structure (structure-type E9,) in certain ternary systems involving Ti, Zr, or Hf with another transition metal and O.", In the Zr-CO-0 and Zr-Ni-0 systems no Ti2Ni-type phases were found to occur. However, there are several interesting aspects of the phase relations in the two systems which have significance from the point of view of the alloying behavior of transition metals. The results of this investigation may also have some importance in studies of the oxidation of Zr-Co and Zr-Ni alloys. In both the Zr-Co-0 and Zr-Ni-0 systems only the 950" isothermal sections were investigated and, as a further restriction, the study was limited to the composition range from 50 to 100 at. pct Zr. A tentative Zr-Co binary diagram has been published by Larsen, Williams, and Pehin. In the composition range pertinent to the present work they report a eutectic at 980°C and 75.9 at. pct Zr, the products of which are the terminal solid solution based on /3 Zr and the compound Zr2Co, and a eutectic at 1080" and 64.8 at. pct Zr whose products are Zr,Co and ZrCo. The solid solution based on /3 Zr is shown to decompose eutectoidally at 826°C into a Zr and Zr2Co. The limits of solubility of Co in a and /3 Zr have not been established. The structure of Zr2Co is not identified in the publication just cited. Dwight has reported that ZrCo has the CsC1-type strcture. The Zr-rich portion of the Zr-Ni diagram has been determined by Hayes, Roberson, and Paasche." The phase relations are very similar to those of the ZrCo system. A eutectic reaction whose products are /3 Zr containing 2.9 at. pct Ni and Zr,Ni occurs at 961°c, and a eutectic between Zr,Ni and ZrNi is found at 985". The solid solution based on /3 Zr decomposes eutectoidally at 808°C. The solubility of Ni in a Zr is not known accurately but is believed to be very small. Smith, Kirkpatrick, Bailey, and Williams7 have found that Zr2Ni has a tetragonal structure of the A1,Cu-type and that ZrNi is orthorhombic. Domagala and McPherson8 have published a constitution diagram for the system Zr-ZrO,. At 950" their diagram indicates that the solid solution of 0 in 0 Zr is stable from 0 to 0.5 at. pct while the phase field of 0 in a Zr extends from 6 to 29 at. pct. These solubility limits were adopted in the present study and no binary Zr-0 alloys were made. No previous data on the phase diagrams of the ternary systems are known to exist. EXPERIMENTAL PROCEDURE The experimental details involved in the preparation of alloys in this laboratory by arc melting have been described in several previous papers"3 and they will not be repeated here. Information concerning the purity of the metals used is given in Table I. Oxygen was added in the form of reagent grade ZrO,. All of the cast specimens in both alloy systems were annealed in air-atmosphere tube furnaces at 950 3' for 72 hr and water quenched. The specimens were protected from oxidation by wrapping them in Mo foil and sealing them in quartz tubes that had been evacuated at room temperature to a pressure of 1 x 10B mm of Hg. The phase boundaries were determined by metallography, and identification of the phases was accomplished primarily by X-ray diffraction methods which employed a powder camera having a diameter of 114.6 mm. The diffraction techniques which are in use in this laboratory have been previously described.' An etchant that proved satisfactory for most of the alloys consisted of 5 pct by vol of AgNO

Jan 1, 1962