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By J. B. Umpleby

The function of gas in the development and production of oil has far-reaching consequences that should be emphasized. The technical aspects of the subject have recently had a great deal of attention but less thought has been given to fundamental concepts underlying oil and gas law and the many customs and practices that have grown up in the industry. I shall review briefly the advance in knowledge of the subject and attempt to relate these concepts to legislative, judicial and operating problems. Early writers on oil and gas in Pennsylvania noted their close association in oil pools and their contemporaneous decline in output; also, that as gas pressure decreases so does production, that new offset wells reduce the output of existing wells, and even that tubing a well lengthens its flowing life. Expanding gas was deduced as the principal expulsive force. These fundamental observations had been made at least as early as 1880.1 They were treated, however, as academic considerations and did not greatly influence law or practice for many years except to instill into all operators an urgent desire to hasten offset drilling in order to obtain as much of the flush as possible. The most noteworthy later advance in knowledge came in 1926 when Beecher and Parkhurst published their paper on Effects of Dissolved Gas upon the Viscosity and Surface Tension of OiL.² This paper added to the old idea of an expelling force the concept of a modifying agent that actually changes the physical characteristics of the oil and facilitates its movement through the pore spaces of the reservoir rock. Largely since the publication of this paper, intensive study and concerted effort have been given to means of using to a maximum, in producing oil, these combined properties of gas. This is shown clearly by the number of papers dealing with the subject, and the new and revived terms now widely used to express thought, such as the expressions gas energy, reservoir pressure, reservoir energy, gas-oil ratio, bottom-hole pressure, beaning, tapered tubing and back-pressure. These terms, some of which are

Jan 1, 1932

By G. E. McElroy

MUCH attention has been directed to mine-air flow in recent years, more especially in Great Britian where there is frequent reference to a theory of fluid flow developed by English engineers. Briefly stated, this theory is that for similar passages of the same relative roughness, in which fluid flow occurs, the conditions of flow are exactly the same for equal values of the product W D V, where W = density of the fluid, D = diameter of the passage through which flow occurs, V = mean velocity of flow, and m = absolute viscosity of the fluid flowing. This, the "Reynolds Criterion" of fluid flow, had its origin in the work of Prof. Osborne Reynolds' more than 40 years ago. Later, Lord Rayleigh amplified the theory2 which has been conclusively proved for small pipes by the experiments of Stanton and Pannel3 over a large flow range, and by Lacey4 over a somewhat more limited range. Concordant results on small pipes have also been obtained by numerous other investigators with single fluids over more or less limited ranges of flow. According to this theory results in one medium, such as water, are immediately applicable to another, such as air; and experimental results on models are (theoretically, at least) applicable to full-scale designs. This is of great importance in aeronautics and can be of considerable value in mine ventilation research. Hodgson, in a recent paper,5 has outlined the application of this theory to mine-air flow and recent English experiments' on the resistance of a timbered mine airway have been expressed in this form.

Jan 10, 1926

By W. J. Feuerstein

STRUCTURAL imperfections in crystals, in recent years, have received the attention of metallurgists concerned with single-crystal properties. Certain etching solutions cause local variations in the rate of etching at dislocations.' Dislocations are expected to be preferred segregation sites for impurities' and Dash" has shown that precipitation of copper occurs preferentially at edge-type dislocations in silicon. Diffusion rates along dislocations are probably higher than rates through more perfect crystalline regions.' These and other phenomena which may be influenced by dislocations may be studied by revealing dislocations as etch pits. This study was undertaken to develop an etch solution for silicon crystals to reveal low-angle grain boundaries associated with dislocation arrays and also etch pits with good contour definition. Additional etches have been reported by Dash," Vogel and Lovell.T rystals were sectioned on crystal lographic planes at various angles from the growth direction for microscopic examination of the etch pits. Experimental Crystals of 75-100 g mass and 3 cm diam were oriented and cut on crystallographic planes. Crystals were grown by Czochralski technique from a quartz crucible. Lapped wafers were chemically polished in a modified CP-4 etch for 1 min (bromine was deleted from the etch solution). The polished wafer was then etched* at room temperature for 5 min. The use of larger amounts of H2O and/or CH2COOH slows the reaction. The Cu(NO3),.3H2O was added to increase the reaction rate and give more definition to the etch pits developed. Some pertinent features concerning the attack of this etch on silicon can be summarized as follows:

Jan 1, 1959

SME Membership Directory Listings of record March 31, 1072 SOCIETY OF MINING ENGINEERS OF AIME

Jan 7, 1972

By H. E. Lee, P. C. Feddersen, D. R. Gittinger, G. W. Dunn, J. B. Schuettenhelm

The new Bunker Hill slag-treatment plant, designed ior, a capacity of 300 to 400 tons of hot slag per day, was "blown in" April 5, 1943. In the ensuing I5-months period, 157,530 tons of slag was processed, with an average recovery of over go per cent of the zinc and practically all of the lead contained. In addition to this high metal recovery, utilization of the waste heat in the gas and fume venting, the process has enabled the generation of 231,376 tons of steam at 250-lb, gauge. Over the first six months opcration the volume of slag treated averaged somewhat under 300 tons per day. Reclaimed dump slag made up only about 1 5 per cent of the plant feed. In October 1943, preparations for the smelting of additional tonnages of dump slag were completed and the plant capacity was increased to an average of about 420 tons of slag per day. During the nine-months interval since that date, monthly averages of 450 toils per operating day have been maintained several times. The new plant (Fig. I) is constructed in close proximity to blast-furnace operations. The fuming furnace and other necessary equipment are housed in an eastward extension of the existing blast-furnace building. Beyond this housed extension the dust-laden gas is conveyed about the perimeter of a large rectangle formed by the flues, cooling towers and baghouses. The course of a 10-ft. balloon flue, which transports the fuming furnace gas, describes the west and south perimeters. This flue connects with a set of cooling towers located at the southeast comer. The flue and cooling-tower system serving the deleading kiln constitute the north side and the two baghouses, serving the kiln and furnace operations, -border the east side. From these baghouses the several discharge gas flows are come biped and conveyed in to the rectangle, being vented to atmosphere by means of a fan through a centrally located zoo-ft. brick stack. In general, the plant design and operation follow quite closely that dictated by experience gained in years of slag-fuming practice by the Anaconda Copper Mining Go., at East Helena, Mont., and the Consolidated Mining and Smelting Co. of Canada, Ltd., at Trail, B.C., and more recently by the International Smelting and Refining Co. at Toocle, Utah. : Fuming operations at the East Helena and the Tooele plants are more or less identical. Trail practice differs chiefly in the methods employed for the storage of the hot feed slag and in the methods utilized for the handling and cooling of the fuming furnace gas. The new Bunker Hill fuming plant closely follows Trail procedure in the treatment of the furnace discharge gas while East Hclcna methods have been adopted for the storage of feed slag.

Jan 1, 1944

By J. H. Westbrook

UNTIL very recently the development of high temperature alloys has been strictly empirical. It is, in fact, a great tribute to the intuition, perseverance, and industry of the practicing metallurgists of this country and abroad that the amazing increases in gas turbine service temperature over the past 15 years have been achieved with so little fundamental knowledge. The result of this development has been the realization of successful but highly complex alloys possessing five, six, or more alloying elements and correspondingly complex microstructures. Within the last few years, considerable effort has been devoted to the identification of the secondary phases in these alloys and to the correlation of the presence or absence of such phases with alloy properties. Little attention, however, has been given the problem of identification of the mechanism (s) by which such phases enhance the properties of the alloy and especially to the assessment of the particular properties of the secondary phase (either in- trinsic or relative to the matrix phase) which are basically responsible for the improvement. Conceivable mechanisms which might apply include dispersion hardening and precipitation hardening. In both cases geometrical factors—particle size, dispersion, volume fraction, etc.—and agglomeration re-

Jan 1, 1958

By V. H. Gottschalk

THE solubility of gases in metals has been of interest since Graham's time in 1866, but, although the subject was actively studied by iron and steel metallurgists during the eighties, the era of painstaking laboratory investigation begins in 1907 with the publication of Sieverts'1 thesis on the occlusion and diffusion of gases in metals. Since then, Sieverts has worked almost continuously in this field, and his views on the subject are the prevailing ones at the present time.2 Probably the most important result obtained by Sieverts, and frequently verified since by other observers, is the discovery that at a constant temperature the solubility of almost all gases in both the liquid and solid state of most of the metals is proportional to the square root of the pressure (for pressure above 100 mm.). The obvious explanation of this fact is that the gas dissolves as atoms and not as molecules, although it has been pointed out a number of times, first by Donnan and Shawl in connection with their work on the solubility of oxygen in silver at 1075° C., that the formation and solution of a compound of the metal and gas would also be indicated by a variation of the solubility with the square or higher root of the pressure. Sieverts4 himself raised the question whether the usual explanation (i. e., that the gas dissolves as atoms) may not be wrong, when he found that the square root law held also for the solubility of sulfur dioxide in molten copper; in which case dissociation into simpler molecules or atoms does not take place. Stubbs5 subsequently showed that Sieverts and Krumbhaar's "constant" for sulfur

Jan 1, 1932

By H. H. Power, C. H. Pishny

When an oil operator becomes a party to a proration agreement he may wonder, with good cause, whether production prorated .today is merely deferred until tomorrow or whether oil might be lost. Various types of evidence obtained from production records when studied quantitatively are of great assistance in arriving at definite conclusions. A study of individual examples cited in this paper leads towards some solution of the problem, particularly when they are considered in the aggregate. Many production curves on various pay horizons were studied. A disappointingly large number of these were of contributory value, but inconclusive. However, there were enough curves of similar type from the Wilcox sand at Earlsboro, Bowlegs, Seminole City, the Cromwell horizon at Little River, and the Simpson dolomite at Valley Center, Kansas, from which reasonably definite conclusions were drawn. Assuming that deferred production is later made up with no increase in ultimate recovery, a curve (Fig. 1) shows the normal flowing and pumping life of a composite well, contructed by the family curve method. The initial production of the well shown is 1700 bbl. daily and the allowed production is 25 per cent. On this basis the average daily allowed rate for the first month is 425 bb1., or the area BCDE, which is equivalent to the area AFDG under the normal decline curve. The potential production for the second month is 1500 bbl. and the allowed production 375 bbl. daily. By this procedure a potential curve for each succeeding month is obtained (points A, H, I, J and K). If the well is opened it should produce somewhere near its potential curve for a short period and then decline at a more rapid rate than the potential curve. This theoretical analysis is basic. Actual examples exhibiting all points raised by the ideal curve are rare. Proration in the Mid-Continent area has been effected mostly by leases rather than by individual wells; hence a well may produce any

Jan 1, 1931

By Courtenay de Kalb

REVISION of the United States mining law is needed. chiefly because of the following reasons: 1. The conceptions as to the characteristics of orebodies that were held at the time the statute of 1872 was enacted have since proved to be in many respects erroneous. 2. The operation of the existing law has been found to work unnecessary hardship upon many claimants to mineral land. 3. The existing statute fails in large degree to encourage development of mineral resources. 4. The existing law often produces conflict between placer and lode-claim rights, working unnecessary injustice to placer claimants. 5. The methods of establishing the rights of locators on United States mineral land are defective, and are not uniform throughout the States within which such lands exist. LAW OF THE APEX The objections to the so-called "law of the apex" are so well known as to require no detailed statement. It is sufficient to point out that the apex rule was based upon the notion that ore deposits consisted of well-formed veins included between definite walls, like the slice of ham in a sandwich. The fact is that veins conforming to that simple type are rare. Irregularity is the rule, and the chief metal production of the United States comes from masses which bear no resemblance to the tabular form of vein. Manifestly the law of the apex fails completely in such cases. Moreover, the tendency is constantly toward the exploitation of ores of lower grade than could formerly be worked, and such deposits exist mainly in the form of large irregular impregnated zones and masses, so that the future. development of our mineral resources would be continuously embarrassed by shadowy claims to extra-lateral rights by the locators of so-called apexes

Jan 2, 1915

By Marius S. Darrow, William B. White, Rustum Roy

The PbS-PbTe systen has been studied by quench-ing and D.T.A. techniques f?om 400' to 1150°C. Runs were made in evacuated silica tubes so that all equilibria are at the vapor pressure of the system. Lattice parameters of the quenched salnples , measured by X-ray diffraction, show a complete crystalline-solution series existing over a narrow temperature range between approximately 805" and 871°C. An exsolution dome extends from a maximum of about 805"C (approximately 30 mole pct PbTe) to 1 and 96.5 pet PbTe at 400°C. A narrow melting region, deternined by D.T.A., extends form 918c (mp PbTe), The shapes of the liquides and solidus curves imply the existence of a minimum at 871°C at approximately 65 pct PbTe. THe exact composition of the minimum could not be established due to the very narrow two-phase region. At compositions containing less than 50 pet PbTe, liquidus temperatures begin to increase, while the solidus remains almost flat to about 15 mole pet PbTe before beginning to vise toward the mp of PbS (1075 C). LEAD sulfide and lead telluride are isostructural (NaC1 type) semiconductors whose electrical and optical properties have been extensively studied and used in recent years. If appreciable crystalline solution exists between these compounds, the variation of physical properties with composition could be of interest. The purpose of this investigation was to determine the extent, if any. of crystalline solution, and to obtain the phase diagram for the system. To the knowledge of the authors, only three studies of the system PbS-PbTe have been reported, and, in chronological order, each investigation found an increasing amount of crystalline solution. In 1956, Yamamoto reported finding no evidence of crystalline solution between the compounds. Sindeyeva and Godov-ikov,' in 1959, found very limited crystalline solution. but only under conditions of excess tellurium concentration. Finally Melevski s3 investigation in 1963 indicated that one solid phase exists in the region from PbS to 7 pct PbTe and from 82 pct PbTe to PbTe at 886'C, with an eutectic at 55 pct PbTe at that temperature. Detailed data on the solvus boundary were not given. EXPERIMENTAL EQUIPMENT AND MATERIALS Commercially produced PbTe and PbS powders were used as starting materials. Batches of specific mole percent composition were accurately weighed and mixed in a plastic bottle, in a shaker mill. An analy- sis of impurity content is given in Table I for pure PbS and PbTe and for two randomly selected batches after the powders were mixed. Individual samples, ranging in weight from 0.2 to 0.5 g, were sealed in evacuated silica tubes which had been thoroughly washed and rinsed with acetone and distilled water. Thus all data taken were at the pressure of the system. Subsolidus relations were studied down to 400°C by heating the samples in a vertical tube furnace for 24 hr. The sealed tubes were quenched in water with quench time from the hot zone not exceeding 1 sec. Temperatures were measured by a chromel-alumel thermocouple and controlled to 53°C for most runs. The number and composition of phases present were determined from powder X-ray diffraction patterns taken at room temperature on a Norelco diffractome-ter, using silicon as an external standard. Above 850°C quenching techniques were, in general, found to be unsatisfactory, and differential thermal analysis (D.T.A.) was used to determine melting relations. The evacuated tubes were recessed about 1 cm at one end to accommodate the differential thermocouple. Al203 was used as the reference material in a similar tube containing the other side of the differential couple. For temperature measurements, a separate thermocouple was placed in the recess of the tube containing the sample to be measured, thus providing an opportunity to obtain thermal, as well as differential, analysis. All thermocouples for these measurements were Pt-Pt 10 pct Rh. Temperature and differential curves were recorded separately on synchronized strip-chart recorders. Thermocouples and recording equipment were calibrated using NaCl and gold standards, using the melting points 801" and 1063 C, respectively, which span most of the temperature range of interest. Heating and cooling rates generally were from 4 to 7°C per min. It was found, in fact. that rates ranging from 1.5 to 25°C per min did not significantly change the data obtained.

Jan 1, 1967

By Gloyd M. Wilkes

The eastern section of the Park City district is drained to an elevation of 6300 ft, by means of the Ontario drain tunnel owned and maintained by Park Utah Consolidated Mines Co. This elevation represents a depth of 920 ft, in Park City Consolidated Mines Company's property. When development below the 900-ft. level was commenced, sinking was attempted through an incline winze in the fissure. The intensely fractured quartzite forming the walls of the vein could not be held after water was encountered, so it was decided that further sinking should be done in a vertical winze far enough in the foot-wall to be in the more solid quartzite outside the fractured zone containing the vein. Progress was good until a depth of 200 ft. below water table was reached, where the flow of water became serious. Sinking progressed 300 ft., to the 1200-ft. level, and there approximately 750 gal. of water per minute was being pumped. The last 20 ft. of sinking cost more than $200 per foot direct charges, whereas the over-all cost for the 300 ft. was $100 per foot. This high last cost was caused by excessive lost time in pumping. Crosscutting to the vein disclosed the fact that the 1050-ft. level had been developed only after drainage had been effected from the 1200-ft. level, but that the 1200-ft. level could not be opened because of the great amount of water encountered when the fractured zone was intersected. The ground in the fractured zone is so finely crushed that it precludes any possibility of economic support when it is wet. Furthermore, mining costs were found to be prohibitive after caving of vein walls had taken place as a result of an attempt to drive drifts before complete drainage had been effected. More than 3000 gal. per minute was pumped from the 1200-ft. level and the water table remained 75 ft. above this plane even after five crosscuts were driven to the fractured zone at 50-ft. intervals along the strike of the fissure from a footwall drainage drift. It was evident, therefore, that complete drainage must be effected before the fractured zone could be opened in any future development. After extensive investigations in this connection, a well-drilling campaign was decided upon to effect drainage of the fissure in advance of sinking and level development, so that all mining operations would be carried on in dry ground. Drilling Procedure A crosscut was driven through the hanging wall of the fissure on the 1050-ft. level, which was the deepest dry level at the time, to a predetermined location from which a vertical hole should reach the fractured zone at about 400 ft. below this level. A drill station was made and a raise was driven over the location for the hole, to act in lieu of a derrick or drill tower. This raise

Jan 1, 1943

By Gloyd M. Wilkes

The eastern section of the Park City district is drained to an elevation of 6300 ft, by means of the Ontario drain tunnel owned and maintained by Park Utah Consolidated Mines Co. This elevation represents a depth of 920 ft, in Park City Consolidated Mines Company's property. When development below the 900-ft. level was commenced, sinking was attempted through an incline winze in the fissure. The intensely fractured quartzite forming the walls of the vein could not be held after water was encountered, so it was decided that further sinking should be done in a vertical winze far enough in the foot-wall to be in the more solid quartzite outside the fractured zone containing the vein. Progress was good until a depth of 200 ft. below water table was reached, where the flow of water became serious. Sinking progressed 300 ft., to the 1200-ft. level, and there approximately 750 gal. of water per minute was being pumped. The last 20 ft. of sinking cost more than $200 per foot direct charges, whereas the over-all cost for the 300 ft. was $100 per foot. This high last cost was caused by excessive lost time in pumping. Crosscutting to the vein disclosed the fact that the 1050-ft. level had been developed only after drainage had been effected from the 1200-ft. level, but that the 1200-ft. level could not be opened because of the great amount of water encountered when the fractured zone was intersected. The ground in the fractured zone is so finely crushed that it precludes any possibility of economic support when it is wet. Furthermore, mining costs were found to be prohibitive after caving of vein walls had taken place as a result of an attempt to drive drifts before complete drainage had been effected. More than 3000 gal. per minute was pumped from the 1200-ft. level and the water table remained 75 ft. above this plane even after five crosscuts were driven to the fractured zone at 50-ft. intervals along the strike of the fissure from a footwall drainage drift. It was evident, therefore, that complete drainage must be effected before the fractured zone could be opened in any future development. After extensive investigations in this connection, a well-drilling campaign was decided upon to effect drainage of the fissure in advance of sinking and level development, so that all mining operations would be carried on in dry ground. Drilling Procedure A crosscut was driven through the hanging wall of the fissure on the 1050-ft. level, which was the deepest dry level at the time, to a predetermined location from which a vertical hole should reach the fractured zone at about 400 ft. below this level. A drill station was made and a raise was driven over the location for the hole, to act in lieu of a derrick or drill tower. This raise

Jan 1, 1943

By J. H. Swisher

The solubility of sulfur and rate of solution of sulfur in pure Lron were measured in H2S + H2 and H2S + H2 H2O gas mixtures. The solubility and diffusivity of sulfur at 1410°Care 0.13 pet S and 1.0 x 10-5 sq cm per sec, respectively. The solubility iS the same, but the rate of sulfurization is slower in the presence of H2O in the reacting gas. Under these conditions, the over-all rate is controlled jointly by a slow surface reaction and by solid-state diffusion; the mechanism for the surface reaction has not been identified. KNOWLEDGE of the behavior of sulfur in solid iron is desirable for the metallurgy of such products as free machining steel, where a high sulfur level is required, and inclusion-free high-strength steels, where the sulfur specifications are very low. The present investigation was undertaken to check previously reported values for sulfur solubility and diffusivity in 6 iron, and to study the poisoning effect of chemisorbed oxygen on sulfurization kinetics in H2-H2S-H2O gas mixtures. All of the experiments were performed at 1410°C. The thermodynamic behavior of sulfur in 6 iron was the subject of a paper by Rosenqvist and Dunicz.' The sulfur solubility at 1400" and 1500°C was determined by equilibrating pure iron specimens with H2-H2S gas mixtures. The maximum solubility of sulfur in 6 iron was alsc determined by Barloga, Bock, and parlee2 by reacting iron wires with sulfur in sealed capsules. In another investigation, the diffusion coefficient of sulfur in 6 iron at temperatures up to 1450°C was measured by Seibel.3 The method used was to measure sulfur concentration profiles in diffusion couples containing radioactive sulfur EXPERIMENTAL Apparatus. A vertical resistance furnace wound with molybdenum wire and containing a recrystallized alumina reaction rube was used for the experiments. The hot zone in the furnace was approximately 2 in. long with a temperature variation of ±3oC. The hot zone temperature was automatically controlled to within ±2°C, and the test temperature was measured with a pt/Pt-10 pet Rh thermocouple before and after each experiment. Flow rates of the reacting gases were obtained using capillary flow meters. Materials. The source of H2S in the gas train was a premixed cylinder containing 5 pet H2S in H2. This mixture then was diluted with additional hydrogen and argon. In some experiments, water vapor was introduced by passing hydrogen and argon through a column containing 10 pet anhydrous oxalic acid and 90 pet oxalic acid dihydrate. The vapor pressure of water above this mixture is well-known.4 Argon was used as a diluent to minimize thermal segregation of H2S in the furnace5 and to reach higher H2O:H2 ratios than could be obtained in mixtures of H2 and H2S alone. Argon was purified by passage over copper chips at 350°C and subsequently over anhydrone. Hydrogen was purified by passage over platinized asbestos at 450°C and then over anhydrone. The H2-H2S mixture was purified by passage over platinized asbestos and then over P2O5. The specimen stock was made by melting and vacuum-carbon deoxidizing electrolytic "Plastiron" in a zirconia crucible. The principal impurities are listed in Table I. In some of the equilibrium experiments, six-pass zone-refined iron was used to minimize impurity side effects. This zone-refined iron had a total impurity level of about 25 ppm. Procedure. Specimens were annealed in hydrogen for a period of at least 2 hr at the beginning of each experiment. The specimens were held in the reacting gas for times varying between 10 min and 17 hr, and cooled to room temperature in a water-cooled stainless-steel block at the bottom of the furnace. The pH2S/pH2 ratios reported are those for gas equilibrium at 1410°C. Calculations based on available thermodynamic data8 showed that the only other gaseous8 species that formed in significant amounts in the furnace were S2 and S. Even when water vapor was introduced into the gas mixture, the concentrations of SO2, SO, and so forth, were negligible. The initial partial pressure of H2S was therefore corrected for its partial dissociation to S2 and S in determining the equi-

Jan 1, 1968

By R. W. Bartlett

The rates of oxidation of tungsten have been determined at temperatures between 1320" and 3170°C and oxygen pressures to 1 amn using a surface -recession measurement technique. Above approximately 2000°C and 10-6 atm the rate is independent of temperature and can be calculated from gas collision theory assuming a constant reaction probability, e, of 0.06. Oxygen molecules react at surface sites where oxygen atoms have previously chemisorbed. This provides a direct pressure dependence at low pressures but at high pressures tungsten oxide molecule s form an adjacent gas boundary layer which lowers the PO2 at the tungsten surface. A correction for this effect using free-convection theory fits the rate data over the entire oxygen-pressure range from 10-8 to 1 atrn as well as data using O2-A mixtures. Below 10-6 atrn and above 2000°C, e decreases with increasing temperature because of desorption of oxygen atoms. Below 2000°C the rate decreases with decreasing temperature at all oxygen pressures following an apparent activation energy of 42 kcal per mole and depending on (Po2)n with n varying between 0.55 and 0.80. MOST of the previous tungsten oxidation studies have employed gravimetric methods and have been limited to temperatures below 1000°C where the weight loss associated with evaporation of tungsten oxides is negligible compared with the weight gain from oxidation.' At higher temperatures, oxygen-consumption rates have been determined from pressure measurements, usually at constant flow rates, by Langmuir,2 Eisinger,3 Becker, Becker, and Brandes,4 and Anderson.5 The sensitivity of this method decreases with increasing pressure and, with the exception of Langmuir's work, these investigations were confined to pressures below 10-6 atm. Above approximately 1300°C, depending on the oxygen pressure, the rate of oxide evaporation is greater than the oxide-formation rate and the recession of the tungsten surface can be measured optically without interference from an oxide layer. This was first done by Perkins and crooks6 who heated tungsten rods in air pressures from 1 to 40 torr at temperatures between 1300" and 3000°C. The present investigation of the oxidation kinetics of tungsten at high temperatures emphasizes oxygen pressures from 10-6 to 1 atm. This is the range of interest for earth atmosphere re-entry applications of tungsten for which little data were previously available. APPARATUS The apparatus is a modification of the type used by Perkins and crooks.' Ground tungsten seal rods, 6 in. long by 0.125 in. diam, were mounted vertically between two water-cooled electrodes, one fixed and the other having free vertical travel. The movable counter-weighted electrode is prevented from undergoing horizontal displacement by three sets of runners mounted at 120-deg intervals. Electrical contact is made by means of a water-cooled mercury pool. A 24-in. vacuum bell jar having a volume of approximately 267 liters was used as the reaction chamber with the sample holder mounted in the middle of the chamber. Power was supplied from an 800-amp dc variable power supply. Temperature readings were made by means of a Latronics automatic two-color recording pyrometer. With this instrument, corrections for emissivity are not necessary provided the spectral emissivi-ties at two closely spaced wavelengths are equal. Supporting measurements were made with a micro-optical pyrometer corrected for emissivity of bare tungsten and window absorptivity. The micro-optical pyrometer was calibrated against a National Bureau of Standards calibrated tungsten lamp and both pyrometers were periodically checked against the melting points of tungsten and molybdenum using the oxidation apparatus. Above 10-6 atm, pressures were measured with an Alphatron gage calibrated against a McCleod gage. At 10-6 atm, a hot-filament ionization gage was employed. A magnified image of the self-illuminated tungsten rod was formed using a 360-mm objective lens mounted outside the bell jar. When the experiment exceeded 1 hr, the image was focused on a ground-glass plate about 10 ft from the tungsten rod at about X8 and the recession of the thickness of this image was monitored with a Gaertner cathe-tometer. When faster rates were encountered, a 35-mm time-lapse cinecamera with a telephoto lens and bellows extension was substituted for the ground-glass plate and cathetometer. Diameter recession rates were determined from the photograph image projected on the screen of an analytical film reader. EXPERIMENTAL PROCEDURE After installing the rod in the apparatus and cleaning it with acetone, the system was evacuated to 5 1 x 10-5 torr. Before oxygen was introduced,

Jan 1, 1964

By Richard McCaffery

WHEN we began the study of blast furnace slags we limited our work at first to a study of those slags containing only lime, alumina and silica. On our paper1 on some of the results of this first work, the solubility of sulfur in slags containing no magnesia was reported and the question of sulfur solubility and slag viscosity discussed. There has been, for a long time, a very great difference of opinion among metallurgists as to he effect of magnesia in blast furnace slags, and the literature is full if expressions of the most contrary opinions on the subject. As a result, our next publication' developed the constitution of slags considered as a four-component system, silica-alumina-lime-magnesia, and advanced an explanation of slag structure which accorded with the facts and with scientific theory. The present paper continues our study of the general subject of slags. As blast furnace slags are included in the silica-alumina-lime-magnesia system, which is a particular case of four-component solutions, we have determined that there are 22 components Table 1), which may enter into the silica-alumina-lime-magnesia system and that 10 or 12 of these components may be present in blast furnace slags which are within the ordinary ranges of composition. To cave a very definite conception of the behavior of these components in a slag, we have developed the theory of the cooling of a four-component solution from the liquid state to the solid and the conclusions that we obtained have been made use of in this paper. On account of the importance of the four oxides and 18 compounds which enter into the silica-alumina-lime-magnesia system, some method of calculating the percentages of the various compounds that are present in the slag when the percentages of the oxides are given, seemed very desirable and we develop L method later herein for doing this, and finally we give illustrations of the composition of a wide series of blast furnace slags and show some applications of these composition data.

Jan 1, 1927

By H. I. Aaronson, C. Laird

Although the past results of X-ray experiments indicate that the broad faces of 0' plates are coherent with their matrix, dislocations lying in arrays have frequently been observed at these boundaries by transmission electron microscopy. Critical experiments employing the latter technique have been carried out in order to determine the origin of these dislocations. It is concluded that 8' plates are essentially coherent with the matrix at their broad faces throughout the aging temperature/time envelope studied. Virtually all of the dislocation arrays observed are deduced to have been formed by plastic deformation accompanying transformation. The proportion of dislocations arising from convexity of the plates is shown to be negligible by comparison with that from plastic deformation. At the higher aging temperatures, a[001] dislocations appeared in moderate numbers. These dislocations were traced directly, however, to the ledgewise dissolution of 0' occasioned by the formation nearby of 0 crystals. On the other hand, since there is a parametric difference normal to the broad faces of the ?' plates, mismatch dislocations do form at their edges. A previous conclusion that these dislocations have Burgers vectors of type a[001] was confirmed directly. The edges of 0' plates were observed to develop octagonal shapes when growing, but circular shapes during dissolution. 1 HIS paper presents the results of an investigation of the interfacial structures of plates of the transitional phase, 8', formed in an A1-4 pct Cu alloy. In a companion paper, Part 11, the effects of these structures upon the migration kinetics of a:?f boundaries are reported. This work is pa.rt of a general program designed to establish the basis of precipitate morphology. The present authors in Al-Ag,1 and whitton2 previously in U-C alloys, have used transmission electron microscopy to examine directly the vander Merwe3-6 networks of dislocations anticipated7 to compensate the small amount of lattice misfit normally founda at the broad faces of Widmanstatten plates. Since the broad faces of 0' plates are considered to be perfectly coherent with the corresponding habit planes in the a matrix,' no dislocations should be present at these faces. Many reports have been published, however, giving evidence to the contrary.10-18 The primary objective of this investigation was therefore to ascertain the nature of these dislocation structures. An attempt to do this is described in the first three sections of this paper. Inspection of the matching of the a and 8 ' lattices at the orientations of the 0:0' boundary corresponding to the edges of 0' plates raises the possibility that these edges may be made up of rather closely spaced edge- type misfit dislocations oriented so as to be sessile with respect to the lengthening or shortening of the plates. Since this structure should severely inhibit migration of the plate edges (Ref. 7, Part II), a situation not originally anticipated,' an experimental determination of the interfacial structure of the edges of 8' plates was clearly in order, and is reported in Section III. Those aspects of the experimental procedure applicable to both Parts I and I1 are presented in the next section. Specific procedures applicable to individual aspects of each investigation, and also the relevant surveys of the literature, are then individually reported in the appropriate sections. I) GENERAL EXPERIMENTAL PROCEDURE The material used in both parts of these studies was the same as that of a previous investigation:" strips of A1-3.93 pct Cu, 0.009 in. thick, prepared as before, solution-annealed at 548°C for 6 hr, and quenched. Details of subsequent aging, and in some cases deformation treatments, are given in the Experimental Procedure sections of the individual parts of both papers. Specimens of the heat-treated strips were electro-thinned as beforeLg and examined in a Philips EM 200 microscope equipped with a goniometer stage. A commercial hot stage, of the grid-heater type and capable of * 30-deg tilt about one axis in the plane of the specimen, was also used for kinetic studies. The usual precaution of calibrating for the additional heat supplied by the electron beam was taken.19 A 16-mm cine cam-I era mounted outside the viewing window was frequently used to record the transformations. Conventional selected-area diffraction and dark-field viewing techniques were used to identify the precipitates in the foils. Normal bright-field images corresponding to two-beam diffracting conditions or dark-field images were employed to characterize the dislocations observed at the interfaces of the precipitates. The application of these techniques to the study of an interphase boundary, and the interpretation of the images,20'21 has been fully described in a previous paper.'

Jan 1, 1969

By A. S. Yue

The movphology of the Mg-32 wt pct Al eutectic has been studied as a function of freezing- rate and temperature gradient. At slow freezing rates a lamellar eutectic was formed; whereas, a rod-like eutectic was generated at fast rates. The inter-lamellar spacing increased as the freezing rate decreased in aggreement with theoretical predictions. Lamellar faults, morphologically similar to edge dislocation models in crystals, were responsible for the subgrain structures in the eutectic mixture. A linear increase in fault density with freezing rate was observed. Fault concentl-ations of the order of 10 per sq cm for a range of freezing rates from 0.6 to -3.0 x 10 cm per sec were estimated. The transformation from lamella?, to rod-like morphologies was determined experimentally to be dependent on the freezing rate and independent of the temperature gradient. Moreover, the number of rods formed per- unit cross-sectional area increased exponentiallv with increasing freezing rote. BRADY' and portevin2 classified eutectic structures into lamellar, rod-like, and globular according to the morphology of the solid phases present. Although this classification is quite descriptive, very little has been reported on the details of the mechanism by which the eutectic structures are formed. Recent work by Winegard, Majka, Thall, and chalmers3 and by chalmers4 on lamellar eutectic solidification suggest that the maximum thickness of the lamellae decreases with increasing rate of solidification due to inadequate time for lateral diffusion. scheilS and Tiller' have shown theoretically that the lamellar widths indeed depend on the solidification rate. However, there has been no experimental evidence to support the theory. Chilten and winegard7 have studied the interface morphology of a eutectic alloy of zone-refined lead and tin. They found that the lamellar width decreased as the freezing rate increased in agreement with the theoretical predictions of scheils and Tiller.' More recently, Kraft and Albright' have investigated the microstructures of the A1-CuA12 eutectic as a function of growth variables. They observed lamellar faults present in the lamellar eutectic, similar to edge dislocation models in crystals. Furthermore, Kraft and Albright reported that they could not designate which extra lamellar was responsible for the formation of a lamellar fault even under electron microscopic magnification. In this paper, the morphology of the Mg-A1 eutectic structure is described. The effects of freez- ing rate on the interlamellar spacing and on the lamellar fault density are presented in detail. The transformation from lamellar to rod-like eutectics is discussed in terms of the freezing rate and the temperature gradient. EXPERIMENTAL PROCEDURE The experimental details of alloy preparation, the decanting mechanism and the determinations of the freezing rate and the temperature gradient have been reported elsewhere. Measurements of plate-edge angles were made with a microscope. The true angles used to determine the interlamellar spacings were determined by a two surface analysis technique.'' Since the decanted interface structure does not represent the true eutectic morphology on the solid,g all measurements were made from an area in the solidified bar behind the interface. Measurements of the apparent interlamellar spacings between the two phases of the eutectic were made on a photographic negative by means of a calibrated magnifier. Each value listed in Table I represents the average of thirty measurements on one negative. In general, these measurements are approximately equal with an error of less than pct. The average rod diameter for each specimen was also measured on a magnified photomicrograph. Each value of the diameter represents the average of fifty measurements. RESULTS AND DISCUSSION The experimental observations and their discussion to be presented here are restricted to the morphology of the eutectic structure and to the effects of the freezing rate and the temperature gradient on the solidification of eutectics. INTERLAMELLAR SPACING It has been shown previouslyg that the micro-structure of the decanted interface and the longitudinal section of the Mg-A1 eutectic is characterized by the presence of both lamellar and rod-like morphologies. The lamellae become more regular as the freezing rate is decreased. A three-dimensional photomicrograph representing a perfect lamellar morphology is illustrated in Fig. 1. The lamellae of the top and longitudinal sections of the specimen are regularly spaced while those in the transverse section are not quite straight and parallel. Their parallelism is slightly distorted because fault lines producing a discontinuity are present. A method for calculating the interlamellar spacings A, is described in Appendix 1. The true

Jan 1, 1962

By A. D. McMaster, M. L. Gimpl, N. Fuschillo

There is interest in the use of rhenium metal films as resistive elements in thin-film circcits, and already some zvork has been done using er)aporated rhenium films. It has been found that rheniim films protected from the atmosphere by an evaporated layer of silicon monoxide show excellent electrical stability. Unprotected films, however, are subject to aging- effects, notably the increase in electrical resistivity as a function of time. This phenomenon can be understood as primarily one of oxidation of the thin films. This paper is concerned with the study of the oxidation and crystallization behavior of such unprotected films. It has been found that the oxidation rates are a function of the substrate temperatures used during the deposition of Lhe metal films. The strictures observed in the films are correlated with the film resistivities and some data are presented to establish the existence of the various types of oxides of rhenium. ThERE is some interest in the use of thin films of rhenium metal as resistive elements in monolithic, thin-film integrated circuits. Some work has been done using evaporated films and it has been found that such films, if protected from the atmosphere by an evaporated layer of silicon monoxide, show excellent electrical stability up to temperatures of 500"." Rhenium films unprotected from the atmosphere tend to age and the electrical resistivity of the films increases as a function of time. Rhenium films, of the order of <100A thick, prepared by electron-beam evaporation techniques are found to oxidize very readily when exposed to dry air at room temperature. It would seem, therefore, that this aging phenomenon could be attributed to the oxidation of the metal films. In this investigation, the oxidation and crystallization behavior of thin films of rhenium evaporated onto silicon monoxide substrates were studied as a function of the substrate temperatures used during the evaporation. The films were examined using electron-microscopy and electron-diffraction techniques. EXPERIMENTAL RESULTS Rhenium metal was evaporated onto suitable prepared substrates which were heated to various temperatures. The evaporations were performed in a vacuum of approximately 5 x 1CT5 torr. The evaporation was carried out at a rate of approximately 10A per omin. The final film thickness was approximately lOOA and the resistance ranged from 5000 to 10,000 ohms per square. The substrates used for supporting the metal films were made by evaporating 75A of silicon monoxide onto freshly cleaved mica. The silicon monoxide film was then floated off the mica by immersing the composite in water. The film could then be picked up on a clean nickel grid. Silicon monoxide substrates were chosen because of their similarity to quartz and glass substrates commonly used for making thin-film resistors. Fuschillo, Gimpl, and McMas-ter have also shown that silicon monoxide films have only minor structural changes at temperatures up to 800°C. This fact simplified the interpretation of any changes observed in the electron micrographs or electron-diffraction patterns obtained from the deposited rhenium films. After the evaporations were completed, the substrates were cooled to room temperature, except where noted differently, before the coated substrates were removed from the vacuum system. All aging of the deposited films was done in a desiccator. The evaporated films were examined in an electron microscope equipped with a hot stage that would permit continuous observations of the samples up to temperatures of 1000°C. RESULTS A series of electron micrographs of the rhenium films deposited on the silicon monoxide substrates are shown to Figs. 1 to 3. In all cases, the metal films are approximately 100A thick and the micrographs were taken 1 hr after the deposition was completed. here was no apparent structure in the films deposited on the substrates held at the higher temperatures. The

Jan 1, 1967

One of the newest and most modern surface mining operations in the East is gathering steam at Mapco Inc.&apos;s Martiki mine in anticipation of yielding 2.7 million tons (3 million st) of coal annually.

Jan 10, 1977

By W. S. Hyler, W. L. Bruckart

The powder metallurgy and arc-cast types of wrought molybdenum stock were studied in rotating beam fatigue. Endurance ratios of unnotched specimens after 5x10 cycles were found to be 0.74 and 0.81, respectively. Fatigue notch factors (K,) of 1.36 and 2.05, respectively, were obtained on V-notched specimens having a theoretical stress-concentration factor Kt = 3.1. MOLYBDENUM and its alloys are rapidly gaining importance as engineering materials of construction for high temperature applications. AS a wrought material, molybdenum and its alloys are outstanding above 1800°F. It is necessary, however, with molybdenum to provide elevated temperature oxidation protection. This is currently being studied by a number of investigators. Thus far, there have been no published data on the fatigue behavior of molybdenum either at room temperature or at elevated temperature. The knowledge of fatigue behavior, particularly notched fatigue behavior, becomes increasingly important as the engineering importance of a material increases, especially from the design standpoint. The work described here was directed toward determination of the notched and unnotched rotating beam fatigue characteristics of molybdenum at room temperature. Also, it was desired to learn whether any difference exists between wrought molybdenum of the powder metallurgy and the are-cast types. Fabrication History of Bar Stock For this work, bar stock was procured from Climax Molybdenum Co. (are-cast type) and from Westing-house Electric Corp. (powder metallurgy type). The processing histories of these materials are listed in Table I. The first lot of are-cast molybdenum was deoxidized by aluminum additions. The second lot was deoxidized by carbon." Both lots of the powder Microstructure A microscopic examination of these materials, as received, revealed the powder metallurgy molybdenum to be free of inclusions and to be finely fibered. On the other hand, the are-cast C molybdenum possessed numerous carbide inclusions, and the arc-cast A appeared to have coarse grained fibers. These are shown in Fig. 1. Owing to the large apparent difference in fineness of fiber between the are-cast A and the powder product and are-cast C, a check was made of the recrystallized grain sizes to determine whether these differences persisted. A series of recrystallization anneals revealed mixed grain sizes in both the are-cast A and the powder product. Variations in grain diameter of as much as 50 times were found after full recrystallization at 1200°C for 30 min. There was no distinction between the two. Arc-cast C was not checked. Room Temperature Mechanical Properties Prior to subjecting the materials to fatigue tests, room temperature mechanical properties were determined. These data, together with the tensil: strength of the notched bars, data,togetherare listed in Table tensil: There were no significant differences in the tensile strengths of the two types of molybdenum. However, the powder metallurgy material was generally more ductile and yielded at a somewhat lower stress than the arc-cast material. Tensile strengths of the notched specimens indicated a slightly greater notch strengthening effect in the are-cast C than in the powder product, lot 2. Room Temperature Fatigue Properties Sample Preparation: Specimens were prepared for use in R. R. Moore rotating beam fatigue machines. These specimens had a continuous radius test section with a minimum diameter of 0.260 in. The specimens were prepared by grinding to shape and polishing to produce a smooth unworked surface. Polishing consisted of rotating a disk in the continuous radius section on which were attached, successively, emery belts of 240, 400, and 600 grit. The specimens were slowly rotated during the operation. The belt speed was high, and rotation was such that polishing scratches were longitudinal. Unnotched Fatigue Properties: Unnotched fatigue data were obtained from a number of specimens of each of the four lots of molybdenum. The results of the tests are presented in Fig. 2. From this figure,

Jan 1, 1956