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By Rush Greenslade

THE oil and gas lease is the basic contract of the oil and gas industry; it is the foundation stone upon which the producing industry, particularly, is based. As the industry is precarious and highly speculative, the foundation contract should be of the utmost integrity and certainty. But right there an anomaly exists; the oil and gas lease is the most obscure, most uncertain, doubtful contract in the realm of law today. That is a condition that must be considered when taking oil and gas leases, and when buying, selling, and holding them. It may fairly be asked why should this industry rest upon so insecure a foundation. Why should not the oil industry rest upon the contract that is the basis of all industry, the warranty deed? There are many contributing reasons, but the principal one is business expediency. The Anglo-Saxon idea of ownership of land is that every land owner owns from the center of the earth to the sky all that is above and all that is below-consequently the oil and gas are owned by the person who owns the surface. That idea is not exactly true with reference to oil and gas, for many states have adopted the doctrine that oil and gas are like wild animals; they are fugacious and migratory and belong to the man that traps them. But, except for that doctrine, we believe that oil and gas are owned by the owner of the surface, wherein we differ from the Latin-American countries where the mineral rights are owned by the government. The United States was settled largely by homesteading. The owners of land were, in the main, farmers, who did not have the means or the faith to drill for oil or gas. The operators or speculators did not want to buy the land on the mere possibility of finding oil; hence a compromise resulted by which the land owner gave the speculator or the operator what he called an oil and gas lease, or a right to go upon his land and drill for oil and gas. What is supposed to be the first oil lease placed on record reads as follows: Agreed this 4th day of July, A.D. 1853, with J. D. Angier of Cherrytree township in the county of Venango Pennsylvania that he shall repair up and keep in order the old oil springs on land in said Cherrytree township, or dig and make new springs, and the expense to be deducted out of the proceeds of the oil, and the balance, if any, to be

Jan 8, 1924

By Rush Greenslade

The oil and gas lease is the basic contract of the oil and gas industry; it is the foundation stone upon which the producing industry, particularly, is based. As the industry is precarious and highly speculative, the foundation contract should be of the utmost integrity and certainty. But right there an anomaly exists; the oil and gas lease is the most obscure, most uncertain, doubtful contract in the realm of law today. That is a condition that must be considered when taking oil and gas leases, and when buying, selling, and holding them. It may fairly be asked why should this industry rest upon so insecure a foundation. Why should not the oil industry rest upon the contract that is the basis of all industry, the warranty deed? There are many contributing reasons, but the principal one is business expediency. The Anglo-Saxon idea of ownership of land is that every land owner owns from the center of the earth to the sky—all that is above and all that is below—consequently the oil and gas are owned by the person who owns the surface. That idea is not exactly true with reference to oil and gas, for many states have adopted the doctrine that oil and gas are like wild animals; they are fugacious and migratory and belong to the man that traps them. But, except for that doctrine, we believe that oil and gas are owned by the owner of the surface, wherein we differ from the Latin-American countries where the mineral rights are owned by the government. The United States was settled largely by homesteading. The owners of land were, in the main, farmers, who did not have the means or the faith to drill for oil or gas. The operators or speculators did not want to buy the land on the mere possibility of finding oil; hence a compromise resulted by which the land owner gave the speculator or the operator what he called an oil and gas lease, or a right to go upon his land and drill for oil and gas. What is supposed to be the first oil lease placed on record reads as follows: Agreed this 4th day of July, a.d. 1853, with J. D. Angier of Cherrytree township in the county of Venango Pennsylvania that he shall repair up and keep in order the old oil springs on land in said Cherrytree township, or dig and make new springs, and the expense to be deducted out of the proceeds of the oil, and the balance, if any, to be

Jan 1, 1924

By C. Ernest Birchenall

AS a basis for further progress in several branches of metallurgy, particularly the study of physical properties of solid solutions and the kinetics of solid-solid reactions, a more complete understanding of the structure of solid solutions and the nature of the metallic bond is- necessary. Any investigation contributing to this understanding should be of primary interest to the metallurgist. Since the metallic bond is characteristic of an assemblage of atoms, it can be studied only where this assemblage exists. One of the most promising approaches to this study of the interactions in metals is through the general problem of binary metallic solutions. Although crystal structures of many solid metallic solutions have been determined and solubility limits for many systems are given in phase diagram studies, progress beyond this is irregular. Electromotive force and vapor pressure determinations have provided thermodynamic activity data for small concentration and temperature ranges in the amalgams and a few other systems.' In two systems, however, copper-zinc and iron-carbon, data are available for the calculation of activities over wide ranges of temperature and concentration. This activity data for the brass system is summarized in the preceding paper.= A detailed study of the solubility and distribution of carbon in iron is given by Smith and Darken.3 Their treatment of interaction energies is applicable only to dilute interstitial solutions. The objectives here will be to derive from activity gats given in the previous paper for the brasses and structural considerations as much new and detailed information as possible about the interactions between copper and zinc in metallic solid solution and the effect of these interactions in determining the short range structure of the equilibrium phases; that is, we shall investigate the energy of interaction between pairs of atoms of the same and different kinds, the deviations of the distribution of nearest neighbors from complete randomness, and show that the conclusions found are consistent with the observed behavior of the brass system. The method of treatment is fairly general for substitutional metallic solid solutions and will be applied to other systems. The determination of vapor pressures of the components of alloy systems is being undertaken in this laboratory to supply more data for this purpose. The information obtained from solid solutions may be extended by careful analogy to liquids as long as the metallic type of bonding is preserved. Since it will be necessary to employ the language of thermodynamics, a brief summary defining the terms used extensively in solution theory is given below. Solution Theory4 An ideal solution is one in which the vapor pressure of the constituent molecules

Jan 1, 1947

By C. Ernest Birchenall

AS a basis for further progress in several branches of metallurgy, particularly the study of physical properties of solid solutions and the kinetics of solid-solid reactions, a more complete understanding of the structure of solid solutions and the nature of the metallic bond is- necessary. Any investigation contributing to this understanding should be of primary interest to the metallurgist. Since the metallic bond is characteristic of an assemblage of atoms, it can be studied only where this assemblage exists. One of the most promising approaches to this study of the interactions in metals is through the general problem of binary metallic solutions. Although crystal structures of many solid metallic solutions have been determined and solubility limits for many systems are given in phase diagram studies, progress beyond this is irregular. Electromotive force and vapor pressure determinations have provided thermodynamic activity data for small concentration and temperature ranges in the amalgams and a few other systems.' In two systems, however, copper-zinc and iron-carbon, data are available for the calculation of activities over wide ranges of temperature and concentration. This activity data for the brass system is summarized in the preceding paper.= A detailed study of the solubility and distribution of carbon in iron is given by Smith and Darken.3 Their treatment of interaction energies is applicable only to dilute interstitial solutions. The objectives here will be to derive from activity gats given in the previous paper for the brasses and structural considerations as much new and detailed information as possible about the interactions between copper and zinc in metallic solid solution and the effect of these interactions in determining the short range structure of the equilibrium phases; that is, we shall investigate the energy of interaction between pairs of atoms of the same and different kinds, the deviations of the distribution of nearest neighbors from complete randomness, and show that the conclusions found are consistent with the observed behavior of the brass system. The method of treatment is fairly general for substitutional metallic solid solutions and will be applied to other systems. The determination of vapor pressures of the components of alloy systems is being undertaken in this laboratory to supply more data for this purpose. The information obtained from solid solutions may be extended by careful analogy to liquids as long as the metallic type of bonding is preserved. Since it will be necessary to employ the language of thermodynamics, a brief summary defining the terms used extensively in solution theory is given below. Solution Theory4 An ideal solution is one in which the vapor pressure of the constituent molecules

Jan 1, 1947

By A. U. Seybolt

The solubility limit of oxygen in columbium has been determined in the range between 775' and 1100°C by means of lattice parameter measurements and microscopic examination. The solubility is a function of temperature and varies, in the range given above, from 0.25 to 1.0 pct O, respectively. BECAUSE of the marked deleterious effect of oxygen upon the mechanical properties of some of the transition metals, it is desirable to know something about the solubility of oxygen in these metals. The brittleness caused by oxygen in solution is particularly marked in the case of the group VA elements, vanadium, columbium, and tantalum. The solubility of oxygen in vanadium has already been reported in an earlier paper,' and Wasilewski2 has given a value (0.9 wt pct) for the solid solubility of oxygen in tantalum at 1050°C. Brauer3 in 1941 investigated the Cb-0 system up to Cb2O5, but made no real effort to investigate the extent of oxygen solubility in the metal. He made the observation, however, that this solubility must be less than 4.76 atom pct (0.86 wt pct) oxygen. This estimate was made from X-ray diffraction results on the alloys CbO, CbO, and CbO; all alloys consisted of the terminal (Cb) solid solution plus CbO, but the last alloy containing 4.76 atom pct 0 showed only three very weak CbO lines. It is surprising that Brauer, by examining only three alloys, arrived at an estimate of the solubility which agrees very well with the results to be reported herein. Experimental Procedure A columbium strip obtained from Fansteel Metallurgical Products was cut into strips, 0.020x1/2x2 in. Two holes, about 3/16 in. in diameter, were made near the ends of the strips in order to hold them against a flat steel block for mounting in a General Electric X-ray spectrometer for lattice parameter measurements. The same holes were used to hang the specimens inside a fused silica vacuum furnace tube which was part of a Sieverts' gas absorption apparatus. The apparatus and method of adding oxygen gas has been previously described.1 According to the supplier, the columbium obtained had the analysis given in Table I. After degreasing the samples, approximately 0.001 in. was etched from each side of the samples in order to remove possible surface impurities from the last rolling operation. For this purpose the following cold acid pickle was found satisfactory: 8 parts HNO3, 2 parts H2O2 and 1 part HF. Various Cb-O compositions were obtained up to 0.75 wt pct O by the gas absorption and diffusion technique. After the sample had absorbed all the oxygen gas added at 1000°C, an additional 24 hr was allowed for homogenization. This treatment appeared to be adequate, as shown by the linearity of the lattice parameter-composition plot. More concentrated alloys were prepared by arc melting mixtures of Cb and Cb2O5 since it was very time-consuming to make Cb-0 alloys in the neighborhood of 1 pct O, or over, by the diffusion method. When the flat strip specimens were used, they were ready for the X-ray spectrometer after cooling from the Sieverts' apparatus. The cooling rate obtained by merely allowing the hot fused silica furnace tube to radiate to the atmosphere (when the furnace was lowered) was sufficiently fast to keep the dissolved oxygen in solution. Arc-melted alloys were reduced to —200 mesh powder in a diamond mortar, wrapped in tantalum foil, sealed off in evacuated fused silica tubes, and then heat treated as indicated in Table 11. The fused silica tubes were quickly immersed in cold water without breaking the tubes after the heat treatments. The tantalum foil prevented reaction between the fused silica and the sample; there was no reaction between the powdered samples and the foil at 1000°C, but some trouble was experienced at 1100°C. At this temperature level a reaction between the sample and the foil was sometimes observed, which resulted in erroneous parameter values. Experimental Results Hardness Tests: Since most of the X-ray samples were in the form of flat strip, it was convenient to obtain Vickers hardness numbers as a function of oxygen content. Compared to the V-O case,' oxygen hardens columbium much more slowly, presumably because of the larger octahedral volume in colum-bium (about 12.0 compared to 9.3Å3 in vanadium), hence, requiring less lattice strain for solution. The plot of VHN vs wt pct O is shown in Fig. 1.

Jan 1, 1955

By J. T. Williams

The equilibria in the V-Zr alloy system were investigated by solidus temperature determinations, thermal analysis, dilatometry, electrical resistance measurements, microscopic examination, and X-ray diffraction analysis. There is a eutectic reaction at 1230°C between a compound, V2Zr, and a solid solution containing 10 pct V in ß zirconium. V2Zr decomposes at 1300°C into liquid and a solid solution containing about 10 pct Zr in vanadium. The eutectic composition is probably about 30 pct V. A eutectoid reaction between V2 Zr and a zirconium takes place at 777°C at a very high rate. The eutectoid composition is 5 wt pct V. The limit of solubility of zirconium in vanadium was estimated to be 5 pct at 600°C. No attempt was made to determine the liquidus for the system. THE recent availability of large quantities of high purity zirconium has stimulated the study of zirconium binary systems. The equilibrium diagram for the V-Zr system has received little attention, however. Wallbauml appears to have made the first report concerning the equilibria in these alloys. He reported the existence of a compound, V2Zr, having the MgZn2 ((214) type of structure with a, = 5.277 kX and c° = 8.647 kX. Anderson, Hayes, Roberson, and Kroll2 made a survey of some potentially useful zirconium binary alloys and found that zirconium probably dissolves a small amount of vanadium. They reported the probable existence of a compound between the two elements and suggested that the zirconium-rich solid solution undergoes a eutectic reaction with this compound. Pfeil," in a critical review of the existing information, estimated that the solubility of vanadium in zirconium is less than 4.7 pct and probably less than 1.8 pct. Rostoker and Yamamoto' proposed a partial diagram for the V-Zr system in a survey paper on vanadium binary alloys. Their diagram indicates the compound, V,Zr, a eutectic reaction at 1360°C, a peritectic reaction at 1740°C, and a limit of solubility of zirconium in vanadium of about 3 pct. They obtained no information on the equilibria in the zirconium-rich alloys. In view of the potential utility of the V-Zr alloys and the incomplete knowledge concerning the equilibria in the system, an attempt was made to establish the constitutional diagram. Preparation of the Alloys Raw Materials: The vanadium for making up these alloys came from the Electro Metallurgical Corp. Zirconium came from two sources. In the beginning of the investigation, sponge zirconium from the Bureau of Mines was used in making some of the alloys. Later, iodide metal made at the Westinghouse Atomic Power Development Laboratories became available. This material was used in the preparation of all the dilatometric and resistance specimens and about two-thirds of the solidus temperature specimens. A typical manufacturer's analysis of the vanadium is shown in Table I. No other analysis of the vanadium was made. The metal contained a dispersed second phase and did not have a sharp melting point. Typical results of spectrographic analysis of the Westinghouse zirconium are shown in Table 11. These data indicate a very high purity. The Bureau of Mines sponge metal was probably less pure but had good ductility. Melting: All of the alloys used in the investigation were made by melting pieces of vanadium and zirconium together in a dc electric arc furnace similar to those of Geach and Summers-Smith, craighead, Simmons, and Eastwood," and others. Melting was done in an atmosphere of helium scavenged of residual air by the preliminary melting of a separate charge of zirconium. Each ingot was turned over and melted at least three more times before removal from the furnace to aid in the attainment of homogeneity. Alloys prepared for use in the investigation are listed with the results of solidus determinations in Table III with the exception of the following compositions upon which no solidus determinations were made: 0.29, 0.54, 4.57, and 5.55 pct V. Analysis: The weight of each ingot made from iodide zirconium was within 0.1 g of the total weight of the initial charge, about 90 g. Since each component of each charge was weighed to the nearest 20 mg for amounts less than 10 g and to the nearest 0.1 g otherwise, the gross composition of an ingot could be calculated accurately. Chemical analysis for the vanadium content of several alloys agreed

Jan 1, 1956

By G. O. Prickett, P. Somasundaran

An experimental progmm based on statistical principles is used for optimizing a flotation operation for the separation of minerals. In this case, flotation of sylvite from sylvinite ore with amine and starch as the flotation reagents was studied to find the optimum reagent levels at various slime levels. The experiments were first done on a two-level three-factor design. Analysis of the results showed that the interactions between various factors were significant. Hence, a first-order linear model of the flotation response would not be accurate. The two-level three-factor design was expanded into a composite design in order to test the fit of a higher-order model. Data were treated to obtain an expression for flotation response as a function of the different variables, to predict the optimum reaaent levels at various slime levels, and also to determine the path of steepest ascent. Tests around the predicted optimum and along the path of the steepest ascent were done until a near-optimum region was obtained. Exploration of the nature of the response surface in that region established the actual location of the maximum response. The optimum amine level was found to be 0.20 lb of amine per ten of ore at all slime levels, while the optimum starch level varied as a function of the slime present. Computer access at the laboratory by means of a teletype terminal on a commercial time-sharing system enabled efficient and accurate treatment of experimental data. The efficiency of experimental investigations can be improved significantly by the use of experimental design and data analysis based on statistical principles. The common approach used in experimental research is to study a property of a system as a function of "one-variable-at-a-time". Several authors'-4 have pointed out the inadequacy and deceptiveness of this method. Results obtained for the effects of a variable on the measured response of the system using

Jan 1, 1970

By B. Tani, K. Anderson, I. Johnson, R. Schablaske

INVESTIGATION of the various rare earth-cadmium binary systems discloses the existence of a compound corresponding to the composition MCd6 in all systems save the La-Cd system. Lattice constants for all of the MCde compounds, except LaCd6 which apparently does not form, and PmCd6 whose synthesis was not attempted, are also recorded herein. Iandelli and Ferro 1 report the existence of the compound CeCd6. No additional information, structural details, and so forth are given. Elliott and Lemons2,3' have measured the vapor pressure of cadmium over CeCd6 and have calculated the activity of cadmium in solid CeCd6. These authors find that CeCd6 exists over a composition range from 5.967 to 6.098 (Cd:Ce ratio) at 584oC, and from 5.971 to 6.118 at 639°C. The following is an excerpt from the paper by Elliott and Lemons: 2 "Recently Mr. F. H. Ellinger of this laboratory has indexed an X-ray diffraction powder pattern of CeCd6.00 which we had prepared by gas phase reaction. The compound has a primitive cubic unit cell with a = 15.783 + 0.001A Based on the volume of the cubes surrounding an elemental cerium or an elemental cadmium atom, Mr. Ellinger finds room for 24.10 CeCd6 formula units in the CeCd6 unit cell; similar calculations based on CeCd2 and CeCd11 yield 24.18 formula units per unit cell. The presence of 24 CeCd6 units per unit cell seems probable with an X-ray density of 8.255 grams per cubic centimeter. The most one can say about in-terstitial~ is that there appears to be room in the crystal even at room temperature." Measurements of the solubility of the rare earths in liquid cadmium4 led to the discovery of GdCd6,

Jan 1, 1964

By Peter T. Luckie, Harold L. Lovell, E. R. Palowitch, A. W. Deurbrouck, James K. Kindig

PART 1: DENSE MEDIUM SEPARATION by E. R. PALOWITCH and A. W. DEURBROUK INTRODUCTION During 1965, 64.9 percent of the 512 million tons of bituminous coal and lignite produced was cleaned mechanically, of which 95 million tons was cleaned by dense medium processes.l The percentage of bituminous coal and lignite cleaned mechanically by dense medium processes rose from 7.0 to 28.5 percent from 1938 to 1965. Dense medium separations include those coal preparation processes which clean raw coal by immersing it in a fluid having a density intermediate between clean coal and reject. As there is a general correlation between ash content and specific gravity, it is possible to achieve the required degree of removal of ash-forming impurities from a raw coal by regulating the specific gravity of the separating fluid. Dense medium processes offer the following advantages over other coal cleaning processes : 1. Ability to make sharp separations at any specific gravity within the range normally required even in the presence of high percentages of the feed in the range of e 0.1 specific gravity units. 2. Ability to maintain a separating gravity that can be controlled with ±0.005 specific gravity units. 3. Ability to handle a wide range of sizes (up to 14 inches). 4. Relatively low capital and operating costs when considered in terms of high capacity and small space requirements. 5. Ability to change specific gravity of separation to meet varying market requirements. 6. Ability to handle fluctuations in feed both in terms of quantity and quality. HISTORY Sir Henry Bessemer patented the first dense medium process in 1858. Solutions of the chlorides of iron, manganese, barium and calcium were proposed as separating liquids; the separation was made in a cone-shaped separator. One large-scale plant using calcium chloride was erected in Germany but soon was abandoned. The Chance process, using a mixture of sand and water, was first

Jan 1, 1968

By G. H. Anderson

During an investigation of the copper-rich portion of the copper-silicon-iron system as part of an extensive research program on P.M.G. alloys, which was begun in 1937 in the research laboratory of the Phelps Dodge Corporation, it became apparent that the binary copper-silicon system below 7 per cent Si needed revision, therefore an investigation was undertaken. Both X-ray methods and microscopic technique were employed. Despite the many investigations that have the clarification of this system as their object, no two successive reports on the system have agreed in placement of the alpha-phase solubility limit, and uncertainty about the secondary phase first to appear has been voiced several times.3,4,5 It was therefore not surprising, when T. Isawa's6 and M. Okamoto's7 works were reported at the time we were finishing up our experimental work, to find essential disagreement between their results and ours. But when C. 5. Smith's latest work on the copper-silicon systema was published just as we were finishing our laboratory report, it was indeed gratifying to find that the latter's diagram and ours checked in all essential features, except the temperature of the peritectoid line above 830" C. Many attempts were made to retain the beta phase during the present investigation, but none was successful. Isawa,6 however, reports that he has been able to obtain X-ray photograms of the beta phase. The structure, he states, is body-centcrcd cubic with a lattiee constant of 2.848 ,&. at 7.2 per cent Si. Okamoto7 and Smith8 both use the designation Kappa for the hexagonal phase, and to avoid confusion this designation will he adhered to in the present paper. Preparation of Samples The alloys were melted in vacuum in a high-frequency furnace. from copper cathodes containing 99.98 per cent Cu, and specially refined silicon supplied by The Electro Metallurgical Co. This silicon is stated

Jan 1, 1940

By G. H. Anderson

During an investigation of the copper-rich portion of the copper-silicon-iron system as part of an extensive research program on P.M.G. alloys, which was begun in 1937 in the research laboratory of the Phelps Dodge Corporation, it became apparent that the binary copper-silicon system below 7 per cent Si needed revision, therefore an investigation was undertaken. Both X-ray methods and microscopic technique were employed. Despite the many investigations that have the clarification of this system as their object, no two successive reports on the system have agreed in placement of the alpha-phase solubility limit, and uncertainty about the secondary phase first to appear has been voiced several times.3,4,5 It was therefore not surprising, when T. Isawa's6 and M. Okamoto's7 works were reported at the time we were finishing up our experimental work, to find essential disagreement between their results and ours. But when C. 5. Smith's latest work on the copper-silicon systema was published just as we were finishing our laboratory report, it was indeed gratifying to find that the latter's diagram and ours checked in all essential features, except the temperature of the peritectoid line above 830" C. Many attempts were made to retain the beta phase during the present investigation, but none was successful. Isawa,6 however, reports that he has been able to obtain X-ray photograms of the beta phase. The structure, he states, is body-centcrcd cubic with a lattiee constant of 2.848 ,&. at 7.2 per cent Si. Okamoto7 and Smith8 both use the designation Kappa for the hexagonal phase, and to avoid confusion this designation will he adhered to in the present paper. Preparation of Samples The alloys were melted in vacuum in a high-frequency furnace. from copper cathodes containing 99.98 per cent Cu, and specially refined silicon supplied by The Electro Metallurgical Co. This silicon is stated

Jan 1, 1940

By G. N. Goldberg, Robert A. Rapp

The steady-state kinetics and microstructures of simultaneous internal oxidation and external scale formation were investigated for the oxidation of Cb-Zr and Ch-Zr-Re alloys in pure oxygen at 1000°C. For each binary alloy, a constant rate of scale formation was observed at steady state; the internal oxidatton zone reached a steady-state, time-independent thickness. The dependence of the scaling rate on zirconium content exhibited a maximum at a low zirconium colttent; more concentrated alloys oxidized at a slower rate than pure columbium. This composition dependence of the scaling rate may be partially attributed to the effect of the internal oxidation process as an intenla1 sink for oxygen, with the formation of voluminous, and relatively impermeable ZrO2 precipitates. However, the morphologies of the ZrO2 internal oxide precipitates also affected the scaling rate. The internal oxide precipitates were distributed uniformly in the external scale. The steady-state thicknesses of the internal oxidation zones were not in agreement with those predicted theoretically from an idealized simple model. However, in this particular alloy systen1 the ideal model is not satisfied experitmentally. For ternary Cb- Zr - Re alloys with Nr10e = 0.02 or 0.05, the steady-state thicknesses of the internal oxidation zones were less than those for the corresponding binary Cb-Zr alloys. For ternary alloys with NRe(0) - 0.05, a more adherent and much less porous external scale was formed, and a reduction in the kinetics of scale formation was observed. A number of authors'-7 have reported linear oxidation kinetics for the reaction of pure columbium at 1000°C in air or in oxygen of about 1 atm pressure. A thin and tightly adherent oxide layer is found at the metal/oxide interface beneath a porous external layer of scale. Although the suboxides CbO and CbO2 represent thermodynamically stable phases at 100O°C, generally only Cb2O5* is identified as a reaction product in quenched specimens. Studies at 1000°C at lower oxygen pressures8,10 (Po2 - 10-4 Torr) show that both CbO and CbO2 do form and that CbO2 is a protective oxide. The growth of CbO2 results in parabolic kinetics until Cb2O5 is nucleated and grows. Apparently because of the large volume change associated with its formation, Cb2O5 is porous and does not serve as a diffusion barrier; linear kinetics prevail after the surface is covered with Cb2o5. On the basis of these observations, several authors5,9,10 have suggested that the linear oxidation of pure columbium at 1000°C in air or oxygen of 1 atm is limited by a Loriers-type mechanism,11 whereby the total rate or reaction is controlled by ionic diffusion through a thin layer of CbO2 which is maintained at a constant thickness throughout the linear oxidation. However, the concept of a Loriers model for a three-phase CbOlCbO2 Cb2O5 scale, with the only oxygen activity gradient across the NbO2 phase, is not self-consistent. Further, the suboxides CbO and CbO2 were not observed in the high-temperature X-ray diffraction study of columbium oxidation by Goldschmidt.8 From investigations in which the large PO2, dependence of the linear scaling rate was demonstrated, the importance of an oxygen adsorption or dissolution step has been suggested.4,5,7,10,12 Thus the mechanism for the linear oxidation of pure columbium remains quite controversial. Since further insight into the oxidation mechanism of pure columbium is not provided by this investigation, the authors wish to emphasize at the outset that their experimental results are not interpreted in terms of a particular rate controlling step for the oxidation of pure columbium. Previous investigations13-18 of the oxidation of Cb-Zr solid-solution alloys in air or oxygen at 1000°C suggest a remarkable dependence upon zirconium content. For an alloy of bulk zirconium mole fraction, N2r(0) equal to 0.05 or 0.10, the oxygen uptake is reported to be as high as four times greater than that for pure columbium;13,14 for alloys with NZr(0) 0.05 or 0.10 the oxygen uptake is reported to decrease with increasing NZr(0); to a minimum uptake of about one quarter that for pure columbium at NZr(0): = 0.50.13-15Since zirconium forms a more stable oxide (ZrO2) than the lowest columbium oxide (CbO), and since columbium exhibits a high solubility19,20 and diffusivity21,23 for oxygen, the internal oxidation of the zirconium component to ZrO2 is expected at a reaction front ahead of the advancing metal/scale interface. The external scale is then formed at the metal/scale interface by the inward migration of oxygen through the scale, probably through a series combination of molecular and ionic diffusion. Internal oxidation in conjunction with external scale formation has been investigated by Maak24 for the oxidation of dilute Cu-Be alloys in pure oxygen at 850°C. For cu-Be and many other binary alloys,24-27 very small, essentially uniaxial internal oxide particles are formed in the most dilute compositions; for somewhat more concentrated alloys. the internal oxide particles precipitate as platelets or needles. From pertinent solutions to the diffusion equation, Maak28

Jan 1, 1967

By O. D. Gonzalez

Existing measurements for the steady-state permeation of hydrogen in a iron above 100°C have been examined for contribution of determinate errors. The analysis leads to a recommended equation for the permeability of hydrogen in a iron: o= (2.9 ±0.5) x 10-3 exp - (8400 ± 400)/RT cu cm (ntp H2) cm-1 sec-1 atm-1/2 THE permeability of a iron to hydrogen has been the subject of numerous investigations over the past 40 years, and at present there are thirteen sets of published results for the rate of steady-state permeation of hydrogen in a iron above 100°C. The numerical values in each set of results are entirely self-consis-tent, but the spread among the sets is too large to be attributed solely to experimental error, i.e., to error other than in the specimen itself. Several reasons have been advanced to explain the disparities, but to date the relative importance of experimental inaccuracy to the spread remains uncertain. The purpose of this report is to examine in detail the sources of determinate errors inherent in the experiments and to assess as far as possible the contribution of the errors to the results. The ultimate goal is the selection of values for the permeability and heat of permeation most nearly representative of hydrogen in a iron. The analysis is limited to those experiments in which the permeation rate was observed at steady state—a condition in which traps for hydrogen within the metal are filled to a fixed level15 so that the trapping mechanism is not reflected in the rate of passage of the gas. Furthermore only data are examined in which surface processes are judged to have little or no influence on the flow. It is hoped with these restrictions to obtain values of the permeability and the heat of permeation which will be as closely related as possible to the mechanism of lattice diffusion. I) DEFINITION OF TERMS; UNITS In this report the data for permeation are given in terms of a coefficient oj permeability, ?, which is defined by the equation: jt=?A/?x{p1/2-po1/2) [1] where jt is the total flow of gas normal to the surface of a membrane of planar geometry, e.g., a disc, of area A and thickness ?x; pi and po are the pressures in the input and output sides, respectively. For flow radial to the walls of a membrane of cylindrical geometry, e.g., a tube, the corresponding equation is: where 1 is the length of the cylinder, and ri and ro are the inner and outer radii, respectively. The flux normal to the surface is given by Fick's law: j= -D(dc/dx) [3] At steady state the concentration gradient will be constant, and integration of Eq. [3] gives for the total flow through a disc of area A and thickness Ax: h =-DA(co - ci) [4] where c, and ci are the concentrations of solute at the output and input surfaces, respectively. When surface control is absent, co and ci are given by Sievert's law c = Kp1/2, and substitution therewith into Eq. [4] gives directly Eq. [I] where ? = DK. Integration of Fick's Eq. [3] in cylindrical coordinates will give Eq. [2] where again ? = DK and is thus shown to be independent of geometry (provided that surface control is negligible). The coefficient of permeability, or simply the permeability,* must be expressed in proper units. In *The term permeability will refer in this report always to the coefficient defined above; permeation will be used to specify the general phenomenon of gas passage through a membrane. this report ? will be expressed in the units of cu cm (ntp H2) cm-1 sec-1 atm-1/2. The variations of D and K with temperature are given by D = Do exp(-Ea/RT) and K = KO exp(-?Hs/RT) where E, is the activation energy for diffusion and AH, the heat of solution, each usually expressed in calories per mole of solute. The variation of permeability with temperature will thus be given (for conditions where surface control is negligible) by ? = ?o exp(-?Hp/RT) where ?0 = DoKo and ?Hp = Ea + ?Hs. The units of ?0 are the same as those of 6, and??Hp will be expressed in calories per mole H. 11) SUMMARY OF PERMEABILITY RESULTS Table I gives the values reported to date for the permeability of H2 in a iron in terms of ?o and ?Hp. Except where noted the parameters listed were taken directly from the numbers reported by the various investigators with only a change in units. The temperature limits within which the listed ?o and ?Hp hold are given in column 7; the limits marked in parentheses in this column indicate the entire temperature range covered in each investigation. The listed values of ?o and ?Hp are those giving a linear plot of ln? against T-1 at the higher temperatures in each set of measurements, and thus presumably represent the case for which surface control was negligible. Column 6 gives values of 9 at a representative tem-

Jan 1, 1970

By N. L. Svensson

The model developed by Tuylor for the calculation of Polycrystalline yield strength has been applied to the case of an aggregate hawing a preferred orientation. In general this procedure requires the specification of texture by means of weighting factors applied to specific orientations. The problem to which the model has been applied is that of the yield-strength aniso-tropy of cold-rolled aluminum whose rolling texture was described as a combination of (110)[112] and (311) [112] In this case yield-strength anisotropy is defined by the rutio of yield strength measured at an angle 8 to the rolling direction to that measured along the rolling direction. The method of calculation of yield-strength ratio as a function of ? is described and the results show good agreement with experimental values. The orthotropic yield criterion suggested by Hill has been applied to the results and the strain ratio R also calculated as a function of ?. This has been compared with calculations using the method suggested by Elias, Heyer, and Smith which does not exhibit suck good agreement with observation. one deficietlcy of the method presented is that the strain ratios used by are those applying to iso-Irobic materials. The method should therefore be reg-clrded only as a first abbroximation to the prediction of anisotropy. THE problem of calculating the stress-strain characteristics of polycrystalline aggregates from the properties of single crystals has attracted attention for a number of years. The most important contributions to this study have been those due to: Sachs,' Cox and sopwith,2 Taylor,3 Kochendorfer,4 Batdorf and Budiansky,5 Calnan and Clews,6 Bishop and Hill,7,8 Kocks,9 Budiansky, Hashin, and sanders, 10 Kroner,11 Cyzak, Bow, and payne, 12 Budiansky and Wu,13 and Lin.14 While the earlier work has been largely superseded, recent developments tend to support Taylor's solution" within the restriction imposed by his assumptions. The essential features of Taylor's approach were: 1) the material is rigid-plastic; 2) each grain experiences the same strain components as the aggregate as a whole (the problem was that of uniaxial deformation with principal strain components in the ratio 3) all regions of each grain deform uniformly; 4) work hardening occurs equally on all slip systems. While Bishop and Hill7 have generally validated this approach, there has been some criticism offered. Kocks? as pointed out that since multiple slip must occur the single-crystal data must be determined from orientations arranged such that polyslip takes place. Boas and Hargreaves,15 and others, have shown experimentally that the strain distribution within grains is not uniform, the strains in the vicinity of grain boundaries being less than those in the center of the grains. Both of these criticisms can be largely offset by the suitable choice of single-crystal critical shear stress. However, for the problem analyzed below, the critical shear stress is not directly used and, consequently, these criticisms lose their importance. The more recent contributions have attempted to obtain a more complete analysis by considering an elas-toplastic material and considering interactions between grains of differing orientations. Lin14 has considered the early stages of yielding for a polycrystalline aggregate having specific regions of defined slip plane orientations. On the other hand, Budiansky and Wu13 have allowed for these interactions for randomly disposed grain orientations and have calculated the polycrystalline stress-strain curves for crystals exhibiting either elastic-ideally plastic or kinematic hardening characteristics. This work has shown that yielding commences when the macroscopic stress is 2.2 times the critical shear stress for slip in a single crystal (7,). The yield stress-strain curve then rises becoming asymptotic to a value of 3.072 7,. This is close to the value obtained by Bishop and Hill (3.06) in their confirmation of Taylor's method. This, of course, is to be expected since, at large strain values, the elastic strains are negligible and the rigid-plastic model is satisfactory. The results of Budiansky and Wu indicate that the result obtained by Taylor is 7.7 pct high at a plastic strain which is two times the elastic strain at the initiation of yield. By defining the anisotropy in terms of relative values, the ratio of yield strength at orientation ?, to that measured in the rolling direction, the effect of the discrepancy in Taylor's solution is considered to be of lesser consequence. Therefore, it is anticipated that an analysis based on Taylor's solution, which can be quite straightforward, should provide a reasonable estimation of the anisotropy of materials having a preferred orientation texture. OUTLINE OF TAYLOR'S METHOD In fee metals there are four possible slip planes (the octahedral planes) and in each there are three possible slip directions (the edges of the octahedron), that is a total of twelve possible slip systems. von Mises16 has shown that at least five independent slip systems must become operative in each grain of the polycrystalline aggregate in order to preserve continuity of strain. With this geometrical requirement as basis and the assumptions previously listed, Taylor determined the operative slip systems for a number of orientations of the tensile stress axis specified in the unit stereographic triangle. For the ith slip system, the critical shear stress

Jan 1, 1967

By G. Y. Chin, M. T. Dolan, W. L. Mammel

The least work analysis of constrained deformation, first proposed by Taylor and recently modified by Chin, Hosford, and Mendorf to include twinning, has been applied to the problem of axisynmetric flow. Calculations were made, for the case of (111}(110) slip and {111}(112) twinning applicable to fcc deformation. The solutions were obtained by linear programming techniques and with the aid of computer methods. The results show that in axisymnzetric tension the onset of twinning tends to decrease the plastic strength anisotropy as compared with the case of defortnation by slip alone. In compression, however, the strength anisotropy is increased as a result of twinning. The [100] and 11111 orientations and their vicinity are unfavorable for twinning in tension and compression, respecticely. With slight modifications, the present results may be applied to bcc metals deform ing by {110}(111j slip and (112} (111) twinning. Implications of present results to wire texture development of low stacking fault energy fcc materials arc discussed. PREVIOUSLY we' have applied linear programming techniques to obtain solutions to Taylor's least work analysis2 of constrained deformation of single crystals undergoing axisymmetric flow, such as occurs in an axially loaded polycrystalline aggregate. These solutions yielded values of the parameter M = o/.r = Y/w which relates the external stress-strain (u-c) curve to the shear stress-shear strain (7-y) curve for the crystal. The value of M is dependent on crystal orientation and hence enters significantly in texture strengthening considerations.3'4 Recently the Taylor hypothesis was modified by Chin, Hosford, and Mendorf' to include mechanical twinning. The latter has now been applied to the problem of axisymmetric flow and the results are reported in this paper. Calculations have been made for {111 )( 110) slip and {111 )(112) twinning applicable to fcc crystals. With minor changes in the indices of the slip and twin systems, the present results are also applicable to bcc crystals which slip on (110) (111) and twin on {112)(111) systems.

Jan 1, 1970

By A. Grant Elliot, H. W. Lavendel

qualitative picture has been developed to describe the oxidation behavior of TaSi2-coated tantalum and CbSi2-coated columbium. These systems have a significantly lower inherent oxidation resistance than MoSi2-coated molybdenum does. This stems primarily from the fact that Ta2O5 and Cb2O5 are nearly as stable thermodynamically as SiO2, whereas MoO2 or Moos are not. Further, diffusion of silicon in the Ta- and Cb-Si system is considerably slower than in the Mo-Si system. These ,factors prohibit the mechanism of selective oxidation of- silicon which accounts for the oxidation resistance 01- MoSi2-coated molybdenum. The silicide can be stabilized by adding suitable Modifiers which increase the thermodynamic stability of the silicate formed during oxidation. Modifiers, such as aluminum, can be inroduced into solid solution in the coating. in controlled amounts through proper selection of the source in the pack cementation process of coating fov~rzatiorz. Addition of aluminum to TaSi2, coatings on tantalum was effective in moderately increasing the oxidation resistance. EXTENSIVE experimental work and analysis have established the nature of the oxidation behavior exhibited by MoSi2- and MoSi2 -coated molybdenum-base alloys, and defined the conditions for maximum protection against oxidation of the substrate.'-* The oxidation resistance of MoSi2 in the temperature-pressure range of 1100°C-PO2 > 10-5 atm to 1900°C— PO2 > 10-1 atm is due to the formation at the surface of a continuous film of SiO2 which results from selective oxidation of silicon. Under the prevailing kinetic conditions, this film is stable toward the molybdenum silicide with which it comes in contact. Initially molybdenum oxidizes also, but it forms volatile species. SiO2, however, nucleates and grows as a condensed phase. Once a continuous film of SiO2 has formed, the oxidation rate falls to that observed for the oxidation of pure silicon indicative of diffusion through the oxide film as the rate-controlling mechanism. This oxidation behavior is of course highly dependent upon temperature and oxygen pressure. Bartlett and Gage13 and Bartlett, McCamont, and Gagelb define precisely this dependence in terms of the oxygen partial pressures and silicon diffusivities required to support a stable SiO2 film. At low temperatures (near 500°C—the "pest" region) silicon diffuses too slowly to be selectively oxidized. Hence, molybdenum and silicon oxidize readily in proportion to their stoi- chiometry. At high temperatures and low pressure, SiOz dissociates to form volatile SiO(g), and a protective film cannot be maintained. Application of the MoSiz/Mo system is limited to temperatures below 1900oC, the eutectic between MoSi, and MO5Si3.5 The oxidation behavior of MoSi2-coated molybdenum is essentially the same as that outlined above with the exception that the MoSi2 is not in equilibrium with the molybdenum substrate. At the temperatures under consideration silicon will diffuse rapidly into the molybdenum eventually converting the coating to MosSi3.4 The rate constant for subsequent decomposition of Mo5Si3 into Mo3Si plus silicon, and/or the diffusivity of silicon through Mo3Si then becomes low enough to allow active oxidation of both molybdenum and silicon with subsequent degradation of the specimen. A stable silica film can be formed but at temperatures and/or oxygen partial pressures higher than those required with MoSi2 present as a source of si1icon.l, 4 Because of the similarity between the silicides of molybdenum and those of columbium and tantalum one would expect similar oxidation behavior for coatings in the respective systems. This is not entirely the case, however, as shown by the experimental results reported herein. Regarding tantalum and columbium disilicide coatings on tantalum and columbium substrates, respectively, the oxygen arriving at the surface of the coating partitions itself nearly equally between the metal and the silicon, and a two-phase oxide layer (Me2O5 plus SiO2) is always formed. The diffusion of silicon in the tantalum and columbium silicides is relatively slow, compared to that in the molybdenum silicides, which further enhances this equipartitioning of oxygen. Thickening of the coating during service by inward diffusion of silicon into the substrate is correspondingly slow, and the effective thickness of the coating at the roots of cracks and defects is only slightly changed providing high probability for premature coating failure. Furthermore, the SiO2 glass that is generated is not thermodynamically stable with respect to the coating. The metal silicide tends to reduce the SiO2 liberating either free silicon or SiO. The situation can be improved by suitably modifying the coating such that the stability of the protective glass which is generated during service is increased. Thus, selective oxidation of silicon and the modifying agent will occur, and the silicide coating will not tend to reduce the oxide layer. Modifying agents can be introduced into the coating by the pack cementation process. Using sources containing the modifier at controlled chemical potentials allows control of the coating composition. Partially substituting aluminum for silicon in TaSi2 coatings by forming a Ta(Si,Al)2 solid solution was effective in moderately increasing the oxidation protection.

Jan 1, 1968

By D. K. Crampton

INTERNAL stress and season cracking in brass have been studied for many years and the technical literature contains many data on various phases of the subject. A résumé of the literature shows certain fairly well established points upon which various authors are mostly agreed: 1. Season cracking is primarily caused by the presence of relatively high internal stresses, or possibly in some cases by external stresses, or both. 2. A specific corrosion is also essential to season cracking: Certain agents, particularly mercurous salts, mercuric salts and ammonia salts; have such a specific corrosive effect. 3. The tendency to season crack under given conditions increases with increasing zinc content, brass containing less than 20 per cent zinc being relatively immune. 4. In alpha brass the season cracks are intercrystalline; in alphabeta brass they lie between the two constituents; and in beta brass they are transcrystalline. 5. The ordinary impurities or added elements in special brasses have little or no effect on the tendency to season crack. 6. Internal stresses can be eliminated, or at least reduced to a safe 'limit by annealing treatments at temperatures that do not produce visible microstructural changes or appreciable softening of the worked brasses. There are, however, some points in connection with the phenomenon of season cracking which have not been thoroughly investigated, or wherein different authors and investigators are not entirely in agreement. The investigations described in this paper were undertaken to determine: 1. The correlation between mercurous nitrate tests and actual season cracking on long-time atmospheric exposure. 2. The quantitative effect of type and degree of drawing operations on the intensity of internal stress and on the tendency to season crack in brass tubes. 3. The possibility of drawing high-brass tubes in such a manner as to prevent the occurrence of harmful stresses rather than to find a remedy for such stresses once having obtained them.

Jan 1, 1930

By J. Gordon Parr, A. J. Goldak

OgdEN et al.1 and Bumps et al.2 suggested that the solubility of aluminum in a titanium extended to 30 pct.* Sagcl,3 Clark and Terry,4 Anderko et al.,5 Ence and Margolin6 and Saulnier and croutzelles,7 subsequently proposed the existence of an intermetallic compound in the region of 25 pct Al. Although Anderko et al.5 suggested that the structure of this phase, Ti3Al, was of the DO,, (Ni3Sn) type, their conclusion was based only upon the results of a powder photograph that included reflections from ? = 0 to ?= 27° (CuK),some of which were reported to be indistinct. Ence and Margolin,6 referring to a 25 pct alloy (but without indicating whether the figure referred to weight or atomic pct) stated: "The structure of Ti2Al is isomorphous with Ti3Sn DO19, as pointed out by Pietrokowsky". But the point was not proven, because Ence and Margolin did not report values of calculated intensities of Ti2Al with the DO,, structure. In fact, the observed intensities they reported are in poor agreement with the values we calculate for DO19 (see Table I). Saulnier and croutzelle7 concluded, on the basis of electron micrography and microdiffraction studies, that the structure of the 25 pct A1 alloy was ordered hexagonal. Our purpose has been to unequivocally determine the Ti3Al structure. Alloys containing 25 pct Al were prepared from iodide titanium and spectrographic standard aluminum by levitation melting. The levitation chamber was evacuated to 10-6 mm Hg before filling with 99.999 + pct A. After casting, the alloy was chilled to liquid air temperature and crushed to -200 mesh in a percussion mortar. The powder, wrapped in molybdenum foil, was annealed (by induction heating) at 1000 "C for 2 hr in the argon atmosphere of the levitation chamber. No sublimate was seen on the foil or elsewhere, and therefore the assumption is

Jan 1, 1962

By Albert H. Fay, William B. Plank

In practically all rock-excavation problem there is need for a careful study of the rock structure, its fault, cleavage or bedding planes, and even the texture of the rock itself. These studies should form the bases upon which an excavation method is selected and they should be carefully considered in predicting the amount and extent of the excavation. The need for such studies was forcibly illustrated in the problems involved in a cut made in 1929, along and underneath a 200-ft. high rock projection for a State highway near the City of Easton, Pennsylvania. The rock mass was badly faulted and also contained a number of cleavage planes at approximately right angles to the fault planes. Much of this structure was visible and could have been studied and analyzed before the work was begun. The State had rigid specifications as to finished grade and slope of cut, which apparently were made without reference to the geologic structure. The contractor complied with the specifications, under the close inspection of the State engineers. A tunnel blast was placed in the base of the cliff, with the result that 65 per cent more rock was broken than was intended by the specifications. About four years after the blast, the writers of this paper studied the circumstances surrounding the operation, to determine the cause of this excess excavation. Scope of Work The section of the roadway involved was about 200 ft. long and on a 6' curve. It was necessary to relocate points on the curve, from which all faults and cleavage planes were located and measured by the use of transit and clinometer. A plan (Fig. 1) showing the blasting tunnel, the roadway, and traces of the faults and cleavage planes on the level of the roadway, was prepared; also 13 cross-sections at varying intervals, showing the original face of the hill and the face after the blast. The original and final profiles of the rock face, taken from the plans of the State engineers, are shown in Figs. 2, 3 and 4.

Jan 1, 1937

By B. B. Zavoico, J. G. H. Crump, P. P. Gregory

West Texas was the scene of greatly increased oil activity during 1937, producing 75,743,000 bb1.l in that year as compared with 61,901,-000 bb1.2 in 1936, an increase of 22.36 per cent. The annual total of wells completed increased from 15863 in 1936 to 28062 in 1937, an increase of 76.92 per cent. Of the total completions in 1937, 2464 were oil wells,2 11 gas wells2 and 331 dry holes.2 The marked increase in the number of oil wells completed in West Texas during 1937 had a substantial effect upon the daily average production per well, which decreased 20.84 per cent from December 1936, when a total of 5310 wells3 produced 5,236,467 bbl.3 for an average of 31.81 bbl. per well per day to December 1937, when 7571 wells2 with a total production of 5,910,257 bb1.2 averaged 25.18 bbl. per well per day. Drilling blocks and checkerboard acreage were being acquired following geophysical work in the northern end of the Permian Basin area, composed of Bailey, Cochran, Hockley, Yoakum and Terry Counties, presaging extension of active development northward. During 1937, at one time 30 geophysical crews were working in West Texas, and an average of 15 to 20 crews was active in this area throughout the year. Discoveries Wasson-Denver Field.—Wasson-Denver field in Gaines and Yoakum Counties was the outstanding field discovery of the year. Production is from porous limestone found at about 5000 ft., and an average well is good for from 300 to 500 bbl. of crude oil per day through 3/4-in. choke. The discovery well was drilled by A. G. Carter and others on the Wasson Ranch, Gaines County, and the field has since been extended into Yoakum County. At the year's end 21 wells had been completed, producing

Jan 1, 1938