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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 Ralph E. Esarey, G. F. Fix

The oil and gas industry in Indiana in 1938 showed considerable improvement over the preceding year. Most of the drilling and development during the year, as in the past several years, was in the Indiana portion of the Illinois Basin, but increasing interest was apparent in the old Trenton area, for possibilities of further production in the Trenton formation and the underlying St. Peter sandstone. Interest in all other portions of the state was at a new peak, since many areas have never been prospected. Natural gas production continued to drop during 1938, since new discoveries have not been able to keep pace with the rapid decline in older areas. Oil production increased considerably, chiefly through the discovery of new fields. Older fields contributed about the same quantity of oil during 1938 as during the preceding year. There were 159 wells completed in Indiana during 1938, an increase of 25 over the preceding year. Of these, 48 were oil wells, 41 were gas, and '70 failed to find commercial production. Forty-three, or about 20 per cent, were wildcat. Six of these were productive—three oil wells and three gas wells. Thirty-nine wells on which operations started during the year had riot been completed by Dec. 31. Fourteen others were temporarily abandoned, with the possibility that several will be drilled to completion in the near future. A new oil field (Heusler) was discovered in May 1938, in sees. 1 and 12, T. 7 S., R. 12 W., Posey County. Production was found in the Waltersburg (Upper (Chester) sandstone at a depth of approximately 1775 ft. At the close of the year, Heusler field had nine producing wells and two drilling. The Point township area, Posey County, near the confluence of the Wabash and Ohio Rivers, held promise of good production from the McClosky lime, but offsets to the, discovery well had only shows of oil. The discovery well declined rapidly in production arid was finally plugged. In the Oaktown field, Knox County, a wildcat came in with a good flow of gas, extending the field to the east, and proving considerably more acreage. A new gas area was discovered in Sullivan County, and four good wells were completed. The discovery well was in sec. 35, T. 8 N., R. 10 W., and had an initial

Jan 1, 1939

By Ralph E. Esarey, G. F. Fix

The oil and gas industry in Indiana in 1938 showed considerable improvement over the preceding year. Most of the drilling and development during the year, as in the past several years, was in the Indiana portion of the Illinois Basin, but increasing interest was apparent in the old Trenton area, for possibilities of further production in the Trenton formation and the underlying St. Peter sandstone. Interest in all other portions of the state was at a new peak, since many areas have never been prospected. Natural gas production continued to drop during 1938, since new discoveries have not been able to keep pace with the rapid decline in older areas. Oil production increased considerably, chiefly through the discovery of new fields. Older fields contributed about the same quantity of oil during 1938 as during the preceding year. There were 159 wells completed in Indiana during 1938, an increase of 25 over the preceding year. Of these, 48 were oil wells, 41 were gas, and '70 failed to find commercial production. Forty-three, or about 20 per cent, were wildcat. Six of these were productive—three oil wells and three gas wells. Thirty-nine wells on which operations started during the year had riot been completed by Dec. 31. Fourteen others were temporarily abandoned, with the possibility that several will be drilled to completion in the near future. A new oil field (Heusler) was discovered in May 1938, in sees. 1 and 12, T. 7 S., R. 12 W., Posey County. Production was found in the Waltersburg (Upper (Chester) sandstone at a depth of approximately 1775 ft. At the close of the year, Heusler field had nine producing wells and two drilling. The Point township area, Posey County, near the confluence of the Wabash and Ohio Rivers, held promise of good production from the McClosky lime, but offsets to the, discovery well had only shows of oil. The discovery well declined rapidly in production arid was finally plugged. In the Oaktown field, Knox County, a wildcat came in with a good flow of gas, extending the field to the east, and proving considerably more acreage. A new gas area was discovered in Sullivan County, and four good wells were completed. The discovery well was in sec. 35, T. 8 N., R. 10 W., and had an initial

Jan 1, 1939

By Eugene S. Perry

The most outstanding event in oil and gas development in Montana during 1936 was the discovery of oil in the Baker-Glendive gas field, in the extreme eastern part of the state. Other notable achievements were small extensions in the Cut Bank oil field; continued favorable results of acidization in the Kevin-Sunburst oil field; and the discovery of oil and gas in commercial quantities about 20 miles southwest of Billings, on what is known as the Mosser dome. Several wildcat wells were drilled. For the coming year of 1937, it is anticipated that the main activities will be confined to drilling in or near known fields. During 1936 Montana had seven fields producing oil, but over 95 per cent of oil production came from four fields, which in order of importance are: Cut Bank, Kevin-Sunburst, Cat Creek and Pondera. Total production for the state was 5,850,893 bbl., which is 1,251,761 bbl. more than the total for 1935. Natural gas was produced and marketed from eight fields, most important being Cut Bank, Baker-Glendive, Kevin-Sunburst and Dry Creek. These four fields accounted for over 85 per cent of total state gas production, which is slightly greater than the 1935 production of nearly 18 billion cubic feet. Increase in gas consumption is due in part to increase in smelter operation. More detailed information pertaining to the various fields is given in Table 1. In the Baker-Glendive field a test 8186 ft. deep, 15 miles southeast of Baker, was completed by the Montana-Dakota Utilities Co. in 1936. The first gas-bearing sandstone (Judith Hiver horizon, Upper Cretaceous) was found at a depth of 528 ft., and a second sand at 1167 ft. Sandstones of the Dakota formation, in which occurred water, were found from 3724 to 3853 ft. White sandstone correlated with the Tensleep (Minnelusa) formation of Pennsylvanian age was found from 5631 to 5751 ft. deep. The lower 1900 ft. of the well (below 6278 ft.) was essentially in limestone and dolomite, and information on correlation of formations in this mass of sediments is not available at this time. The upper portion of this part of the well contained much anhydrite. Cherty and dolomitic limestone below 7000 ft. may be equivalent to limestones of the Madison formation. The thickness of strata beneath the Dakota formation was

Jan 1, 1937

By H. C. Fiedler

The solubility of sulfur in Si-Fe was determined by the metallographic examination of heat-treated and quenched samples. In the absence of manganese, the solubility in 3.1 pct Si-Fe was found to be about 0.010 pct at 1000o C, 0.015 pct at 11000C, and 0.020 pct at 1150°C, which is substatntially less than hitherto reported. Increasing the silicon content was found to decrease the solubility of sulfur, which is consistent with the increase in the activity coefficient of sulfur with increasing silicon content that has been reported for Fe-Si alloys. Manganese additions were studied in alloys containing 3.1 pct Si and between 0.013 and 0.015 pct S. At low manganese levels the solubility product of manganese sulfide was found to be lower than previously reported. THE solubility of sulfur in pure polycrystalline iron has been reported by Rosenquist and Dunicz1 and by Turkdogan et al.2 Samples were equilibrated in atmospheres containing different ratios of H2S/H2. Both groups of investigators found a solubility limit in y iron of 0.013 pct at 1000oC and 0.031 pct at 1200°C. In addition, Rosenquist and Dunicz1 found a solubility limit in a iron of 0.020 pct at 900°C. Ainslie, Hoffman, and seybolt3 found significantly higher sulfur contents in polycrystalline iron samples than in single-crystal samples after heating at 890°C in a sealed tube containing a mixture of powdered iron and FeS made with s35. Whereas the single crystals contained 0.013 and 0.016 pct S (± 0.005 pct), the polycrystalline samples contained between 0.016 and 0.026 pct S. Autoradiographs suggested that the excess sulfur in the polycrystalline samples was due to the segregation of sulfur in solution at grain boundaries. Ainslie and seybolt4 have reported on the solubility of sulfur in 3 pct Si-Fe. Their samples were sealed in capsules containing hydrogen and sufficient sulfur as cobalt sulfide to saturate the sample. After heat treating, the sulfur-rich phase on the surface was removed by abrading, and the sulfur content of the sample was taken as the equilibrium value for that temperature. Before the equilibrating heat treatment, the samples were heated to 1300°C to coarsen the grains. The resulting grain size, which was about 3/18 in. in diam, was considered sufficiently large to preclude a sensible increase in sulfur solubility due to grain boundary segregation. They reported the solubility to be 0.029 pct at 900oC, 0.063 pct at 1000oC, 0.076 pct at 1100°C, 0.122 pct at 1200°C, and 0.098 pct at 1300°C.

Jan 1, 1968

By John B. Malcom

The discovery of tungsten-bearing quartz outcrop- pings in Vance County, N. C., by the Hamme brothers in 1942, made international news in the mining industry and was, in fact, one of the major ore discoveries made in the U.S. during the last 25 years. Operations began at the Hamme mine in 1942, but after 16 years of successful operation, the mine was closed down in 1958 under adverse market conditions. By that time, it had produced nearly 20 million lbs of metallic tungsten. Because of the square-set timber mining method then in use, mine operating expenses were high, actually representing 78% of the total operating expenses at the property. In timber work alone, 160 men were employed. Approximately 500,000 bd ft of timber were placed monthly at a direct supply cost of $1.00 per ton of ore mined.

Jan 4, 1962

By Rossiter W. Raymond

THE most important event in the history of mining in the United States was the discovery of gold in California, which led to the rapid development, not only of a new industry, but of a new empire. The settlement of the Pacific slope was making but slow progress under the inducements of a scanty commerce in furs and hides. The liberal grants offered by the government to agricultural pioneers in Oregon had attracted to the Willamette valley and other favored points in that territory a limited population; but the government of the Mexicans in California was positively unfavorable to enterprise. It is true that gold was known to exist in the country. Rumors of it were current among the trappers, and placers had actually been worked in what is now Los Angeles County ; but the padres of the neighboring mission of San Fernando had discouraged the business as demoralizing to their flocks ; and the existence of the precious metal was not widely known; still less was its distribution north¬ward suspected. The discovery of gold, January 19th, 1848, at Sutter's saw-mill, on the south fork of the American River, afterward famous as Coloma, in Eldorado County, was the beginning of the new epoch. This discovery was made by James Wilson Marshall, a partner in the mill, who observed in the debris washed down by the tail-race a glittering fragment of a mineral unknown to him. Suspecting it to be gold, he sought for further specimens, and obtained, in the course of a few days, several ounces of it. Tests subsequently

Jan 1, 1875

By B. H. Sage, W. N. Lacey

Variations in the composition of the liquid phase of natural reservoirs which are continuous through significant ranges in elevation have been noted by petroleum technologists. In general, there is a greater gas-oil ratio and the gravity of the oil is higher in production from the upper parts of the formation. In the present paper the possible changes in composition with elevation which would result from the attainment of thermodynamic equilibrium in a uniform gravitational field have been evaluated for a naturally occurring hydrocarbon liquid, a binary hydrocarbon liquid phase and a binary hydrocarbon gas. The results indicate a progressive decrease in the mole fraction of the components from methane through the butanes with increasing depth, accompanied by a corresponding increase in the amount of the heavier components making up the system. The magnitude of these variations is perhaps insufficient to explain completely the variations in the properties of the liquid phase that are encountered at various elevations within a particular producing horizon. However, the changes are significant and the treatment presents an example of the application of thermodynamic data to the evaluation of the properties of hydrocarbon fluids under the conditions approaching those encountered in natural reservoirs. Theoretical Considerations Muskat1 has discussed the work of earlier authors relating to the equilibrium relationships of multicomponent systems in a gravitational field. He also presented explicit solutions for several cases and discussed the physical significance of gravitational concentration gradients. In engineering work it is customary to consider the pressure, the temperature and the composition of a phase to be the independent variables sufficient to establish its state. This procedure neglects the effect of gravitational or other types of fields upon the energy associated with the system and assumes, among other things, that the pressure is uniform in

Jan 1, 1939

By W. N. Lacey, B. H. Sage

Variations in the composition of the liquid phase of natural reservoirs which are continuous through significant ranges in elevation have been noted by petroleum technologists. In general, there is a greater gas-oil ratio and the gravity of the oil is higher in production from the upper parts of the formation. In the present paper the possible changes in composition with elevation which would result from the attainment of thermodynamic equilibrium in a uniform gravitational field have been evaluated for a naturally occurring hydrocarbon liquid, a binary hydrocarbon liquid phase and a binary hydrocarbon gas. The results indicate a progressive decrease in the mole fraction of the components from methane through the butanes with increasing depth, accompanied by a corresponding increase in the amount of the heavier components making up the system. The magnitude of these variations is perhaps insufficient to explain completely the variations in the properties of the liquid phase that are encountered at various elevations within a particular producing horizon. However, the changes are significant and the treatment presents an example of the application of thermodynamic data to the evaluation of the properties of hydrocarbon fluids under the conditions approaching those encountered in natural reservoirs. Theoretical Considerations Muskat1 has discussed the work of earlier authors relating to the equilibrium relationships of multicomponent systems in a gravitational field. He also presented explicit solutions for several cases and discussed the physical significance of gravitational concentration gradients. In engineering work it is customary to consider the pressure, the temperature and the composition of a phase to be the independent variables sufficient to establish its state. This procedure neglects the effect of gravitational or other types of fields upon the energy associated with the system and assumes, among other things, that the pressure is uniform in

Jan 1, 1939

By H. M. Wilten

THIS article presets a view of a problem encountered in petroleum refining in the deterioration of equipment used in condensation of vapors and cooling of liquids. Discussion is limited to the problems of shell- and tube-type exchangers and condensers. In this service shell- and .tube-type equipment is gradually displacing other types and, for this reason, its economic importance ill oil-refining practice is also increasing. Considering oil - refinery practice during the last two decades one can readily see many important improvements in the apparatus used. Briefly, the present equipment is safer, more efficient, and Ignore economical. Improvement in apparatus used for the condensation of distillates has, in my opinion, been less than that in other essential distilling apparatus. So it is hoped that this discussion will stimulate research among the producers as well as among the consumers of this equipment with a view to ameliorating this condition.

Jan 1, 1937

By P. P. Scott, George C. Howard

A field remedial procedure utilizing a kerosene-cement slurry as a water plug-off agent in fractured formations was evaluated both in the laboratory and in the field. This procedure has proved to be capable of effectively shutting off water without causing permanent impairment of the oil production. Success was attributed to the fact that an immobile cement slurry, when placed in a water-producing strata, will set and form an impermeable barrier; whereas when placed in an oil-producing section the cement will retain a relatively high permeability and may be removed by acidizing. INTRODUCTION One of the most perplexing problems facing the oil industry is the selective exclusion of water production from oil or gas-producing wells. This problem has been studied by many investigators in an attempt to develop a material that is not only capable of reducing water production but is also capable of being selective in that it will not impair oil production in either fractured or intergranular type reservoirs. A study of these two types of formations indicated that two distinct types of materials for controlling water production might be required — a completely liquid plugging agent for intergranular formations and a semi-liquid or slurry type plugging agent for fractured formations. This paper is limited to the control of water production from fractured formations. A common source of water in the vicinity of oil bearing rock reservoirs is water which previously has entered and, because of its higher density, generally lies near the bottom of the formation. When the deepest point of penetration of a well into such an oil and water-bearing formation is above the level of the water, and the dynamical gradients due to the flow of oil overbalance the difference in densities between oil and water, water production becomes a problem. Then the water level rises in the shape of a cone and is produced from the lower depths. Other investigators1,2,3,4 have developed theories which define the pressure gradients and contours of this cone in a homogeneous formation and have shown that the placement of a plug in the bottom of a well is only slightly effective in temporarily reducing the flow of water. Assuming that the manner of flow of bottom water from fractured formations to a well is generally similar to the flow in homogeneous formations, then it would be expected that some form of coning, perhaps of less symmetry, would also occur. Then, because of the similarity of the manner of flow of water, placement of a vertical plug in a fractured formation would also probably be ineffectual for controlling water production. However, as has been shown by electric model flow study,' the placing of a plug in a well and an impermeable horizontal streak in the formation might prove to be a means for materially reducing or even eliminating water production in a fractured formation. An indication of the difference in effectiveness between horizontal and vertical plugs based on theory developed from study of the flow of water and oil in rock reservoirs is depicted in Fig. 1. These curves show the expected

Jan 1, 1955

J. A. MATHEWS, * Syracuse, N. Y. (written discussion?).-The reagent described by Mr. Archer seems to be a selective reagent, useful in one particular field. Nevertheless, the field is one in which it is likely to prove of considerable value, because there is a great deal of alloy steel FIG. 1.-ETCHED 1 HR. IN ARCHER'S FIG. 2.-ETCHED 1 HR. IN ARCHER'S REAGENT. PLOD 60. X 188. REAGENT. IZOD 10. X 188. heat-treated to approximately the properties mentioned in the paper. If it is found, by further tests, to be applicable to a wider range of compositions than merely chrome-nickel steels, for the most part discussed by Mr. Archer, its value will be thereby increased to just the extent to which it can be applied. In view of the fact that certain of these chrome-nickel steels, very similar in physical properties and hardness, show very different results in the Izod or notch test, and in view of the fact that when such differences are noted in the fracture the brittle steels usually

Jan 5, 1919

By R. F. Hehemann, S. T. Zegler

The w phase in zirconium alloys containing more than G pct Nb can form in a difjUsionless manner during quenching or with composition change during aging at temperatures below 550°C. The latter treatment establishes a metastable equilibrium between an w phase containing 5 pct Nb and a ß phase containing 45 pct Nb. The superconducting transition temperat~ire of quenched Z?-10 pct Nb and Zr-15 pct Nb alloys is increased by aging at 375°C and both alloys exhibit the same Tc after prolonged aging. The superconducting transition both in the quenched and in the aged alloys is relatively sharp (occurring ovev a temperature range of <0.5°K), and is interpreted in terms of the microstructure that characterizes the ß-w) mixture and proximity effects postulated for thin-film superconductors. At elevated temperatures alloys of the transition elements from groups 4 to 6 in the periodic table exhibit wide ranges of mutual solubility in the bcc structure. Except for compositions that are high in a group 4 element? the bcc structure can be retained at room temperature by quenching and several systematic studies of the influence of composition on superconductivity in bcc alloys have been reported.&apos;&apos;2 The high-temperature bcc form (ß) of the group 4 elements—titanium, zirconium, hafnium—is not retained upon quenching but instead transforms marten-sitically to the hcp structure (a). The Ms temperature can be lowered by alloying the group 4 metals with a solute from a higher group and with a critical amount of solute the martensitic transformation can be suppressed. The 3 phase, however, is not retained without modification. Rather, a metastable phase, w (in particular in titanium- and zirconium-base alloys), occurs over a fairly wide range of compositions above that required for suppression of the martensitic transformation.3,4 As in the formation of a, the transformation of ß to w occurs in a diffusionless manner during quenching and the temperature for its initiation (ws) is lowered by increasing solute content. The ws temperature can be well below room temperature and reversibility of the transformation allows w that forms on cooling to low temperatures to disappear again when the sample is returned to room temperature.5 In Zr-Nb alloys the w phase can also be formed during aging at temperatures below 550°c.5 In this treatment, a metastable equilibrium is established between a niobium-rich ß phase and a zirconium-rich w phase. The present study of Zr-Nb alloys was undertaken to examine the influence of microstructure: as controlled by composition and heat treatment, on the superconducting transition temperature, Tc. MATERIALS AND PROCEDURE The alloys were prepared from zirconium crystal bar that was spectrochemically pure except for 30 ppm of Al, 40 ppm of Cu, 100 ppm of Fe, and 1 ppm of each B and Pb. The niobium used was 99.5+ pct pure containing according to the suppliers&apos; (Stauffer Chemical Co.) analysis a maximum of 50 ppmO, 60 ppm of N, 30 ppm of C, 5 ppm of H, 200 ppm of Ta, 50 ppm of Mo, and 15 ppm each of Fe, Co, and Ni. The alloys were prepared in the form of buttons weighing approximately 4 g by arc melting on a water-cooled copper hearth in an inert-gas atmosphere. All alloys were heat-treated in the ß-phase region for 3 days at 1000°C and water-quenched. For heat treatment, the specimens, 0.5 cm in diam by 1.0 cm long, were wrapped in zirconium foil and sealed in an inert-gas atmosphere inside quartz capsules. Quenching was done by breaking the capsules under water. Subsequent aging treatments of Zr-10 pct Nb and Zr-15 pct Nb alloys were done by placing the specimens in a lead bath at 375°C and quenching in chilled brine. The phases present in the quenched and aged alloys were identified by optical and X-ray metallography. X-ray powder patterns were taken at room temperature with a 114.6-mm-diam Debye-Scherrer camera and CuK-a radiation. Superconducting transition temperatures were determined from magnetic-permeability measurements6 in a 10 oe field. The superconducting transition temperature was determined from a plot of galvanometric deflection as a function of temperature by extrapolation of the linear portion of the curve to zero deflection. In Figs. 1 and 3 the arrows indicate the temperature range of the transitions. RESULTS AND DISCUSSION Superconductivity in Quenched Alloys. In Fig. 1 Tc for alloys quenched from 1000°C is plotted against nominal composition. Indicated also in Fig. 1 are results of metallographic studies. Alloys containing less than 5 pct Nb transform martensitically to a during quenching from 1000°C and Fig. 1 demonstrates that Tc increases significantly as the niobium concentration in a is increased. On the basis of the Bardeen-Cooper-Schreiffer theory of superconductivity7 it seems most likely that this increase in Tc results from an increase in the density of electronic states as zirconium is alloyed with niobium. This increased density of states has been revealed clearly in low-temperature specific-heat measurements.8 The martensitic transformation to a is suppressed when the alloy content exceeds 5 pct Nb. In the range from approximately 6 to 30 pct Nb, quenched alloys consist of a mixture of B and w phases and the amount

Jan 1, 1967

By P.V. Roundy, G.R. Mansfield

Public lands in Florida were first withdrawn from entry by President Taft on July 2, 1910, as a conservation measure because of their possible phosphate content. The reserve thus established was subsequently modified by further withdrawals and by restorations, so that on Jan. 1, 1934, it contained 66,796 acres, of which only a small part had been definitely classified. The reserved land was in scattered parcels, ranging from less than 40 acres to 320 or more, distributed in many counties. For administrative purposes and for final disposal of any of the numerous parcels, mineral classification of the land is legally necessary. In 1934 and 1935 the United States Geological Survey, under two successive grants from the Public Works Administration, prospected some 83 tracts of these lands in Polk County, comprising in all about 3300 acres, and six tracts comprising 240 acres in Citrus and Marion Counties. The tracts in Polk County were all in the so-called land-pebble field and the others in the hard-rock field. The Survey field party was under the direction of P. V. Roundy, from whose unpublished report the material in this paper is largely taken. The foreman of the prospecting crew was J. H. Wingate of Zephyrhills, Fla. The individual tracts were identified through the cooperation of the General Land Office, by transitman Hugh B. Crawford. This prospecting work fitted well the classification adopted for Public Works projects in general: it could not be done on any considerable scale under the Survey&apos;s usual appropriations; it gave employment to unemployed labor; and it may be expected ultimately to repay the Government in royalties more than the cost of the exploration. Commercial, Prospecting Methods Commercial methods of prospeeting for phosphate in Florida have been briefly described by Mansfield.&apos; In the hard-rock field, where the floor of the phosphate deposit is extremely irregular, it is customary to drill a.:

Jan 1, 1938

By P. V. Roundy, G. R. Mansfield

Public lands in Florida were first withdrawn from entry by President Taft on July 2, 1910, as a conservation measure because of their possible phosphate content. The reserve thus established was subsequently modified by further withdrawals and by restorations, so that on Jan. 1, 1934, it contained 66,796 acres, of which only a small part had been definitely classified. The reserved land was in scattered parcels, ranging from less than 40 acres to 320 or more, distributed in many counties. For administrative purposes and for final disposal of any of the numerous parcels, mineral classification of the land is legally necessary. In 1934 and 1935 the United States Geological Survey, under two successive grants from the Public Works Administration, prospected some 83 tracts of these lands in Polk County, comprising in all about 3300 acres, and six tracts comprising 240 acres in Citrus and Marion Counties. The tracts in Polk County were all in the so-called land-pebble field and the others in the hard-rock field. The Survey field party was under the direction of P. V. Roundy, from whose unpublished report the material in this paper is largely taken. The foreman of the prospecting crew was J. H. Wingate of Zephyrhills, Fla. The individual tracts were identified through the cooperation of the General Land Office, by transitman Hugh B. Crawford. This prospecting work fitted well the classification adopted for Public Works projects in general: it could not be done on any considerable scale under the Survey&apos;s usual appropriations; it gave employment to unemployed labor; and it may be expected ultimately to repay the Government in royalties more than the cost of the exploration. Commercial, Prospecting Methods Commercial methods of prospeeting for phosphate in Florida have been briefly described by Mansfield.&apos; In the hard-rock field, where the floor of the phosphate deposit is extremely irregular, it is customary to drill a.:

Jan 1, 1938

WALLACE E. PRATT, Wichita Falls, Tex. (written discussion *).-The age of the oil in the southern Oklahoma fields, Mr. Powers concludes, is Pennsylvanian, or in part, possibly, pre-Pennsylvanian. In a later paper,1 he recognizes the Ordovician age of the small production from the Bullhead A. Daney, No. 14, in the Healdton field. But nowhere does Mr. Powers admit the possibility of oil of Permian age in southern Oklahoma. Yet shallow oil in the adjacent north Texas fields. (Electra, Burkburnett, and Petrolia), which are generally conceded to be closely related to the fields of southern Oklahoma in geological aspect, may very well be of Permian age. Dr. Udden has already discussed this question,2 noting the organic nature of the limestone, outcropping near Electra, together with other evidence that organic material was present if not abundant, originally, in Permian rocks: The Permian rocks in north

Jan 3, 1918

By H. W. Mead, C. E. Birchenall

SELF-DIFFUSION of iron in austenite is a process which may play a significant role in some of the practically important reactions which occur in solid irons and steels. It also provides a system in which the interaction of vacancies on substitutional sites and atoms in interstitial positions may be investigated. For both purposes, accurate values of the diffusivities are required. Two sets of previous measurements exist, each containing features which require checking. In the course of an investigation to determine the rate of diffusion of iron in certain steels, Garwick and Rosenqvist&apos; measured the self-diffusion coefficient of iron in a 0.10 pct* C steel and obtained a dicated that while at lower temperatures D increased with increasing carbon content, at the higher temperatures it first increased and then decreased. At the same time the activation energy decreased linearly from a value of 69,000 cal per g-atom for pure iron to 33,000 cal per g-atom at 1.06 pct C. This rapid decrease in activation energy implies that iron at higher temperatures within the austenite range would diffuse more slowly in high carbon steels than in steels of lower carbon content. Experimental Procedure The radioactive iron used in this work was obtained from Oak Ridge National Laboratory. The unit consisted of about 1 microcurie each of Fe7 and Fe It was allowed to decay for two years. At the end of this time most of the Fe with a half-life of 46.3 days, had decayed, while most of the original Fe(half-life 2.91 years) still remained. The iron as chloride was extracted into an ether layer, using the method of Ashley and M~rray. After evaporation of the ether the iron chloride was dissolved in 250 ml of aqueous solution containing 2.4 gpl Fe. The compositions of the steels used are listed in Table I. Disks of ¾ in. diam and about ¼ in. thick were machined from these steels for use in diffusion couples. The disks were surface ground on both sides to ensure parallel opposite faces. One face of each disk was polished through 000 emery paper. Half of the prepared disks were plated with radioactive iron. For this, 1 ml of the radioactive iron

Jan 1, 1957

By Alex Boozenny

The results of potential measurements between 1) a titaniurn electrode in NaCl-TiCl, melts and a graphite-cizlorine reference electrode and 2) a titanium electrode in NaC1-Nu "melts and a graphite-chlorine reference electrode show that the following relationship expresses the equilibrium relationship between the TiCl, and the dissolved metallic sodium concentrations, expressed in mole fraction units, in dilute NaCl welts at 850°C. The results of potential measurenments between a graphite electrode in NaCl-TiCl, melts that were saturated with TiCl, and a graphite-chlorine reference electrode, when combined with the standard free energy data given in literature, gave the following expression for the equilibrium relationship between the TiCl, and TiCl, concentrations, expressed in mole fraction units, in dilute NaCl melts at 850°C. These relationships are for melts in equilibrium with pure titanium. In impure systems, less sodiurn and more TiCI, can be copresent with a given concentration of TiCl,. AFTER 10 years of existence, the titanium metal industry still relies on the original Kroll and the sodium reduction processes for the only important means of converting titanium-bearing ores to titanium metal via production of titanium tetrachloride as an intermediate. Through years of modification and development these two processes have evolved to a point where any further major economic advances in the field of titanium metal production must be achieved through implementation of processes which are distinct departures from simple magnesium or sodium reduction of titanium tetrachloride. Concurrently with the refinement of the Kroll and sodium reduction processes, industries and government have sponsored research and development in the field of producing titanium by electrolysis of oxides,&apos; carbides,&apos; and halides3&apos;4 in fused salt media. However, the incomplete understanding of the physical chemistry of fused salt systems has in many cases hindered the development of promising new titanium production processes to the point where they will have a clear advantage over the processes presently employed. Fortunately the volume of information on fused salt physical and electrochemistry is increasing at an accelerating pace. The first approaches tbward investigating the electrochemical behavior of fused salt systems have been the measurements of equilibrium potentials of metals immersed in melts containing their halides.&apos; Some work on the kinetics of fused salt electrochemical processes has been reported.&apos;09" Some descriptions of the structural composition of fused salt systems are also available. The work described herein is a continuation of the study of metal electrode potentials in fused salts. Specifically, this contribution to the growing store of fused salt chemistry information presents a description of the equilibrium relationships between the concentrations of titanium dichloride, titanium trichloride, and metallic sodium in fused sodium chloride. The investigation of the titanium dichloride-titanium trichloride equilibrium relationships is not completely new. Kellog and Krye and Melgren and opie15 have presented the results of chemical analysis of salts containing titanium chlorides. Flengas and lngrahaml&apos; have published the results of an investigation of these equilibrium relationships obtained by measurement of electrode potentials in a fused NaCl-KC1 mixture. The investigation described herein differed from that of Flengas and Ingraham principally in the use of straight NaCl as the solvent in place of the more costly and more difficult to purify mixture. This investigation was conducted in three parts. First, the equilibrium potentials of titanium in sodium chloride containing known concentrations of titanium dichloride were measured. A graphite-chlorine electrode was employed as reference. Second, the equilibrium potentials of titanium immersed in sodium chloride containing known concentrations of elemental sodium were measured. Third, the equilibrium potentials of graphite immersed in titanium tetrachloride-saturated sodium chloride containing known concentrations of titanium trichloride were measured. The results of these three related investigations are presented in the above order. The results are combined with the thermodynamic properties of titanium chlorides and sodium chloride, obtained from literature, to give the titanium dichloride-titanium trichloride-elemental sodium equilibrium concentration relationships. In the test, whenever a melt contains titanium chlorides in predominantly divalent form, the melt

Jan 1, 1962

By K. G. Davis, P. Fryzuk

The diffusivity of silver in liquid tin has been determined, using the capillavy-reservoir technique, over the temperature range 250° to 500°C. The new value, D = 2.5 x 10&apos;* exp(-2480/ RT) sq cm per sec, differs from that obtained by other workers in an earlier investigation. The analysis of data from the capillary-reservoir technique is discussed. In a recent investigation of the solidification of dilute alloys, values for the diffusion constant of silver in liquid tin were required in the analysis of the formation of impurity substructures. AS a result, measurements were made of the diffusion constants in the temperature range 250° to 500°C (melting point of tin 232°C), for the alloy concentrations used in the solidification experiments and at higher concentrations, to verify previous determinations.I)2 The capillary-reservoir method was adopted, using experimental procedures similar to those followed by Ma and Swalin,1 with the main exception that radioactive silver was used in the present investigation to facilitate solute-concentration measurements. EXPERIMENTAL PROCEDURE a) 100 ppm Samples. Glass capillary tubes of 2 mm inside diameter and approximately 5 cm- long were sealed at one end, evacuated, and filled with tin of 99.999 pct purity. The region of shrinkage near the mouth was cut off, and the tubes were then placed in a graphite holder and immersed, with the open end up, in an unstirred bath of alloy containing 100 ppm Ag 110, where they remained for periods of up to 30 hr. On removal from the bath they were cooled by an air blower. The bath was kept under a small positive pressure of argon, and the temperature controlled to within +1°C. A 10-hr diffusion period was used in the majority of the tests, scatter on runs of less than 5 hr being rather large. The procedure outlined above was chosen in preference to putting alloy in the capillary and pure tin in the bath, in order to avoid segregation when the tubes filled with alloy were first solidified. To minimize segregation when the diffusion period was complete and the capillaries again solidified, the earlier samples were held in thin-walled silica tubes which could be cooled very rapidly. Later tests were made in precision-bore Pyrex tubes, to eliminate effects caused by variations in the capillary diameter. No consistent differences in diffusivity as measured in the two types of tube were detected. After removal from the glass tubing, the samples were sectioned into 2.5 mm lengths and counted for y activity, using a scintillation counter with fixed geometry. Samples were also drawn directly from the bath and counted, so that values for C/C,, the ratio of the weight of Ag 110 in the sample to that in the bath, could be obtained. b) 5000 ppm Alloy. To check for possible effects of concentration, the silver content of the bath was increased to 5000 ppm. Complete mixing was found to have taken place in the capillary after a 10-hr period at 300°C. It appears that the greater density of the alloy was sufficient for buoyancy forces to cause instability in the alloy-tin interface, leading to rapid convective mixing. For the 5000 ppm alloy, therefore, the bath was of pure tin and the capillary tube was filled with alloy. With this arrangement, values of D consistent with those for the 100 ppm alloy were obtained, Fig. 1. CALCULATIONS OF DIFFUSIVITY The terminology used applies to a capillary of pure tin immersed in a bath of alloy. 1) Error-Function Method. under the present experimental conditions, the rod of liquid tin into which silver is penetrating may be considered semi-infinite. Assuming the concentration at the mouth of the tube to remain constant at Co, the concentration C at distance x from the mouth of the tube at time / is given by3 Plots of the inverse error function of (1 -C/Co) vs .v gave straight lines passing through the origin with slope 1/2-, x being corrected for shrinkage both on solidification and while cooling to the melting point (total correction about 6 pct at 500°C). Values for log D obtained in this manner are shown in Fig. 1. A least-squares fit to the relation D = Do exp(-Q/RT)

Jan 1, 1965

By James P. Munroe

Appalling as has been the loss of life in the last 51 months, there is one slight compensation: no longer will there be in the world a cripple, in the old meaning of the term. Men handicapped by wounds or disease, there will be, unfortunately, and in numbers beyond what the world has known since the wars of Napoleon; but neither they nor the industries from which they were called off to war will be "crippled" in the sense in which both would have been had mankind not learned the lesson of conservation and come to understand that the most important field for such conservation is not in the forests and the mines but among men and women. From the beginning of the Great War, France, Great Britain, Belgium and most of the other Allies have studied the problem of restoring the soldiers and sailors injured through war to physical and economic efficiency; and from their experiences, especially from that of Canada, the United States has learned much. Consequently, our task of preparing for the return of our disabled men has been easier and, in some ways, more comprehensive than theirs. Complex as are the details of the machinery which the United States has set in motion to take care of the men injured by wounds or disease, the plan itself is simple. Taught by European experience, the Surgeon-General of the Army and the Bureau of Medicine and Surgery of the Navy have provided, on both sides of the Atlantic, every known surgical and medical facility for restoring the injured or diseased man to a physical condition as nearly normal as possible. While in the hospital in Prance or England, on the transport coming to America, and in the hospital here, the disabled man is incited in every way to believe in his future efficieney, to want to be a normal worker, to desire to retake his place in that society of workers from which he went, temporarily, to do the greater work of preserving civilization. Furthermore, since purposeful occupation is now regarded as an essential form of treatment with most men in the hospital, especially in the convalescing stage, many of these men will have been actually started on the road to earning before they are discharged from the army surgeon&apos;s care.

Jan 1, 1919