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By O. C. Wheeler

During 1938, Colombia witnessed greater activity in oil prospecting and development than in any previous year in its history; more wells were drilled, more potential production established, more geological and geophysical work was accomplished, and more leases and concessions were acquired. Many companies, including the Texas, Socony Vacuum, Richmond (subsidiary of the Standard Oil of California), the Shell, and Tropical, contributed to this activity. Probably the most noteworthy development was in connection with the Barco Concession, which forms part of the Maracaibo Basin in eastern Colombia, adjacent to the Venezuelan frontier. There a great deal of preparatory work was accomplished in addition to camp and other construction, 20 producing wells were drilled and work was begun on the construction of a 12-in. pipe line to transport the oil to the port of Covenas, a distance of 260 miles. It is reported {hat 58,000 bbl. daily initial production was established during the year and is awaiting an outlet through this pipe line. Leasing and exploratory operations in Colombia continued active throughout the year; applications were made for concessions covering more than 1,100,000 acres of national lands and, in addition, leases were taken up on large areas of privately owned lands. Under Colombian law

Jan 1, 1939

By O. C. Wheeler

During 1938, Colombia witnessed greater activity in oil prospecting and development than in any previous year in its history; more wells were drilled, more potential production established, more geological and geophysical work was accomplished, and more leases and concessions were acquired. Many companies, including the Texas, Socony Vacuum, Richmond (subsidiary of the Standard Oil of California), the Shell, and Tropical, contributed to this activity. Probably the most noteworthy development was in connection with the Barco Concession, which forms part of the Maracaibo Basin in eastern Colombia, adjacent to the Venezuelan frontier. There a great deal of preparatory work was accomplished in addition to camp and other construction, 20 producing wells were drilled and work was begun on the construction of a 12-in. pipe line to transport the oil to the port of Covenas, a distance of 260 miles. It is reported {hat 58,000 bbl. daily initial production was established during the year and is awaiting an outlet through this pipe line. Leasing and exploratory operations in Colombia continued active throughout the year; applications were made for concessions covering more than 1,100,000 acres of national lands and, in addition, leases were taken up on large areas of privately owned lands. Under Colombian law

Jan 1, 1939

By William M. Shepard

The Tintic mining districts of central Utah com- prise one of the major silver-lead producing areas in the United States. Ore valued at nearly $450 million has been produced from these districts since the initial discoveries, in 1869, of veins cutting the Silver City monzonite stock. Subsequent production from the famous manto-type "ore runs", which characterize the Main Tintic district, was followed during the past 40 years by discovery of the blind orebodies of the East Tintic district, including the famous Tintic Standard mine and the most recent discovery, the Burgin mine, currently being brought to full production by Kennecott Copper. The occurrence of blind orebodies of exceptional size and grade in both the Main and East Tintic districts has made this area a field laboratory of major importance for the study of geochemical dispersion halos and alteration features associated with known ore, and has led to the discovery of additional concealed orebodies. The larger share of the basic data-gathering and interpretation has been done by members of the U.S. Geological Survey who have been studying the Tintic mining areas since before the turn of the century. These studies have been supplemented and expanded by the geological staffs of the local operating mining companies, by exploration geologists and by students.

Jan 4, 1966

By A. E. Gorum, I. Cornet

Fatigrle of ionic crystals has been studied primarily in magnesinm oxide. under cyclic stress dislocations move irrreversibly; they multiply; slip bands form and grow; cracks mucleate and propagnte, and failure occurs. The use of ionic crystals such as MgO is advantageorus in such investigations because they are optically transparent. Individual dislocation Intersections with {100} surfaces may be observed with a standard microscope, using etch-pit techniques. Slip, deformation, crack .formation, and fracture in MgO crystals under cyclic stress are compared with cotrresponditzg processes in metals. ThE effect of cyclic loading in metals has been studied for many years. The appearance of slip lines is readily observed and the ensuing fracture may also be seen. From these observations it is possible to predict the behavior of a material and make an educated guess as to what is happening internally, but the actual changes taking place within the structure are not readily apparent. If one could obtain a material in which the individual glide components could be observed, it would be invaluable in determining the actual slip distribution resulting from cyclic loading as well as the distribution of slip in the neighborhood of a growing crack. Such a material is magnesium oxide. Dislocation arrays may be observed by means of etch pits

Jan 1, 1961

By John Birkinbine

Among the notable deposits of iron-ore, the Iron Mountain at Durango, Mexico, is prominent. But, although it has been noticed in records of travel and official reports for three centuries, the statements made concerning it have been so largely alloyed with improbabilities that general credence has not been given to data relating to the Cerro & Mercado, that being the name by which this remarkable mountain of ore is known. Location. Geographically, the mountain is centrally located, being situated immediately at the City of Durango, which is distant in direct lines (as the crow flies) as follows: From the Rio Grande River at El Paso, Texas, in the north, 510 miles; from the same stream at Laredo, Texas, in the northeast, 410 miles; from Tampico, in the east, 475 miles; from the City of Mexico in the southeast, 520 miles; from Mazatlan in the west, 110 miles. At El Paso, the standard-gauge Mexican Central Railroad, and at Laredo, the narrow-gauge Mexican National Railroad, enter Mexico. Tampico is a prominent Mexican port on the Gulf of Mexico, and Mazatlan occupies a similar position on the Gulf of California. To reach Durango from Laredo or Tampico, spurs of the Sierra Madre Mountains must be crossed, and between Mazatlan

Jan 1, 1885

By Arnold S. Epstein

Tlze green electroluminescence occurring at liquid-nitvogen temperature in epitaxial gallium phosphide diodes is exarnined using the donor dopants silicon and sulfur. Zinc is used as the p-type diffusant. Two tt~ain peaks are found, namely til 0.56 and 0.535 p. The intensity of the gYeen peak occurring at 0.56 is found to oary as -4"' wlzere Jf is the forward current density and to first order appears to be dependent on the concet~tvation of ionized donovs. Tile vadintive lifetinze fov this process is -10-'sec. The intensity of the 0.56-p lu~ninescence is nt least several ovdevs of magnitude greate,, at liquid-nitvogen temperature than that noted jor the 0.538 radiation for current densities up to about 35 amp per sq cm. The variation oj- the intensity of. the 0.538-p peak with current density caries according to the donor dopant. With sulfur as the donor one has a J12 dependence, whereas when silicon is the donov a J1.5 dependence is noted. Tl~e above can be fitted to a In molecular process (in first order) such as a band to band recombination. The constant B fir band to band vecombination) is found from our experitt~etlt to be of the order of 2 CZI cm per sec, zcl~ereas for tlze impurity vecombination peak (0.56 p]) tile A cotzstor~t is of the order of. 7 x 10-' cu cm per sec. The structuve o/. the diodes at liquid-nitvog-en tett~peruture is oj tlze double injection type, and by carefi~lly selecting. the thickness of the structure one can regulate the onset of the 0.538-p radiation. The diode clzavaclevistics follow an I-Vx laiv where x is >1. Llregatiue resistance in these structures con be correlated with saturation of tlze 0.56- peak. ThE development of high-purity, large single crystals of epitaxially grown gallium phosphide is the ultimate aim of the studies to be reported. While a number of papers and reviews' have been presented on properties of gallium phosphide grown from gallium solution and from the melt, less attention has been paid to the properties of epitaxial gallium phosphide grown from the vapor. In the studies to be reported we have examined the effects of shallow donor impurities, primarily silicon and sulfur, at liquid-nitrogen temperature, on both the electrical and green electroluminescent properties of carefully characterized single-crystal epitaxial Gap. I) EXPERIMENTAL PROCEDURES A) Material Preparation and Properties. The samules used in this investigation were single-crystal n-type epitaxial gallium phosphide. he single crystals were synthesized from the elements by vapor transport and epitaxial deposition on single-crystal gallium arsenide substrates. Typical transport agents used were chlorides. The growth procedures are described in more detail in Ref. 2. The samples were grown in the (111) orientation and had thicknesses up to 480 . Following the growth, the GaAs substrate was removed from the epitaxial Gap by etching in nitric acid. The Hall effect and resistivity of these n-type samples were measured as a function of temperature and analyzed for impurity content and compared with spectroscopic emission analysis. The results are given in greater detail in Ref. 3 but a summary is noted in Table I. In Table I, AED denotes the donor ionization energy, Nd is the donor impurity concentration, lvA is the acceptor impurity concentration, NI is the total impurity concentration, Rip vs temperature is the measured Hall mobility-temperature relationship from liquid nitrogen to about 400"K, n(77"K) is the measured carrier concentration at liquid nitrogen, and R/p(77'~) is the measured Hall mobility at liquid nitrogen. Good agreement is noted between electrical and emission analysis for the major donor impurity, silicon, in the two materials where it is a major constituent. In the case of the two samples SC90-6 and AP138-3(111) B which were sulfur-doped the ionization energy found from the electrical data is in good agreement with that reported for sulfur.4 The acceptor impurities are not known, although from the presence of magnesium in the samples as indicated by emission analysis and its known role as an acceptor in GaP,4 magnesium could be present as an acceptor. Similarly, since silicon is known to be an amphoteric impurity4 it may also be present as an acceptor in the Gap.* The *A small band has been noted at 0.625 11 in samples SC90-6, SC76-4, and SC77-4, suggesting according to Ref. 5 that sillcon could be present as an acceptor In these samples since these authors have found this peak to represent a donor-silicon emission. presence of calcium deduced from emission analysis is not correlatable with the electrical analysis and its presence as an electrically active impurity should be questioned. B) Sample Preparation and Diode Fabrication. The original slices were of the order of 2 sq cm in area witi the (111)B face up. The material was cleaved and sectioned and the best pieces selected (i.e., those which visually appeared to have the least strain and defects). The samples were polished, lightly etched, and cleaned in trichloroethylene. Zinc was diffused in a closed tube at 800°C to form a p-n junction. Diodes were made from these samples. The depth of junction varied, but did not exceed 10 p depth. The back side of the slice was lapped back and a low-resistance n-type contact was formed (at 600°C in forming gas) to an Au-Mo tab with a hole in the middle for

Jan 1, 1968

By F. J. Budin

Steel supports are increasingly used in metal mines for junctions, chambers, and other wide openings and for semi-permanent areas such as haulageways, shaft stations, and pump rooms. Steel lasts longer-especially in wet mines and where foul air is present-and is procurable in different sizes that will carry heavier loads than any timber of equivalent cross section. The chief advantage of steel supports is that less excavation is needed than with timber support of the same strength, so that faster progress can be made. Since there is no possible way to calculate the exact weight on supports, sizes must be chosen by experience. Any adjustment and cutting of steel supports underground would be costly and time-consuming, and it is therefore advisable to cut sets beforehand at the surface workshops. This requires standardization of sets. All these problems have been recognized at Bawdwin Mines, Burma, where mining is difficult, slow, and very expensive. The lead-silver ore is very brittle, with hanging and footwall rock of unconsolidated rhyolite tuff. During the rainy season from May to October water penetrates into the mine, and where soft rock is present disintegration into a loose mass around openings can be expected. For this reason heavy 10x10-in. timber caps break quickly in drifts and crosscuts, and timber rots in a very short time. An average increase of 50 pct in both maintenance work and costs could not be avoided.

Jan 3, 1960

CHARLES KIRCHHOFF, Chairman. ALBERT SAUVEUR, Vice-Chairman. HERBERT M. BOYLSTON, Secretary, Abbot Bldg., Cambridge, Mass. John Birkinbine, J. Esrey Johnson, Jr., Felix A. Vogel, William H. Blauvelt, William Kelly, Leonard Waldo, James Gayley, . Richard Moldenke, William R. Walker, Henry D. Hibbard, Joseph W. Richards, - William R. Webster. Henry 1%1. Howe, E. Gybbon Spilsbury, Frederick W. Wood. Robert W. Hunt, A. A. Stevenson, The Board of Directors of the Institute has authorized the holding of a meeting under the auspices of the Iron and, Steel Committee in New York City, October 16 and 17, 1913. Gratifying responses have been received to the request of the Committee for contributions, the following papers being already assured: 1. H. M. Howe, Equilibrium Temperature for A, in Carbon Steel. 2. H. M. Howe, The Divorcing of the Eutectoid in Meteorites. 3. H. M. Howe and A. G. Levy, Determination Of the Position of Ae3, in Carbon-Iron Alloys. 4. G. .K Burgess, J. J. Crowe and H. S. Rawdon, Thermal and Microscopical Examination of Professor Howe's Standard Commercial Steels. 5. H. Dl. Hove, Discussion of the Existing Data as to the Position of Ae3,. 6. J. H. Hall, Shock Tests of Cast Steel. 7. H. F. Miller, Jr., The Design of Regenerators for Open-Hearth Furnaces. 8. E. Stütz, Paper on the "Scoria Process." 9. Albert Sauveur, Mayari Steel. 10. Felix A. Vogel, Briquetting. 11. J. E. Johnson, Jr., Paper on " Cast Iron."

Jan 6, 1913

By F. H. Wilson

Copper base alloys containing various amounts of aluminum and silicon are of considerable commercial interest. In particular the alloy containing 7 pct aluminum and 2 pet silicon shows an attractive combination of high strength with excellent, machinability. Since there is no evidence ill the literature that this ternary system has been studied since the recognition by Smith1 and Anderson2 in 1939 of the kappa phase of the binary copper-silicon system, the determination of the equilibrium phase relationships in the copper corner of the ternary diagram has been undertaken to provide a fundamental basis for understanding the behavior of these alloys. Phase boundaries have been determined by the micrographic examination of quenched samples while points on the liquidus surface have been obtained by thermal analysis. The results, of sufficient precision to serve their major purpose of providing a guide for the control of the manufacture of alloys in the region covered, are presented in a series of both isothermal and vertical sections of the diagram. Alloys StVdied For a rough survey of the copper corner of this ternary system the compositions listed in Table I (Series A) were employed. The results of examinations of these alloys indicated that the compositions listed in Table 2 (Series B) would further clarify regions of greater complexity. All alloys were prepared as 1200 g heats, the copper being melted under charcoal, and then first silicon and then aluminum were added. An excess of 0.05 pet silicon was allowed to cover deoxidation losses. Two small bars 5/8 by 1 1/4 by 5 1/4 in. were cast using Durville type casting equipment. Ailalyses were made on all alloys using material which was hot-rolled at 800 or 850°C and annealed 17 hr at 650°C. All analyses were found to be within 0.05 pet of the nominal composition. Since the precision of analysis is not much better than this, the points of both isothermal sections and vertical sections at fixed aluminum and silicon contents have been plotted at the compositions indicated by the nominal composition.

Jan 1, 1949

By W. A. Anderson

Recrystallization of cold-worked metals has long been known to proceed by a process of nucleation and growth.' When a cold-worked metal is heated to a temperature at which recrystallization will ensue, nuclei of new grains, essentially strain-free, appear and grow. As the process proceeds, nuclei continue to appear and to grow, until the cold-worked matrix has been entirely consumed and recrystallization has been completed (Fig. I). Conducted isothermally, a measurement of the fraction of the matrix recrystallized plotted against time, yields an isothermal recrystallization curve, showing the time course of the recrystallization process (Fig. 2).2 Evidently, then, the rate of recrystallization is determined by the rate at which nuclei form and the rate at which they grow. The rate of nucleation N is the number of nuclei that form in unit time in unit volume of the unrecrystallized matrix, and the rate of growth G is the increase in radius of the recrystallized grain per unit time. In recent years attempts have been made to determine N and G as these vary with the well-recognized variables affecting recrystallization: time, temperature, degree of deformation, etc.1 Such studies yield information that is more fundamental than that conveyed by the conventional recrystallization diagram,' since the rate of recrvstallization is thus analyzed into its two component rates3 Methods are now available by which N and G can be measured, and analytical expressions have been developed for the interrelationships among N, G, the isothermal recrystallization curve, and the final grain size, which greatly facilitate analysis.2-4 The application of these methods has been demonstrated recently for the recrystallization of silicon ferrite.2 Data on N and G in dependence upon the recognized recrystallization variables are, however, very fragmentary;" values of N and G have been determined for some metals, but the effect of temperature, which would yield the fundamentally important activation energies, has been too little studied. Thus far there has been no detailed study of the recrystallization of any one metal in terms of X and G ovcr appreciable ranges of the variables time, temperature, degree of deformation, and original grain size. It is the purpose of the present paper to provide such a study, employing aluminum.

Jan 1, 1945

By Fritz Wald, Martin Weinstein, Herbert E. Bates

ONE of the methods for preparing a fiber-reinforced composite is that of directional solidification of a eutectic melt. Its major drawback lies in the fact that the matrix in this case is a pure constituent (or a terminal solid solution of fixed concentration) and the ratio of fiber to matrix volume is fixed. Only very few, if any, pure metal matrices possess technically useful properties, and the necessity for alloying is the inevitable consequence of this fact. Nevertheless, structures similar to binary eutectic ones can be obtained in higher-order systems by pseudoeutectic reactions of a type where crystallites and a solid-solution matrix are simultaneously precipitated from a liquid.1"3 Trials to solidify such alloys directionally—the matrix consisting of a solid solution of chromium, nickel, and silicon and the reinforcing phase being Cr3C2— will be reported elsewhere.4 This note describes constitutional studies carried out primarily to determine -the position of the pseudoeutectic and further to insure that no undesirable reactions between the reinforcing phase and components of the matrix occur in the solid state at elevated temperatures. In the investigation it was specifically desired to reinforce a matrix which is as close as possible to the 80/20 Nichrome composition with Cr3C2 to insure good oxidation resistance and improve the strength at high temperatures. No konstitutional information on the quaternary C-Cr-Ni-Si svstem in the range of interest was found in the literature. Nevertheless, the two most important ternaries c-cr-Ni5 and have been completely investigated. On C-Cr-Si some investigations have been conducted,7"9 and C-Ni-Si was studied with a few alloys in the course of the present investination 9 Eight alloys were prepared to investigate the changes in the constitution of the ternary C-Cr3Ce-yNi eutectic5 with silicon contents up to 10 wt pct. Five alloys were made with varying chromium and carbon contents around compositions containing -60 to 70 wt pct Ni and 5 to 6 wt pct Si. The latter alloys were designed to locate the y(Ni-Cr-Si-C)-Cr3C2 pseudoeutectic reaction and to determine the maximum chromium content in solid solution compatible with a two-phase equilibrium between y and Cr3C2 only. The alloys were prepared from electrolyte nickel, semiconductor-grade silicon, high-purity chromium (99.999 pct pellets), and semiconductor-grade graphite. They were melted inductively in high-purity alumina crucibles under flowing argon. Twenty-gram charges were prepared and investigated by optical microscopy (including hot-stage investigations), X-ray powder methods, and electronmicroprobe analysis. The alloys were studied in the as-cast condition and also after a homogenization annealing treatment of 48 days at 900°C in evacuated quartz ampoules. The structures of all alloys based on the ternary eutectic plus silicon in the as-cast state consisted generally of an inhomogeneous solid solution and at least two other phases. Annealing of the alloys showed that the solid solution was homogenized but that an incomplete solid-state reaction had taken place in all alloys with silicon contents over 5 wt pct. This reaction is clearly visible in Fig. 1 around the large Cr3C2 crystals (gray areas). Below this concentration, the alloys consisted of a homogeneous matrix and precipitates of Cr3C2 plus graphite, Fig. 2. The Cr3C2 was entirely unreacted here. From these observations and subsequent X-ray and microprobe investigations, it was deduced that the

Jan 1, 1969

By A. W. Gray

Page CRUSHING STRENGTH...................... 659 The Black Dynamometer....................659 A Standardized Procedure for Crushing Strength Tests...... 660 Influence of Height of Test-piece upon Apparent Strength ..... 662 Influence of Packing Pressure and of Packing Time........ 662 Application of the Logarithmic Law...............665 Influence of Amalgamation Variables.............. 665 Influence of Temperature................... 669 The Transition Region Near 70" C............... 671 Influence of Packing Pressure at Various Temperatures ...... 673 Influence of Age upon Alloy and Amalgam........... 676 DIMENSIONAL CHANGES DURING THE HARDENING OF AN AMALGAM .......................... 678 The Black Amalgam Micrometer............... 678 Thermostated Dilatometer Designed by the Author........ 681 Graphical Representation of Reaction Expansions......... 683 The Typical Reaction Expansion Curve ............. 684 Influence of Packing Pressure................. 686 Influence of Trituration Time................. 687 Influence of Temperature................... 688 Influence of Mercury-alloy Ratio................ 689 Influence of Packing Time................... 689 Influence of Annealing the Alloy................ 691 Influence of Size of Alloy Particles...............691 Extension of the Typical Expansion Curve........... 693 Influence of Thermal Softening and of Reamalgamating a Hardened Amalgam.......................... 634 Curves Obtained with a Variety of Dental Alloys ........ 694 Copper Amalgam ...................... 694 PRACTICAL APPLICATIONS OF THE RESULTS.......... 695 Phenomena which reveal chemical and physical processes that probably go on in many alloys at temperatures not far removed from their melting ranges are observable in dental amalgams. These amalgams should. therefore. be of even more interest to the metallographer, the metallurgistl the chemist. and the physicist than to the dentist who uses them for saving decaying teeth. For this reason I am here de-

Jan 1, 1919

By Donald D. Carr, Lawrence F. Rooney

Perhaps no other mineral commodity in this volume has as many uses as limestone and dolomite. These carbonate rocks are the basic building blocks of the construction industry, the material from which aggregate, cement, lime, and building stone are made. Carbonate rocks, and their derived products, are used as fluxes, glass raw material, refractories, fillers, abrasives, soil conditioners, ingredients in a host of chemical processes, and much more. Although the use of limestone and dolomite goes back before recorded history, new uses and products are continually being found. Carbonate rocks form about 15% of the earth's sedimentary crust and are widely available for exploitation. Found extensively on all continents, they are quarried and mined from formations that range in age from Precambrian to Recent. Reserves of carbonate rock are large and will last indefinitely, although high-purity deposits may be absent or have limited avail- ability in certain areas. Limestone and dolomite are so useful and so abundant that in 1972 more than 690 million tons were produced in the United States. In fact, about 75% of all stone quarried or mined in the United States was carbonate rock. Sand and gravel was the only mineral commodity produced in greater quantity. In this chapter we have sought to provide the general reader an overview of carbonate rocks, their composition, distribution, production, and uses, with emphasis on developments since 1960. In doing so we borrowed extensively from our recent report on the applied geology of limestone and dolomite (Rooney and Carr, 1971). The literature on the limestone and dolomite resources of the United States and Canada is so vast and diverse that one can easily become mired down in print. We tried to list those references that are easily accessible and that provide the economic geologist with a starting point for more intensive study. The table listing selected references on limestone and dolomite resources in Canada and the United States reflects our attempt to be selective rather than exhaustive and to direct the reader to the best sources of detailed information.

Jan 1, 1975

By J. F. Enrietto

Internal friction measurements were used to determine the effect of manganese on the solubility and precipitation kinetics of nitrogen. Manganese, in concentrations up to 0.75 pct, has little effect on the solubility at temperatures above 250°C. On the other hand, at Concentrations as low as 0.15 pct, manganese inhibits the formation of iron nitrides, especially Fe4N, even though it may not form a precipitnte itself. The precipitation and solubility of carbides and nitrides have been extensively investigated in the pure Fe-C and Fe-N systems.1-3 In recent years, some effort has been ispent in studying the influence of substitutional alloying elements on the behavior of carbon and nitrogen in ferrite.4 -7 In particular Fast, Dijkstra, and Sladek have investigated the effect of 0.5 pct Mn on the internal friction and hardness during the quench aging of Fe-Mn-N alloys.', ' They found that at low temperatures (below 200°C) the presence of 0.5 pct Mn greatly retarded quench aging. For example, after 66 hr at 200°C very little precipitation had taken place in the iron alloyed with manganese, whereas precipitation was complete after a few minutes in a pure Fe-N alloy. The effect of varying the manganese content and the details of the precipitation process were not mentioned in these papers. Fast' postulated that manganese causes a local lowering of the free energy of the lattice with a resulting segregation of nitrogen atoms to these low energy sites. The segregated nitrogen atoms are bound so tightly to the manganese atoms that they cannot form a precipitate. The internal friction measurements of Dijkstra and Sladek tended to confirm the concept of segregation of nitrogen around manganese atoms, and the increase in free energy on transferring a mole of nitrogen atoms from a segregated to a "normal" lattice site was computed to be - 2800 cal. Dijkstra and Sladek9 distinguished between two types of precipitates: ortho, a nitride of appreciably different manganese content than that of the matrix, and para, a nitride with a manganese content essentially that of the matrix. With each type of precipitate a solubility, again designated ortho or para, can be associated. Since the internal friction maximum in alloys which were aged several hours at 600" C dropped almost to zero, Dijkstra and Sladek9 concluded that the ortho solubility must be very low. The effect of temperature on the ortho and para solubilities has no1: been investigated. There are obviously several gaps in our knowledge concerning the influence of manganese on the behavior of nitrogen in a-iron. It was the purpose of the experiments described in this paper to determine the following: 1) The ortho and para solubilities of nitrogen as a function of temperature. 2) The details of the precipitation process at elevated temperatures. 3) The effect of varying the manganese concentration on the above phenomena. EXPERIMENTAL PROCEDURE Internal friction is conveniently employed in studying the precipitation of nitrides and/or carbides from a -iron because it is one of the few parameters, perhaps the only one, which is not affected by the presence of the precipitate itself. For this reason, internal friction techniques were heavily relied upon in the present experiment. A) Preparat of -. All specimens were prepared from electrolytic iron and electrolytic manganese. Alloys containing 0.15, 0.33, 0.65, and 0.75 wt pct Mn were vacuum melted and cast into 25 lb ingots. After being hot rolled to 3/4 in. bars, the ingots were swaged and drawn to 0.030 in. wires. The wires wen? decarburized and denitrided by annealing at 750° C for 17 hr in flowing hydrogen saturated with warer vapor. To obtain a medium grain size, - 0.1 mm, the wires were then heated to 945oC, allowed to soak for 1 hr, furnace cooled to 750°C, and water quenched. Subsequent internal friction measurements showed that this procedure reduced the nitrogen and carbon concentrations of the alloys to less than 0.001 wt pct. The wires were nitrided by sealing them in pyrex capsules containing anhydrous ammonia and annealing them for 24 hr at 580°C, the nitrogen being retained in solid solution by quenching the capsule into water. Immediately after quenching, the wires were stored in liquid nitrogen to prevent any precipitation of nitrides. By varying the pressure of ammonia in the capsule, it was possible to produce any desired nitrogen concentration. B) Internal Friction. The internal Friction measurements were made on a torsional pendulum of the Ke type,'' a frequency OF 1. or 2 cps being used. For

Jan 1, 1962

By P. D. Zemany, G. W. Sear, B. W. Roberts

Vanadium metal is embrittled by hydrogen at a temperature as low as 250°C when held in the presence of manganese metal and water vapor in a rough vacuum. It is established that the property changes are caused by the catalytic decomposition of water vapor at the vanadium surface and the diffusion into and solution in the vanadium of the resultant hydrogen. It is found that manganese is a necessary component of the catalyst. The manganese is transported in the vapor phase by an unknown molecule. A deuterium tracer experiment demonstates the role of water vapor in the embrittle-ment process. VANADIUM metal foils were observed to become embrittled' at a temperature of about 300 °C when held in the presence of manganese metal and a small amount of moist air, This paper describes the investigation to find the embrittling agent and an understanding of the relatively low temperature reactions that are involved. Experimental The vanadium metal foil used was prepared by cold-rolling and pack-rolling 32 mil sheet" in a series of steps down to 1 mil foil. The original observation was confirmed by sealing vanadium foils of 3 x 10 sq cm into individual Pyrex tubes with manganese powder† and a con- trol tube containing only the vanadium foil. These tubes were evacuated to 10 -5 mm Hg without baking and sealed. After heat treatment for 200 hr at 300°C, the control foil showed no change in duetility, whereas the foil contained in the manganese— containing tube was embrittled. The visual appearance of each was unchanged. A series of Pyrex sample tubes, about 2.5 cm diam and 25 cm long, were prepared, each containing a 3 x 10 sq cm piece of foil and 5 g manganese powder at the lower end of the tube. By reducing the time of anneal and the temperature of these samples, it was found that embrittlement could be created at 250°C in a time as short as 1 hr. Since the vanadium metal used here has been drastically cold-worked by rolling, it is assumed that it contains a maximum number of dislocations. To check the possible necessity of dislocations in this low temperature reaction, a vanadium foil sample was annealed in Vycor for 2 hr at 800°C to re crystallize and reduce the dislocation concentration. Metallographic examination showed grains which were not visible before annealing. The embrittlement procedure was carried out at 300°C and 3 hr. Upon checking the foil no embrittlement was observed. Further experiments demonstrated that about 6 hr at 300°C are required to create embrittlement in the foil. This delay in the onset of embrittlement in the vanadium foil suggests but does not prove that dislocation channels play a role in the embrittlement phenomena. If manganese metal is necessary for this low temperature embrittlement, do other elements in the transition metals group yield the same result? To check this qualitatively, a group of elements of similar atomic radii were obtained and sealed as before into Pyrex tubes with a sheet of vanadium foil. These tubes were annealed at 250°C for 6 hr and included (with radii)-2 A1 (1.4A), As (1.25A), Be (1.2A), Co (1.25A), Cr (1.45A), Cu (1.25A), Fe (1.25A), Ga (1.2A), Ge (1.25L%), Mn (1.3A), Ni (1.25A), Si (1.2A), Ti (1.45A), Zn (1.3A), air, H,O, 10 cm Hg of dry hydrogen, and MnO, powder. Upon testing the above sample foils for brittleness, only the manganese-containing tube yielded a brittle foil. Manganese Transport—To eliminate contact of manganese metal powder and vanadium foil, sample tubes were prepared with fritted glass barriers. The embrittlement reaction was still found to occur. Thus, the mode of transfer of manganese is certainly vapor transport. A vanadium foil was embrittled by this mechanism in an evacuated Pyrex tube for 8 hr at 300°C. By means of X-ray fluorescence analysis,' the amount of manganese added to the surface was established at 5 ±2 x 10 -6 g per sq cm. Since the average rate of manganese deposition is known, an effective average pressure of an assumed carrier compound can be computed. ___ P = M/T v2p mkT

Jan 1, 1959

By d&apos, C. Antonio, S. H. Reichman

In the course of our studies of the annealing behavior of vapor-deposited silver films we have determined the electrical resistivity as a function of annealing temperature for films in the thickness range of 630 to 3240A. Fig. 1 shows the resistivity of the silver films vs film thickness in as-deposited and annealed conditions. The films were prepared by depositing 99.999 pct pure silver from molybdenum boats onto Vycor substrates. Deposition was conducted at a residual pressure of 5 x 10"6 Torr at rates of 20 to 408, sec-'. Thicknesses were determined using a multiple-beam interferometer. During annealing, resistance was measured using the four-probe method. Measurements were made every 5°C during two consecutive anneals to 300°C under a continuous vacuum of 2 x X6 Torr. The heating and cooling rates during annealing were approximately l° and 2°C min-', respectively. Typical resistivity vs temperature curves are shown in Figs. 2 through 4. There is an inflection point evident at 120°C on Fig. 2, the first anneal of a 3240A film. This inflection point was found on all films above approximately 1!00A on both first and second anneals. Below 1400A the inflection occurred at approximately 180°C. Figs; 3 and 4 show the first and second anneals of a 1370A film. The inflection point occurs at 180°C on the first anneal and approximately 120°C on the second. Our interpretation of this phenomenon is based on oxygen liberation from the film surface. It is well-documented that the presence of oxygen on silver surfaces causes a reversible increase in resistivity.1"3 The liberation of this oxygen, for example during vacuum annealing, would therefore cause a decrease in resistivity as observed on Figs. 2, 3, and 4 as a change in slope. This is accounted for by the decomposition of Ag20 on the film surface. The free energy of AgzO becomes positive between 125" and 225°C.4 The thickness dependence of the inflection points can be explained as an orientation effect. The films used in this study were preferentially oriented with their (111) planes parallel to the Substrate.''~ In addition it has been sten that the thinner films, below approximately 1500A, possess a decided "hill and valley"

Jan 1, 1969

By H. E. Stamm, H. H. Spain, R. C. Rumble

This paper presents a reservoir analyzer study of the performance of the Woodbine formation in the East Texas basin. The study was made possible by the compilation of available information on the configuration. thickness and the pressure drawdown of the formation. The investigation was made of the pressure variations in the basin incident to production from the several Woodbine reservoirs. In addition, the apparent compressibility of Woodbine water was evaluated so that the potential water yield of the formation could be determined. The distribution of permeability of the Woodbine sand and the interference between producing areas were also investigated. In conjunction with this basic study of the Woodbine sand, an acceptable match of the production-pressure relationship in the East Texas Field was established on the analyzer. INTRODUCTION When production is taken from a reservoir contiguous to an aquifer, the resultant pressure gradient causes a water influx into the reservoir. For some years it has been the practice to predict the performance of water drive reservoirs with mathematical equations that relate the water influx into reservoirs to their pressure behavior. A rigorous solution of these equations is quite complex: hence, the conventional method requires the simplifying assumptions that the formation have constant thickness, permeability and poiosity, and that it have a known and regular shape. It is necessary to use performance records of the reservoir in question to determine the equation constants that make the results of the mathematical calculations duplicate the reservoir history. The values of the constants determined in this manner sometimes differ so greatly from theoretical or measured values that the constants appear unreasonable. The equation constants comprise such factors as the thickness, porosity and permeability of the formation, and the viscosity and compressibility of water. Usually the thickness, porosity and viscosity are known within a reasonable degree of certainty. whereas the formation permeability and the water compressibility are known with considerably less certainty. Hence. permeability and compressibility values are arbitrarily selected that will make the mathematical equations duplicate the reservoir behavior. In many reservoir studies the value of the compressibility of water thus selected has exceeded the reported value by a factor of from severalfold to manyfold. Whether this excessive value results from the inadequacy of the mathematical approach to take into account the shape irregularities and the heterogeneities of the aquifer, or is due to some type of formation compaction and decrease of porosity has not been established. Because of the significance of the potential water yield of formations with reference not only to oil reservoirs but to water resources as well, it is very important that a representative value for the effective water compressibility be determined. One of the best known examples of a field for which it has been possible in the past to predict the future reservoir pressure is the East Texas Field. Until about 1943 it was possible by means of mathematical equations to duplicate past pressure behavior and to predict with a high degree of accuracy the reservoir pressure of the field. Since 1943, however, the calculated pressures have deviated progressively from the observed pressures to such a degree that in recent years, it has

Jan 1, 1951

By H. H. Spain, R. C. Rumble, H. E. Stamm

This paper presents a reservoir analyzer study of the performance of the Woodbine formation in the East Texas basin. The study was made possible by the compilation of available information on the configuration. thickness and the pressure drawdown of the formation. The investigation was made of the pressure variations in the basin incident to production from the several Woodbine reservoirs. In addition, the apparent compressibility of Woodbine water was evaluated so that the potential water yield of the formation could be determined. The distribution of permeability of the Woodbine sand and the interference between producing areas were also investigated. In conjunction with this basic study of the Woodbine sand, an acceptable match of the production-pressure relationship in the East Texas Field was established on the analyzer. INTRODUCTION When production is taken from a reservoir contiguous to an aquifer, the resultant pressure gradient causes a water influx into the reservoir. For some years it has been the practice to predict the performance of water drive reservoirs with mathematical equations that relate the water influx into reservoirs to their pressure behavior. A rigorous solution of these equations is quite complex: hence, the conventional method requires the simplifying assumptions that the formation have constant thickness, permeability and poiosity, and that it have a known and regular shape. It is necessary to use performance records of the reservoir in question to determine the equation constants that make the results of the mathematical calculations duplicate the reservoir history. The values of the constants determined in this manner sometimes differ so greatly from theoretical or measured values that the constants appear unreasonable. The equation constants comprise such factors as the thickness, porosity and permeability of the formation, and the viscosity and compressibility of water. Usually the thickness, porosity and viscosity are known within a reasonable degree of certainty. whereas the formation permeability and the water compressibility are known with considerably less certainty. Hence. permeability and compressibility values are arbitrarily selected that will make the mathematical equations duplicate the reservoir behavior. In many reservoir studies the value of the compressibility of water thus selected has exceeded the reported value by a factor of from severalfold to manyfold. Whether this excessive value results from the inadequacy of the mathematical approach to take into account the shape irregularities and the heterogeneities of the aquifer, or is due to some type of formation compaction and decrease of porosity has not been established. Because of the significance of the potential water yield of formations with reference not only to oil reservoirs but to water resources as well, it is very important that a representative value for the effective water compressibility be determined. One of the best known examples of a field for which it has been possible in the past to predict the future reservoir pressure is the East Texas Field. Until about 1943 it was possible by means of mathematical equations to duplicate past pressure behavior and to predict with a high degree of accuracy the reservoir pressure of the field. Since 1943, however, the calculated pressures have deviated progressively from the observed pressures to such a degree that in recent years, it has

Jan 1, 1951

By D. F. Kaufman, H. R. Spedden, A. M. Gaudin

MANY studies of comminution have been made to ascertain the size distribution of the product and to evaluate the work of comminution in the light of the size distributions of the feed and product. Up to now, these studies have been essentially statistical in character, that is, a certain lot of feed was subjected to comminution in some specified way, and the aggregate product was fractionated into sizes, thereby losing all knowledge of individual relationship of feed to product pieces. Radioactive tracers offer a means to do something in this respect which could not be done before, namely, to follow the rupturing of some particular piece in its normal environment of other pieces. That is, it permits going beyond the usual statistical limitations of size distribution studies to what may be termed a personalized or individualized study. The purpose of this paper is to present some preliminary experiments conducted with this tool. The method employed was to mark radioactively some constituent of a feed. It is possible, of course, to consider the preparation of two lots of material of which one is radioactive and the other is not, and to blend the two ahead of the comminuting step; but to do so is open to the objection that the two preparations may not be identical. Therefore a technique has been chosen that removes this objection by merely taking out a size fraction of a comminution feed, rendering that fraction radioactive by exposure to a neutron flux, and then by returning it to Table I. Size Distribution of Offspring Albite Particles Originally 28/35 Mesh and in Admixture with Other Sizes After Grinding 2 min in a Steel Ball Mill Specific Activity ' Cumu- Corrected Distrl- latlve Size for Back- butlon In Distri- Fractlon ground, Weight, Product, button, of Product, cpm/gm g Pctb Pct Mesh (A). (W) (P) (ZP) + 28 0 56.0 0 100.1 28/35 62.6 54.0 24.8 75.3 35/48 62.8 59.4 27.7 47.6 48/65 41.1 53.0 16.2 31.4 65/100 29.6 45.7 10.2 21.2 100/150 23.7 37.0 6.6 14.6 150/200 23.3 25.1 4.4 10.2 200/270 20.1 19.0 2.9 7.3 270/400 17.8 21.2 2.9 4.4 -400 22.9 25.2 4.4 — 100.1 a These activity determinations were made in rapid succession in the order given. The specific activity (Ao) of the active 28/35 mesh fraction of the feed was measured at the beginning, after the measurement on the 65/100 mesh size fraction of the product, and; The end. The decay-corrected activities at those times were 246.7, 241.0. and 236.9 cpm per gm. The weight (W0) of the active 28/35 mesh fraction in the feed was 55.0. b Example of calculation for P in the 65/100 mesh oroduct frac- A W tion; A = 29.6, W = 45.7, Ao = 242.7, Wo = 55.0: P = — x — Ao Wo = 0.102 = 10.2 pet. the remainder of the charge for the comminution experiment. A relatively simple procedure was developed by which albite, containing sodium, was activated in the M.I.T. cyclotron. The cyclotron makes highspeed deuterons which impinge on a beryllium target, thereby producing a concentrated neutron flux. The mineral was exposed to this flux for 2 hr. This treatment changed enough of the sodium to sodium 24 (14.8 hr half-life, 1.4 mev ß) as to make detection and measurement easy. The nuclear reactions taking place were: 11Na23 (n,?) 11Na24 (irradiation) 11Na24 ß,?,? 12Mg24 (decay) The detailed technique of the experimentation was as follows: 40 kg of hand-sorted, lump albite were crushed to pass 10 mesh. After careful mixing of the lot, a screen analysis was made. The whole lot of material was fractionated on standard Tyler screens from 14 down to 200 mesh. Samples for experiments were compounded from these fractions in accordance with the screen analysis. When it was desired to make an experiment in which, for example, the 28/35 mesh size fraction was to be studied, the blend of size fractions was made as indicated above, except that the 28/35 mesh size fraction was added only after irradiation in the cyclotron. The blended charge containing the activated albite was ground for 2 min in a laboratory ball mill with a steel ball charge of controlled size distribution. The ground product was carefully sized on a set of Tyler screens in a Ro-tap. Each size was analyzed for radioactivity by the use of an end-window Geiger-Mueller counter and standard scaling circuit. This analysis was carried out in detail as follows: a 20-g sample was placed in a Petri dish, packed carefully to obtain reproducible geometric distribution with reference to the Geiger-Mueller tube, and the activity was counted for a 2-min period. Several determinations of the activity of the active size fraction in the feed were made at various times to establish the decay in activity with time. Linear interpolation was used to evaluate the activity that the active size fraction in the feed would have had at any given instant. The ratio of the observed activity in a size fraction of the product to the activity that the active size fraction in the feed would have had at the same time gives the fraction in the product size that came from the irradiated size in the feed. The general formula for finding the distribution, P, of a specific individual size fraction in the feed

Jan 1, 1952

By C. O. Lee, Z. W. Bartlett, R. H. Feierabend

The Grand Isle sulfur mine is located in the Gulf of Mexico, approximately seven miles off the coast of Grand Isle, Jefferson Parish, La. The deposit is on acreage covered by oil, gas, and mineral leases originally issued in favor of Humble Oil & Refining Co. by the State of Louisiana which were continued, maintained, and redesignated by the U.S. Department of the Interior after passage of the Outer Continental Shelf Lands Act. The sulfur deposit was discovered in 1949 when Humble Oil & Refining Co. penetrated more than 200 ft of sulfur-bearing limestone in a zone between 1813 and 2075 ft below sea level. In 1954, Humble drilled ten more sulfur prospect holes, eight of which encountered sulfur ore. On September 19, 1956, Freeport Sulphur Co. acquired from Humble Oil & Refining Co, the sulfur rights underlying the tracts, and the actual design of the installation began the same month. The first structural contract was awarded in December 1957 and offshore erection began in June 1958. The initial phase of construction has been completed and production by the Frasch process commenced in April 1960. The estimated total cost of the project is $30 million, of which $8 million is the extra cost incurred by the necessity of offshore operations. More than $22 million was expended before production was started. GEOLOGY OF DEPOSIT Grand Isle is the third largest sulfur deposit in the U.S. The orebody embraces several hundred acres, but its outer limits are yet to be defined to the northeast, east, and south. Most Gulf Coast sulfur deposits occur in a caprock mantle of calcite (referred to as limestone), anhydrite, and occasionally gypsum, which covers the apex of an intrusive mass of salt. Commercial quantities of sulfur are usually confined to the calcite or limestone member. Most often such limestone is completely enclosed by dense anhydrite below and impervious sediments above, which effectively form a closed reservoir. The depth of the Grand Isle orebody ranges from 1800 ft to 2500 ft below sea level. Within the present boundary, the sulfur-bearing limestone varies in thickness from 220 ft to 425 ft, while the sulfur content varies an average of about 15 pct in the leanest hole to an average of about 30 pct in the richest. Rock containing less than 5 pct sulfur is not classed as ore, and holes assaying less than 20,-000 long tons per acre of sulfur in place are not considered commercial offshore. The sulfur enrich-

Jan 1, 1961