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By J. D. Mooney

(San Francisco sleeting, September, 1915) THE accompanying chart has been drawn for the convenience of engineers as a means of quickly determining the correct number of plies of conveyor belts operating under specific conditions. The calculations are based on the average safe strength (factor of safety, 15) of the various standard rubber conveyor belts. The, calculations assume maximum loading conditions; that is, the belt is considered as carrying the greatest load that it will handle without spillage at ordinary belt speeds. This not only produces the most economical operating conditions, but also the maximum tension in the belt. The chart is a graphical representation of the formula: p = kgW (L + 1OH) Where, p = the correct number of plies k = a constant, depending on the type of drive g = the weight in pounds per cubic foot of material handled W = the width of the belt in inches L = the length of the belt in feet (approximately twice the center distance). H = the difference in elevation between the head and tail pulleys, in feet. For a simple drive, with a bare pulley, k = 1/250,000 For a simple drive, with a rubber-lagged pulley, k = 1/300,000 For a tandem dive, with bare pulleys, k= 1/375,000 For a tandem drive, with rubber-lagged pulleys, k = 1/455,000 The chart is drawn for a simple drive, with a bare pulley (k =1/250,000;

Jan 9, 1915

EDMUND NEWTON, Minneapolis, Minn. (communication to the Secretary?).-In discussing the question of the deoxidation of steel and material suitable for performing this function at the end of the heat, it would seem logical also to include the question of prevention of oxidation in the steel or the formation of iron oxide, FeO. I refer to the use of manganese in the basic open-hearth and basic Bessemer processes. The advantages of high manganese in pig iron for these processes have evidently been clearly understood in Germany for a number of years, although little has been written in regard to the exact manner in which the benefits are obtained. In this country, while we make no steel by the basic Bessemer process, our basic open-hearth process is becoming more and more important. Until 10 years ago, in this country, manganese in the pig iron for this process was considered of little value and by many writers it was spoken of as a disadvantage. During the past 10 years, however, in certain parts of the United States, higher contents of manganese in basic pig have been used with considerable success, although there is apparently nothing in our technical literature to show the reasons for this trend. A German book, "The Basic Open-Hearth Steel Process" by Carl Dichmann does, however, offer an explanation. Dichmann says that if the charge for either of the above-mentioned processes contains 3 per cent. of manganese or above, satisfactory steel.

Jan 6, 1917

By W. W. Tyler, A. C. Wilson, L. B. Nesbitt

INVESTIGATIONS of thermal conductivity and impact strength of the titanium alloy RC-130-B and 316 stainless steel were undertaken because of interest in strong, nonmagnetic, commercially available alloys of low thermal conductivity for use in low temperature experiments. Measurements of electrical resistivity and thermoelectric power were also made for some of the samples studied. The titanium alloy designated as RC-130-B is manufactured by Rem Cru Titanium Inc. It contains 0.14 pct C, 3.99 pct Al, and 4.7 pct Mn. A general discussion of properties of the two phase Ti-4Mn- 4A1 alloys is given by Finlay and Vordahl.' The alloy is machinable and has a yield strength greater than 130,000 lb per sq in. at 0.2 pct offset. The 316 stainless steel sample used for both conductivity and impact strength measurements was obtained from the Allegheny-Ludlum Steel Corp. and is designated as Allegheny metal 18-8M, Type 316, Grade 316. The sample had received 25 pct minimum final cold reduction and had a Brine11 hardness rating of 255. Several impact tests were made on a sample of 316 stainless which had not received the 25 pct cold reduction. Also several data points are reported giving thermal conductivity and electrical resistivity for a sample of 304 stainless steel taken from stock. Figs. 1 and 2 give thermal conductivity and electrical resistivity data for the titanium alloy and for

Jan 1, 1954

By H. F. Dawes

In China all minerals are, theoretically at least, the property of the Emperor, and the Imperial permission must be got from him for the privilege of working them. A direct tax is levied on this privilege, and by simple command, the Emperor can close a mine at any time. Occult geomantic influences are a large factor in determining the opening or the arbitrary closing of a mine. The location with reference to points of the compass, graves and natural objects, may be really or professedly considered as indicating that those influences are favorable or unfavorable. The consequence, is, of course, that for the authorization and encouragement of any considerable enterprise, friends' at court, practical politics, and more or less bribery, are required. As a result, most Chinese mining is illicit, and is carried on in a small way only. Often along a single vein, or over a small section of mining country, a few individuals obtain rights over all the openings, most probably by loaning money to the head-men of the operators and holding the mines as security for the debt. In such cases, perhaps, for better security, all the ore is reduced in the works established by the creditors, who also handle all silver produced..As the head-men are, for the most part, improvident, and the laws and customs for the collection of' debts are stringent and peculiar, the " officemen" or creditors acquire in time what is practically an ownership of

Jan 1, 1892

By W. V. Youdelis, W. H. Bear, G. Cochrane

HERETOFORE, there has been very little study of the effects of various metallurgical factors on the behavior of thermoelectric materials, the need for which is evident if optimum processing and design of thermoelectric devices is to be realized. Accordingly, we have undertaken such an investigation on the thermoelectric materials bismuth and Bi-Sb alloy and in this paper present some preliminary results which merit consideration, in particular the relatively high thermoelectric power and figure of merit values obtained for the Bi-12Sb (at. pct) alloy powder compacts. The thermoelectric parameters for ingot and powder compact specimens are determined and the results are compared with published data for single crystals. Preparation of Materials. The bismuth and antimony used in this investigation are six nines pure. Melting and casting of the ingots was carried out in air for expediency, since most oxidation unavoidably occurs during the preparation of the powder by filing of the ingots. Chill cast ingots of pure bismuth were prepared by pouring the melt into split copper chill molds, and unidirectionally solidified ingots of bismuth and Bi-Sb alloy were obtained by slow directional cooling in pyrex tubes. All melts remained bright during melting and casting, indicating minimum oxidation. Powder for the powder compact samples was obtained by filing the ingots with a fine and coarse file to give a variation in the particle size of the compacts. The particles in the fine powder compacts varied in size from approximately 28 pct less than

Jan 1, 1970

By James B. Duke, Ernest W. Greene

An idea of what is meant by "Ultrafine Minerals Or Slimes" as used in the title can be had by an examination of Fig. I. Particle size distributions are presented for a crude kaolin clay, a coarse fraction and a fine fraction. The crude kaolin as mined was blunged with water, degritted through a 325-mesh Tyler screen, and dispersed with sodium silicate. The dispersed crude was then centrifuged in the laboratory into the coarse and fine fractions shown in the figure. The distribution curves were obtained by the well known sedimentation technique of Casagrande' using a long arm centrifuge to obtain equivalent spherical diameters down to 0.2 microns on the finer fraction. Fig. 1 shows the coarse fraction kaolin to be 50% finer than 3 microns, while the crude kaolin is 50% finer than 1.4 microns, and the fine fraction 50% finer than 0.6 microns. For comparison 53 microns on the horizontal scale would represent Stokesian diameters which would just pass a 325- mesh Tyler screen, taking into consideration the Andreasen sieve correction factor of 1.22 X the screen opening.' Another helpful comparison is the surface areas, which in square meters per gram, are 0.044 for 53 micron particles, 0.77 for 3 microns, 1.65 for 1.4 microns, and 5.0 for 0.46 micron particles. Fig. 2 is an electron micrograph of a similar fine fraction kaolin showing the hexagonal plate- like particle shapes.

Jan 10, 1962

By S. A. LoPilato, J. T. Smith

SEVERAL techniques have been evaluated for cooling the throat area of rocket-nozzle inserts to prevent erosion or fracture of the inserts during exposure to high operating temperatures and pressures. Self-cooled composites, such as infiltrated tungsten, have shown considerable promise for these applications. These composites can be fabricated by infiltrating the refractory matrix with a lower-melting metal or non-metal which is insoluable in tungsten. During firing, the lower-melting substance undergoes a series of continuous endothermic phase changes which absorb sufficient heat to maintain the nozzle matrix material at or below a safe operating temperature. At present, the state-of-the-art has reached a point where the refractory matrix density and microstruc-ture have been established as the critical parameters to be controlled for optimum self-cooled performance.'" Nondestructive testing has been utilized to ensure that porous tungsten billets were of uniform density and free from cracks or other defects prior to fabrication into rocket nozzle inserts. Ultrasonic-velocity techniques have been employed because of their reliability and reproducibility. The purpose of this note is to present and interpret the test data developed for porous tungsten matrices. For evaluation purposes, tungsten powders with Fisher subsieve sizes of approximately 4 and 18 p have been obtained for study from four commercial sources: the General Electric Co., Wah Chang Corp., Fansteel Metallurgical Corp., and Kennametal, Inc. Porous tungsten matrices were fabricated from the powders by hot pressing in induction-heated graphite die assemblies. Typical billets ranged from 3 in. diam, 2 in, high to 5 in. diam, 5 in. high. The ultrasonic-velocity measurement technique employed was through transmission, pulse echo at a frequency of 1.0 mc using matched barium titanate crystal transducers. The testing equipment included a pulsed ultrasonic generator, an amplifier, a specimen holder, and an oscilloscope, as shown in Fig. 1. The porous tungsten thickness was measured to i 0.0005 in, with precision micrometers while the oscilloscope achieved 0.02 psec time measurement accuracy. The time for a sound wave to pass through the billet, the bulk wave velocity, was calculated to 0.5 pct using Eq. [l]: V-} where V = bulk wave velocity, in. per psec, T = specimen thickness, in., and / = time, psec. To develop inspection standards, the bulk density of a porous tungsten billet was determined by the ASTM water-immersion technique.3 The ultrasonic-velocity measurements were completed at seventeen positions for each billet and averaged to develop a characteristic standard velocity for a particular tungsten powder at several density levels. A plot of ultrasonic velocity vs density is presented in Fig. 2 for six different tungsten powders. This graph has been established as

Jan 1, 1967

By C. B. Smith, A. G. Guy

The power and convenience of tensor analysis are employed in deriving the equations that describe three-dimensional diffusion in an n-component system plus vacancies. A "Kirkendall coordinate system, '' defined in principle by Kirkendall markers, is used in defining the intrinsic diffusion coefficients that are of primary interest. The defining equations are then transformed to local cartesian coordinates and to fixed cartesian coordinates, the latter being convenient for experimental measurements. Finally, it is shown how the intrinsic diffusion coefficients can be calculated from the experimentally determined quantities. It is generally recognized that any treatment of the essential diffusion phenomena in metallic systems—the jumping of atoms from one lattice position to another—must be based on movement of the atoms past Kirkendall interfaces.' A logical extension of this idea is the proposal that, fundamentally, diffusion must be described mathematically in terms of "Kirkendall coordinates." The basic equations thus obtained may then be transformed into other coordinate systems, when such transformation leads to simplification of either the experimental or mathematical treatment of diffusion data. Tensor analysis is clearly the appropriate mathematical tool for this purpose, since it provides methods both for determining general equations that are valid for all coordinate systems and for conveniently transforming the equations from one coordinate system to another system related to the first in some known fashion. For the present purpose three coordinate systems are used, and it is convenient to begin with a description of the relations among these three systems. FICK LAW FOR KIRKENDALL COORDINATES The reference coordinate system, and the one that is useful for most experimental measurements, is a cartesian coordinate system, xi (i = 1, 2, 3), fixed with respect to some point in the specimen, such as an end of the alloy bar undergoing diffusion. A second set of coordinates, the Kirkendall coordinate system, is one that in principle can be described by the location of inert markers (Kirkendall interfaces). A convenient mathematical relation between Kirkendall coordinates, x'i, and the reference cartesian coordinates, ii, is obtained by specifying that the Kirkendall coordinate system coincide with the cartesian system at time, t = 0. After diffusion has occurred for some time, t = t, the Kirkendall coordinate system will differ from the reference system in the manner shown schematically for the one-dimensional case in Fig. 1. The third coordinate system is Darken's1 local cartesian-coordinate system, xi, which is identical with ii in orientation and units, but which moves with the point under consideration in the Kirkendall coordinate system. Even though most diffusion problems are essentially one-dimensional, there is an advantage in first carrying out the analysis of the three-dimensional problem to gain a clearer insight into the assumptions that are made in the usual one-dimen-

Jan 1, 1962

By E. R. Atkins, G. H. Smith

Results of laboratory tests are presented to show that lire value of "m", in the Archie expression dernlined by the shapes of the particles in the system. Tile value of m "the shape factor", is constant for a system of particles of a given shape for a range of F - + values. Applying this concept, one can predict F - + relationships for mixtures of particles with different shapes, and these predicted relationships are useful in electric log interpretation. It is suggested that an equation of the form 1/F -10mcan be used to describe the properties of natural formations containing varying amounts of sand and clay. From this work and values of "a" and "m" reported in the literature, it appears that in many cases rocks in the same geological horizon have a common primary porosity but contain varying amounts of a particular clay. It is concluded that the equation can be applied to a rock-water system only when values of "a" and "m" have been established for the particular system. INTRODUCTION The petroleum literature contains many reports of the results obtained by determining formation resistivity factor F and porosity + of rock samples from oil fields all over the world. The usual practice is to use data from a large number of samples from a number of fields to find an average relationship between F and +. Several such average relationships have been advanced. In the absence of data on a particular formation or field, it has been the practice to use the average relationships to give a rough approximation of the F - + relationship. The purpose of this paper is to report on basic relationships that exist between F and + for naturally occurring particles in water solutions. Other workers' have found the same relationships apply to the diffusion of hydrogen through packed beds of dry particles. In the work discussed here, relationships for application to unconsolidated sands or shales containing mix- tures of particle shapes are derived. These relationships, developed for unconsolidated formations, may apply to consolidated formations. EXPERIMENTAL To evaluate F- relationships for unconsolidated rocks, the results of laboratory measurements on simple slurries of clay or sand will be used. Such laboratory studies are concerned with the electrical behavior of water-containing rocks. The wet rock constituents are electrically similar in slurries and in rocks. Archie2 defined formation resistivity factor as All resistance measurements were made using a 1,000-cycle impedance bridge with an oscilloscope as the null detector." The accuracy of this bridge was better than * 0.15 per cent. For the particular apparatus employed, no additional reactance was required to achieve balance for samples with resistances between

By William F. Harris, Joseph Easha

FOR many years basic control of refinery operations depended on visual observation of small chill specimens poured at various intervals during processing. The oseto of these samples was related to the physical and chemical properties of the metal. Since the =setn is dependent on many factors other than oxygen content, this method, while giving a general indication of the condition of the copper, does not accurately measure the oxygen content. For the last 3 years a modified vacuum fusion procedure which enables the operator to determine the oxygen content of the copper within 1 5 min of sampling has been in use at the Westinghouse Copper Mill. For use with this apparatus a sampling technique has been developed which gives oxygen values representative of the oxygen content of the wire bar. The sampling technique is based on a statistical study, which compared the oxygen content of the laboratory sample of copper poured at the same time a wire bar was being poured, with the oxygen content of the wire bar. The apparatus used for the determination of oxygen in copper is shown in Fig. 1 and is essentially the same as previously described but with one important modification. A very porous fritted glass disc has been inserted in the tubing between the manom- eter and 40/50 ground glass joint. The fritted disc retains the copper vapor and copper particles in the furnace section and prevents contamination of the mercury in the manometer. Without the disc the manometer became difficult to read after a few weeks of operation. In earlier work1 it had been established that the simplified vacuum fusion apparatus used at the Copper Mill gave essentially the same results as a con-vential vacuum fusion apparatus. However, for this study it was necessary to determine the difference, if any, between the oxygen content of the wire bar and the oxygen content of the small chill sample used for the oxygen analysis. This correlation was established by taking a chill sample at the same time wire bars were being poured. The wire bar being poured at the time the chill sample was taken was marked and removed for further analysis. The copper is sampled at various times during refining and cast into laboratory size samples with the mold shown in Fig. 2. The mold is made of cold rolled steel and is 2 in. high and 2 1/2 in. in diam. The large upper portion of the cast sample is used for measurement of the conductivity of the copper, The lower portion which is a rod about 1/4 in. diam by 3/4 in. long is used for determination of the oxygen content. This portion of the sample weighs about 5 g which is approximately the size sample used for the analysis. The only preparation neces-

Jan 1, 1962

By E. W. McAllister

THE decision of the California Oil Umpire's1 office to accept well potentials established from subsurface-pressure data has brought to the attention of many operators for the first time the application of such data to production problems. This paper reviews the development and application of subsurface-pressure data in Kettleman Hills, where these data have been used in production work since 1932. The Kettleman Hills field was discovered in October 1928. The first subsurface-pressure surveys were made early in 1932 and by the middle of 1933 the two major operators in the field were making routine pressure runs in their respective wells. Shortly thereafter, these companies agreed to exchange pressure data, and later a third company entered into the agreement. This made it possible to analyze the effects upon the reservoir pressure of past production practices, which are discussed in the latter part of the report. It is interesting that many of the applications of subsurface-pressure data discussed herein were anticipated by C. L. Clarks and C. B. Kimberlin‡ in a reports dated March 1933. PRODUCTIVITY INDEX In the majority of individual well problems involving the use of subsurface pressure data, it is necessary to use a factor known as the "productivity index," which indicates the ability of a well to produce and represents the number of barrels of oil or oil and water per day that will enter the well bore for each pound per square inch pressure drop made opposite the producing interval of the well. The productivity index may be determined from pressure and production data for one or more rates of flow and a static or shut-in pressure survey or from production and pressure data for two or more rates of flow. Productivity indices may be based upon either net oil or total fluid production. All indices referred to in this report are based upon net oil. The value of the productivity index for Kettleman Hills wells decreases generally with time and it is not uncommon for the index to vary in value at any specific time for various rates of flow. The decline of the productivity index may be attributed partly to the loss of reservoir pressure. As. the reservoir pressure decreases, gas originally in solution is released from the oil, congesting the flow of fluids through the formation and increasing the viscosity and surface tension of the oil; thus the flow resistance of the fluids through the formation is increased, resulting in a decrease of the productivity index. For convenient reference, the productivity indices for each well are plotted against time and a curve is drawn through the points showing the trend of the average index value. Plotted on Fig. I are index values for five

Jan 1, 1941

By H. L. Eiselstein, F. P. Huston, B. B. Betty

An extensive program for the establishment of creep data on high-nickel alloys has been in progress during the past seven years. This paper presents the accumulated data on two solid solution alloys, cold-drawn, annealed Monel and cold-drawn, annealed Inconel. Data on these two alloys in other conditions will be published at a later date. Monel, a nickel-copper alloy, is normally considered a corrosion-resistant material, but it will be shown that it also has considerable creep strength, validating its use at temperatures up to and including 900°F. Inconel, a nickel-chromium-iron alloy, is definitely a heat-resisting alloy possessing good creep strength and oxidation resistance up to iiooOF., and because of its oxidization resistance has been used successfully at much higher temperatures for lightly stressed parts. The literature contains but meager data on the creep properties of high-nickel alloys. Howevcr, Bennett and McAdam have presented a substantial quantity of creep data for cold-drawn Monel.1 The material as tested was not representative of mill production for it was cold-drawn to a reduction of area of 40 per cent as against 13 per cent, which is the mill standard for Monel. Twenty-two individual tests were run on each alloy in the investigation described in the following pages. The data and curves presented herein represent an integration of all the tests to obtain the most accurate picture of the creep properties of these alloys. Neither of the two alloys was found to be embrittled by the combination of temperature and stress, as evaluated by room-temperature tensile and impact tests that were made following creep testing. These data indicate that no tendency toward embrittlement exists. It is recommended that 6300 lb. per sq. in. be used as a working stress for cold-drawn, annealed Monel at 900°F. and 13,200 lb. per sq. in. for cold-drawn, annealed Inconel at the same temperature. Table 8 lists recommended working stresses, based on 80 per cent of the stress to produce a minimum creep rate of 0.01 per cent per 1000 hr., for Monel and some steels. Equipment The equipment used for these tests consists of Colville creep-testing machines manufactured by the Tinius Olsen Testing Machine Co. The load is adjusted, depending on the stress level, to give an error in the stress of not more than ± 0.1 per cent. This is based on considerations of lever sensitivity and the stress used for the standard (A.S.T.M. Tentative Standard E22-38T) 0.505-in. diameter creep specimen having a 2-in. gauge length. The single-specimen furnaces are provided with primary and secondary windings, from

Jan 1, 1945

By Richard V. Hughes, Rudolf J. Pfister

The necessity for getting more water into sands of low permeability in any secondary-recovery water-flood operation in order to recover all the available oil always has been a major problem. In the early days of water-flooding the addition of soda ash and caustic soda to fresh input waters was recommended and tried without success in the Bradford field. The most frequent difficulty was sand plugging. The use of natural and artificial brines often has been suggested for water-flooding, in the belief that laboratory observations of decreasing fresh-water throughput rates in measuring water permeabilities of consolidated sand cores might be partially explained by swelling of clays. A review of available literature bearing on the subject and related laboratory experiments are presented herein, offering an explanation for failure in use of soda ash and caustic soda waters and supporting the recent concept that every water used for input purposes in the secondary recovery of oil should possess such physical and chemical characteristics as to keep the clay content of the producing sands in a permanently flocculated condition. Produced brines meet this requirement. Their use is recommended as a means of increasing intake rates of tight sands and oil recoveries, as a solution to brine-disposal problems, and as a means of conserving a natural resource. Introduction There is a general belief among those engaged in the secondary recovery of oil by water-flooding that one of the most important requirements for the success of any such project is an adequate supply of good, fresh water. Fresh waters have the advantages of being more easily stabilized than salt waters and of being usable about the lease for all purposes. The use of brines for water-flooding never has been given much consideration in the Pennsylvania Grade area. The use of brines in Mid-Continent operations has been considered largely as a substitute for fresh waters, which were economically unobtainable for many operations. Estimated recoveries for some water-drive fields indicate that less of the original oil in place will be left upon abandonment than with the above-average practices used in Pennsylvania Grade water-flood operations. Lower residual oil saturations than 25 pct of the pore space following the water-flooding of Third Bradford sand cores in the laboratory are unusual. In comparison, water-flushed sands surrounding any virgin oil pool are found to be practically devoid of oil. Such lower natural residual oil saturations may be the result of a time factor much longer than economic under artificial water-flood operations, but neither the producer of primary oil nor the producer of oil by secondary recovery can obtain maximum recoveries unless full advantage is taken of all natural forces and

Jan 1, 1947

By Richard V. Hughes, Rudolf J. Pfister

The necessity for getting more water into sands of low permeability in any secondary-recovery water-flood operation in order to recover all the available oil always has been a major problem. In the early days of water-flooding the addition of soda ash and caustic soda to fresh input waters was recommended and tried without success in the Bradford field. The most frequent difficulty was sand plugging. The use of natural and artificial brines often has been suggested for water-flooding, in the belief that laboratory observations of decreasing fresh-water throughput rates in measuring water permeabilities of consolidated sand cores might be partially explained by swelling of clays. A review of available literature bearing on the subject and related laboratory experiments are presented herein, offering an explanation for failure in use of soda ash and caustic soda waters and supporting the recent concept that every water used for input purposes in the secondary recovery of oil should possess such physical and chemical characteristics as to keep the clay content of the producing sands in a permanently flocculated condition. Produced brines meet this requirement. Their use is recommended as a means of increasing intake rates of tight sands and oil recoveries, as a solution to brine-disposal problems, and as a means of conserving a natural resource. Introduction There is a general belief among those engaged in the secondary recovery of oil by water-flooding that one of the most important requirements for the success of any such project is an adequate supply of good, fresh water. Fresh waters have the advantages of being more easily stabilized than salt waters and of being usable about the lease for all purposes. The use of brines for water-flooding never has been given much consideration in the Pennsylvania Grade area. The use of brines in Mid-Continent operations has been considered largely as a substitute for fresh waters, which were economically unobtainable for many operations. Estimated recoveries for some water-drive fields indicate that less of the original oil in place will be left upon abandonment than with the above-average practices used in Pennsylvania Grade water-flood operations. Lower residual oil saturations than 25 pct of the pore space following the water-flooding of Third Bradford sand cores in the laboratory are unusual. In comparison, water-flushed sands surrounding any virgin oil pool are found to be practically devoid of oil. Such lower natural residual oil saturations may be the result of a time factor much longer than economic under artificial water-flood operations, but neither the producer of primary oil nor the producer of oil by secondary recovery can obtain maximum recoveries unless full advantage is taken of all natural forces and

Jan 1, 1947

By G. N. Goldberg, Robert A. Rapp

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

Jan 1, 1967

By Norman F. Schulz, Emert W. Lindroos, Strathmore R. B. Cooke

DURING the course of an investigation of the effects of various starch products on hematite and quartz in regard to their separation by flotation, it was found that whereas most starches flocculated suspensions of hematite in water, they did not flocculate similar suspensions of quartz. However, a derivative of whole corn starch containing approximately one tenth aminoethyl group (-—CH,CH2NH2) per glucose unit proved to be an exception. This aminoethyl starch was a very good flocculant for both hematite and quartz, and also possessed the property of depressing both minerals in cationic flotation tests. In view of the widespread use of starch as a flocculating agent of solids in tailing water, pulps, and for coal slimes, ore and various other purposes in sulphide and nonsulphide flotation, attention is called to the effective surface activity of aminoethyl starch in flocculating suspensions of the two minerals investigated. Test Materials The starch products employed included Globe Pearl starch No. 144 and fresh aminoethyl starch, both supplied by the Corn Products Refining Co. Dr. A. L. Elder" has kindly furnished a description The minerals used in the various tests are listed in Table I. Their specific surfaces were determined by the air permeability method, which gave results reproducible to within plus or minus 3 pct. Surface areas obtained by krypton adsorption were greater than the air permeability values by a factor of 2.0 for quartz and 62.4 for hematite. Starch Adsorption on Mineral Surfaces Starch adsorption data were obtained by agitating for 1 hr measured volumes of neutral starch solutions of known concentrations with weighed quantities of finely divided mineral of measured specific surface. The mineral then was separated from the pulp liquor by centrifugation and the residual starch content determined by chemical analysis. The analytical procedure consisted of oxidizing the starch with an excess of dichromate in acid medium at elevated temperature and titrating the excess dichromate by the ferrous ammonium sulphate—potassium permanganate method. Analytical results were reproducible to within less than 1 pct. Adsorption data obtained in unbuffered solutions near the neutral point are plotted in Fig. 1. The adsorption on either mineral was far greater for the aminoethyl starch than for the Pearl starch. Flocculation The degree of flocculation was determined for a given pulp by measuring the time required for the supernatant liquid to reach a certain degree of clarity. This was accomplished by passing a standard light beam through the pulp, contained in a glass settling tube, and measuring the time required after agitation ceased for the intensity of the transmitted beam to reach a predetermined value. Starch reagent was added to each pulp in small uniform increments, and the settling time was determined after each such addition. Increase in pulp liquor volume due to the added starch reagent was ignored in these tests. Pulps were maintained at or near neutrality. of the preparation of the aminoethyl starch: "Three hundred and sixty grams of powdered unmodified corn starch was slurried in 3 liters of water and stirred during gelatinization. Eighty-six grams of ethylenimine was added slowly during reflux which was continued for 4 hr. The yellow solution set to a gel upon cooling. This was broken up and neutralized with HC1. The thick paste was dried on hot rolls. Adsorbed polyethylenimine and salts were removed from the yellowish products by washing first with acidified aqueous '60 per cent' alcohol. The white product contained nitrogen corresponding to about one aminoethoxy group per ten glucose residues." Only laboratory samples of this starch derivative have been prepared. The starch reagents for use in flocculation, flotation, and adsorption tests were made up by dispersing the appropriate quantities of air-dry starch in cold water, adding boiling water, and heating for 30 min at 120°C under pressure. When used ip adsorption tests, the starch solutions first were cleared of insoluble matter by centrifugation.

Jan 1, 1953

By Strathmore R. B. Cooke, Emert W. Lindroos, Norman F. Schulz

DURING the course of an investigation of the effects of various starch products on hematite and quartz in regard to their separation by flotation, it was found that whereas most starches flocculated suspensions of hematite in water, they did not flocculate similar suspensions of quartz. However, a derivative of whole corn starch containing approximately one tenth aminoethyl group (-—CH,CH2NH2) per glucose unit proved to be an exception. This aminoethyl starch was a very good flocculant for both hematite and quartz, and also possessed the property of depressing both minerals in cationic flotation tests. In view of the widespread use of starch as a flocculating agent of solids in tailing water, pulps, and for coal slimes, ore and various other purposes in sulphide and nonsulphide flotation, attention is called to the effective surface activity of aminoethyl starch in flocculating suspensions of the two minerals investigated. Test Materials The starch products employed included Globe Pearl starch No. 144 and fresh aminoethyl starch, both supplied by the Corn Products Refining Co. Dr. A. L. Elder" has kindly furnished a description The minerals used in the various tests are listed in Table I. Their specific surfaces were determined by the air permeability method, which gave results reproducible to within plus or minus 3 pct. Surface areas obtained by krypton adsorption were greater than the air permeability values by a factor of 2.0 for quartz and 62.4 for hematite. Starch Adsorption on Mineral Surfaces Starch adsorption data were obtained by agitating for 1 hr measured volumes of neutral starch solutions of known concentrations with weighed quantities of finely divided mineral of measured specific surface. The mineral then was separated from the pulp liquor by centrifugation and the residual starch content determined by chemical analysis. The analytical procedure consisted of oxidizing the starch with an excess of dichromate in acid medium at elevated temperature and titrating the excess dichromate by the ferrous ammonium sulphate—potassium permanganate method. Analytical results were reproducible to within less than 1 pct. Adsorption data obtained in unbuffered solutions near the neutral point are plotted in Fig. 1. The adsorption on either mineral was far greater for the aminoethyl starch than for the Pearl starch. Flocculation The degree of flocculation was determined for a given pulp by measuring the time required for the supernatant liquid to reach a certain degree of clarity. This was accomplished by passing a standard light beam through the pulp, contained in a glass settling tube, and measuring the time required after agitation ceased for the intensity of the transmitted beam to reach a predetermined value. Starch reagent was added to each pulp in small uniform increments, and the settling time was determined after each such addition. Increase in pulp liquor volume due to the added starch reagent was ignored in these tests. Pulps were maintained at or near neutrality. of the preparation of the aminoethyl starch: "Three hundred and sixty grams of powdered unmodified corn starch was slurried in 3 liters of water and stirred during gelatinization. Eighty-six grams of ethylenimine was added slowly during reflux which was continued for 4 hr. The yellow solution set to a gel upon cooling. This was broken up and neutralized with HC1. The thick paste was dried on hot rolls. Adsorbed polyethylenimine and salts were removed from the yellowish products by washing first with acidified aqueous '60 per cent' alcohol. The white product contained nitrogen corresponding to about one aminoethoxy group per ten glucose residues." Only laboratory samples of this starch derivative have been prepared. The starch reagents for use in flocculation, flotation, and adsorption tests were made up by dispersing the appropriate quantities of air-dry starch in cold water, adding boiling water, and heating for 30 min at 120°C under pressure. When used ip adsorption tests, the starch solutions first were cleared of insoluble matter by centrifugation.

Jan 1, 1953

By Anna H. Connard

SUMMARY The discussion focusses on developments in the debt/equity swap market since the Marte project was negotiated in early 1988. It emphasises carrying forward the recent market trends to anticipate the breadth and scope of debt/equity conversions for mine development in the 1990s. Secondary market prices of LDC paper, conversion values and political influences in the host countries and the use of near debt and commodity-based instruments as components of mine financing in debt/equity deals will be placed in the perspective of recent trends and expectations for the future. THE MARTE PROJECT The Marte mine is a gold porphyry deposit in Chile's high Atacama, for which financing was put together at the beginning of 1988. The Marte project was financed by a combination of common equity and loans. It was unusual that the equity infusions were made under different programs. Some of the international equity was infused with fresh funds via DL 600. Other common foreign equity was provided through the conversion of Chilean bank debt under Chapter XIX. On the loan side,. export credits for the import component of machinery and equipment were sought. Local bank financing was negotiated for the remainder of ' the project's anticipated cost. The debt conversion market in Chile was at its apex in terms of interest, activity and government support when the mine financing was arranged. The price of Chilean paper in the secondary market hovered about 62 to 66 cents per U.S. dollar of face value. Meanwhile, the Chilean government was negotiating conversion redemptions significantly closer to full face value. The government differentiated between debt paper exchanged for corporate investors who had sourced that paper in the secondary market, and debt paper held by bank investors who would incur a transaction loss in the conversion. The use of a combined DL 600lChapter XIX equity financing created different yield calculation bases for the various investors. Chapter XIX prevents remittance of profits before year 5 and capital repatriation before year 11. Investors choosing this vehicle have either for a corporate policy in the target project not to declare dividends until repatriation is allowed, or they have to seek uses for the peso liquidity that would be generated through dividend declarations in the early years. However, DL 600 investors face no such waiting period on dividends, nor do they have restrictions imposed on cashing out of the investment before the 11th year. Therefore, any equity structure with components of both investment mechanisms will have inherent differences in cost basis and future income flows for the various participants. This equity imbalance is defensible if the investment motivations of the parties are analyzed: a mining investor using fresh funds looks for a hurdle return on equity calculated at conservative commodity prices, with as much flexibility to reap upside benefits as possible; a mining investor choosing to invest through a debt conversion mechanism will realize a modest short term gain on the conversion, reducing his effective cost basis, but sacrificing some return because of the waiting period on repatriation of dividends. INVESTMENT OBJECTIVES A bank investor exchanging his own paper for an equity participation in a mining project realizes a conversion loss on the transaction. He seeks a risk adjusted acceptable hurdle rate of return to recoup that loss over time. Motivation for the bank investor to take that loss may be derived partly from a strategy to diversify its existing portfolio by internal policy and externally regulated guidelines. The bank will compare yields on its loan portfolio to that country with anticipated dividend flows discounted back at a risk adjusted rate. It will analyze the project with return objectives of yield enhancement over time and with

Jan 1, 1990

By A. L. Lee, M. H. Gonzalez, R. F. Bukacek

Experimental viscosity data for methane are presented for temperatures from 100 to 340F and pressures from 200 to 8,000 psia. A summary is given of the available data for methane, and a comparison is presented for that data common to the experimental range reported in this paper. Correlation of the data is presented, and predicted values are given for temperatures up to 460F and pressures up to 10,000 psia. INTRODUCTION The increasing ranges of temperature and pressure at which fluids are produced, transferred and processed in the petroleum and chemical industries stress the need for accurate information on physical properties, both for engineering calculation and for improving the methods used to estimate physical properties. A survey of the literature reveals that disagreements between published data on the viscosity of methane are common and that most investigations have been conducted over restricted temperature and pressure ranges. This situation made it desirable to undertake an investigation with a scope common to most of the literature data available. APPARATUS AND MATERIALS The apparatus used in this investigation was the capillary tube viscometer'described by Dolan,10 with modifications introduced in the general design and operation of the instrument. It has an effective pressure range from 14.7 to 10,000 psia and a temperature range from room temperature to 400F. The design of the viscometer is based on the establishment of a manometric head between two vessels containing the test fluid and a volume of mercury. The reservoirs are connected by a capillary tube through which the test fluid flows and a tube through which mercury flows. A pressure gradient is established by elevating one of the vessels above the other, the resulting flow of mercury displacing the test fluid through the capillary. The schematic diagram of the system (Fig. 1) shows the arrangement of the equipment auxiliary to the viscometer. The density cells assembly (E, Fig. 1) was not used in this investigation since reliable data are available on methane. 23 The assembly consists of a bank of eight 316 stainless steel pycnometers. Experimental values of the density of a natural gas19 and i-butane14 samples have been obtained for pressures up to 8,000 psia and temperatures up to 340F. The methane used was obtained from the Southern California Gas Co. Mass spectrometric analysis showed a composition of 99.8 percent CH4, 0.1 percent C2H6 and 0.1 percent C3H8. EXPERIMENTAL VALUES AND ACCURACY OF DATA Determinations were carried out at several temperatures. With the temperature in the cabinet controlled at a given level, a series of runs were made at various pressures. To establish pressures lower than that obtained from the methane cylinder, it was necessary to vent the gas slowly to the atmosphere until the desired pressure was reached. The consistency of the test run time for a particular condition can be used as a criterion for the accuracy of the data. A further check is obtained by comparison of the viscosity values obtained using different driving heads. To establish the instrument's reproducibility, a large number of runs were made at three completely different conditions of temperature and pressure. Data obtained were analyzed statistically to determine the most reliable value for the variance of the experimental data. It was found that the variances of the data taken at different experimental conditions were not statistically equivalent, but they were small. The largest variance was found at 8,000 psia and 100F, where the standard deviation was 0.385 micropoise. Therefore, 99.9 percent of the data can be expected to fall within 1.15 micropoises of the population mean, except for the intervention of systematic errors in operation.

By Wayne L. Worrell

Thermodynamic data for the stable carbides and oxides of chromium, molybdenum, and tungsten have been critically eualuuted and are used to determine the stable condensed phases at 1 atm total pressure in each metal-carbon-oxygen system. Pourbaix-Ellingham diagrams have been constructed and are used to estimate the minimum temperatures neces.see)*y to oblain these metals by corbolhermic redlrction under reduced pressures. USING recently reported data for the carbides and oxides of chromium, molybdenum, and tungsten, the stable phases in the Group VI metal-carbon-oxygen systems at specific temperatures and pressures can be determined. The thermodynamically stable regions in each metal-carbon-oxygen system can be completely pictured using a Pourbaix-Ellingham diagram in which the two coordinates are oxygen potential (-RT In Po2) and temperature. Worrell and chipman' have described and constructed such diagrams for the metal-carbon-oxygen systems of vanadium, columbium, and tantalum. Downing2 has used similar diagrams to provide a description of the reactions in submerged arc furnaces. One of the examples which he cited was the Cr-C-O system; however, an improved diagram is presented in this paper using recently obtained data for the carbides of chromium. Although some of the oxides and carbides of the Group VI metals exist over slight ranges of composition,3 all solid phases are represented as stoi-chiometric compounds in the subsequent diagrams. Any error introduced into the calculated equilibria by neglecting the compositional variation of these phases is less than the uncertainty in the thermodynamic data. In a Pourbaix-Ellingham diagram for a three-component system, the phase rule requires that at equilibrium four condensed phases specify a point, three condensed phases determine a line, and two condensed phases define an area. To obtain a well-defined area at high oxygen potentials and teniperatures, the initial carbon to oxygen mole ratio is specified to be more than sufficient to reduce the oxide but not enough to convert all the metal to carbide. Thus, the lowest regions in the subse- quent Pourbaix-Ellingham diagrams represent areas in which the metal and its carbide are the stable condensed phases. Cr-C-O SYSTEM A) Thermodynamic Data. To simplify the subsequent calculations, all thermodynamic data are presented in the form of linear Gibbs-energy-of-formation* equations which were derived for the temperature range 505° to 2000°K and are reasonably accurate over the entire temperature ranges of the diagrams. The thermodynamic data for the compounds occurring in the Cr-C-O system are summarized in Table I. Several volatile chromium oxides have been reported,4 but their influence is negligible in the Cr-C-O system. Thermodynamic data for CO and CO2 were taken from the compilation of Coughlin.5 The only solid chromium oxide sufficiently stable to exist below 1800°K in the Cr-C-O system is Cr2Os.11 The Gibbs-energy-of-formation equation for Cr2O3 was obtained by revising the data tabulated in Coughlin,5 using the heat of formation of ah' and the high-temperature thermal data for chromium.7 In 1953 Richardson8 re-evaluated the original work of Kelley and coworkers,9 who measured the thermodynamic properties of the chromium carbides. However, the high-temperature equilibrium results of Boericke9 yield values for ?G°f of Cr2O3 which are 2 kcal more positive than the accepted data. His results for the chromium carbides are based on the same questionable equilibria. Gleiser10 recently determined the Gibbs energy of formation of Cr3C2 and the equation in Table I was calculated from her data and the thermal data of Kelley and coworkers.9 Thermodynamic data for the Cr7C3 and Cr23C6 carbides were obtained by combining the Cr3C2 data

Jan 1, 1965