Search Documents

By R. E. Ogilvie, N. L. Peterson

Intevdiffusion and intrinsic diffusiorz coefficients were determined in the uranium-niobium system from diffusion couples analyzed with an electron microbeam probe. A Previously unveported intermediate phase, designated in this report as the delta phase, was found to exist along the mobium-rich side of the miscibility gap. Its composition width was determined from the concentration gradients in the diffusion couples. The presence of this phase was also confirmed by microhardness analysis and metallographic observations. THE excellent corrosion resistant properties, high-temperature strength and reasonable nuclear properties of niobium have prompted its use as an alloying element with uranium and as a possible cladding material for reactor fuel elements. Hence the formation and growth of intermetallic phases as well as diffusion data for the uranium-niobium system are of considerable practical importance to metallurgists and nuclear engineers. Diffusion zones may exhibit varying degrees of complexity dependi.ng upon the mutual solubility of the metals involved, and the intermediate phases which may form. In the simplest case where the metals exhibit a calmplete range of solid solubility, a single phase region is produced. Generally, however, the metals may react to produce a multiphase diffusion zone containing several layers of intermetallic phases. A number of investigatorsl-6 have analyzed the concentration gradients present in diffusion couples in order to investigate phase equilibria and solu- bility limits. If diffusion is the rate-controlling process in establishing a concentration gradient, the compositions at the interfaces of the intermediate phases will represent the equilibrium values expected from the phase diagram at the temperature at which diffusion has taken place. No published information is available at this time on diffusion in the uranium-niobium system. A number of investigators7-" have contributed information to the construction of the uranium-niobium phase diagram from other than diffusion techniques. There is good agreement on the high uranium side of the phase diagram, but the high niobium side of the miscibility gap still remains somewhat in doubt. The phase diagram as determined by B. A. Rogers, et al.7 is shown in Fig. 1. The present work was aimed at obtaining fundamental information about the solubility limits of the miscibility gap and diffusion in the uranium-niobium system. A Kirkendall effect, which might be expected on the basis of the rather large difference in melting points between uranium (1132°C) and niobium (2415" C), was also investigated. The concentration gradients were measured by an electron microbeam probe technique, similar to that used by Castaing,l2 Adda and philibert,13, l4 and Macres.4

Jan 1, 1961

By Robert H. Richards

In the latter part of December a batch of amalgam was retorted and the tin in the retort uncovered while at a low red heat, and allowed to cool slowly to a temperature more suitable for ladling into moulds. It was then ladled and made what appeared to be nice, white, malleable block tin. On February 15th our attention is called to the fact that the tin is brittle, and on examination we find that the molecular condition of the pigs has changed to the extent of one-half its material. The change shows itself by an enlargement appearing on the surface something like crystallization, and comes in spots. The condition of the metal in these spots is very peculiar. It has changed from a malleable metal to a brittle one, with a structure somewhat resembling stibnite, and a color very considerably darker gray than tin. The analyses of the two parts of this tin pig showed the following results: Mercury. Tin. Specific Gravity. Crystalline part,.....2.62 97.24 6.175 Malleable part,.....2.38 97.50 7.387

Jan 1, 1883

By H. R. MacMichael

THE rate, at which zinc ore can be sintered varies widely, depending on the characteristics- of the ore. A coarse table concentrate already roasted to a very, low sulfur content may sinter at the rate of-8.6 tons per hour per 100 sq.ft., of wind-box area. At the other extreme is a finely ground flotation, concentrate, with considerable sulfur remaining in the ore as delivered to the sinter plant, for which corresponding rate may be only 3.8 tons per hour, or 44 per cent of the first rate. A usual, size-of sinter machine in zinc plants is one with wind-box 3.5 by 33 ft., making 115.5 sq. ft. of area, and using a 100-hp. fan. Such a machine with the coarse concentrate described would produce 10 tons of sinter per hour; and with the fine, flotation concentrate would produce only 4.4 tons per hour. Ore of the latter class is -sintered at the plant of the Mexican Zinc Co. (subsidiary of the American Smelting & Refining Co.) at Rosita, Mexico. ; Consequently, an unusually large sintering capacity per ton of ore to be treated is required, and provision was made for treatment of 9000 tons concentrates per month, preroasted to. 5 to 9 per. cent sulfur. For this duty three of the usual 33-ft., 100-hp. sintering machines would have been needed.. Considering the auxiliary equipment. necessary for proportioning, handling, and mixing charge, as well as means for disposition of the sinter, a three-unit plant becomes-very complicated, especially if the capacity should be doubled later. After much study it was decided to build a single sintering unit of ample capacity for the work, the plant thus being much simpler and cheaper in construction as well as in operation (Figs. 1 and 2). The sintering machine was built with a wind-box 5.25 by 60 ft. (315 sq. ft.) and provided with a 300-hp. fan.

Jan 1, 1932

By B. H. Caudle, A. R. Khan

The oil production performance of thin-oil-column type reservoirs producing entirely by natural water drive are discussed in this paper. The dimensionless production histories were obtained in a series of scaled porous-medium laboratory-model tests under varying effects of rate of production, mobility ratio across moving boundary, ratio of oil- and water-sand thickness and mobility ratio across fixed boundary including the effects of different residual oil saturations in the water-invaded regions. This scaled-model study of thin oil columns indicated that greater recovery of oil results for lower values of the following: rate of production, mobility ratio across the moving boundary, water-sand thickness relative to the oil-sand thickness, and mobility ratio across the fixed boundary or residual oil saturation in the water-invaded region of oil sand The results of the study are given as dimensionless production history plots which may be used to predict the performance of the field they represent. INTRODUCTION Oil fields producing under natural water drive can be classified into two major groups: (1) an "edge-water drive" reservoir group in which the water is encroaching from the reservoir periphery, and (2) the group of reservoirs in which the oil-sand is entirely underlain by an aquifer. Reservoirs in the second group are further subclassified as "bottom-water drive" reservoirs and "thin-oil-column" reservoirs. The latter reservoirs are characterized by their relatively equal oil- and water-sand thicknesses and by having both the oil and water zone relatively thin. When oil is produced from a water-drive reservoir by a partially penetrating well, water breaks through sooner or later before all of the displace-able oil is recovered. Many analyses of this general situation have been made with varying degrees of realism in their approaches, both theoretical and experimental5.6 in nature. Pertaining to the scaled laboratory model studies of natural water drives using porous media, detailed investigations have been made by Henley, et al.7 on bottom-water drive and by Caudle8 on edge-water drive reservoirs. No laboratory model studies, however, have been made to investigate the performance characteristics of thin-oil-column reservoirs. This paper presents the results of a study on scaled models of thin-oil-column reservoirs, operated under varying conditions corresponding to the actual field practices. SCALING PARAMETERS The object of scaling is to produce a one-to-one relationship between physical and dynamic parameters of the model -and prototype. The most comprehensive treatment of scaling techniques for oil reservoirs is given by Geertsma, et a1.,9 which covers two methods for arriving at dimensionless groups for scaling. Table 1 lists the scaling parameters suitable for creating kinematic and dynamic similarities between the model and the prototype in the variables considered for the thin-oil-column reservoirs. In order to achieve similarity it is essential that the dimensionless groups listed in Table 1 have equal values in the model and the protorype simulated. Since it has been established that the role of interfacial forces is neglible in gross fluid movement in a reservoir no attempt was made to scale capillary forces- Although there are reports describing Scaling criteria for these forces,10,ll consideration of the necessary but restrictive conditions for

Jan 1, 1970

By H. P. Stuwe

It is investigated whether a model of sphere packing permits the computation of the lattice parameters and their variation with concentration in various a phases; it does, except in phases containing silicon. Several observations indicate that a particular role is played by the "E-atoms" in the lattice. THE phase is formed by many alloys of the transition elements.'-' Its structure has been described by Bergman and Shoemaker,5,8 Dickins, Douglas, and Taylor,7 and Kasper, Decker, and elanger.' There are five kinds of crystallographically equivalent positions for the 30 atoms in the unit cell which have been designated by these authors I, 11, 111, IV, and V or, in the same sequence, A, B, C,D, and E, as shown in Fig, 1. For the purposes of the present paper two elements of the lattice will be discussed separately: The lattice planes perpendicular to the c-axis which are made up by the atoms A, B, C, and D and which determine the a-parameter; and the close-packed "vertical rows" of E-atoms which determine the c-parameter. asper,9 and Frank and kasper10 described the a phase and other complex structures as sphere packings. In these papers particular attention is paid to the coordination polyhedra. Lattice positions with an equal number of nearest neighbors are considered equivalent regardless of their crystallo-graphic description. This seems to work very well for the explanation of ordering phenomena in the a phase as far as information on this is available." If the description of the phase as a sphere packing is valid it should be possible to draw two further conclusions: 1) It should be possible to calculate the lattice parameters from the atomic radii of the components, and 2) It should be possible to predict the variation of the lattice parameters with concentration within one phase field. Both points are discussed in this paper. PROCEDURE Measurements of lattice constants were done with a symmetrical back-reflection X-ray camera. With Cr-radiation, about a dozen a1 lines could be observed with most samples. From the (550/710)- and 720-lines the a-value was computed. With this value the c-parameter was calculated from the (333)- and (413)-lines. Finally, the position of all the other lines was computed from the lattice parameters thus obtained. In this way the validity of the indexing could be checked and, at the same time, this proce- dure gave an estimate of the accuracy of the lattice parameters. A correction was made for film shrinkage. The atomic radii used in the computations are the Goldschmidt radii for coordination number 12. Actually, some of the atoms have a coordination number of 14 or 15, but the error thereby introduced is small. * For the computation of lattice constants from the atomic radii an "average atomic radius" of all components was used, i.e., complete disorder was assumed. Although this seems to be true for some systems like OS-Cr,4 it is not true in others.11,13,14 The ordering model, however, which has been suggested by Kasper on the basis of extensive research lets both kinds of atoms contribute to both the ''vertical rows" and the lattice planes perpendicular to them, so that even with ordering of this kind the assumption of complete disorder cannot introduce a very serious error in calculating lattice parameters. RESULTS Bergman and shoemaker6 gave a table of the interatomic distances in the Fe-Cr phase. If we disre-

Jan 1, 1960

By R. J. Stokes

This paper compares the room-temperature mechanical behavior of magnesium oxide crystals containing 'fresh' and 'grown in' sources. 'Fresh' dislocation sources introduced by cleavage or mechanical contact move and multiply to generate slip bands at 3000 psi. Macroscopically the crystals yield smoothly at 6000 psi and can be quite ductile. When 'fresh' sources are eliminated by chemical polishing the crystals have to rely on 'grown in' sources to initiate slip. They then deform elastically up to extremely high stresses (-30 to 50,000 psi) yielding with a sharp stress drop down to the level at which Ifresh' sources operate. Grown in' sources are considered to be associated with impurity wecipitate particles or inclusions. Annealing crystals at 2000°C dissolves these particles thereby eliminating sources for slip. The crystals then become consistently stronger (> 70,000 psi) approaching within 1/10 of the theoretical strength. Dislocations of the grown-in network do not move under stress to nucleate slip. It is proposed that they are locked electrostatically. DISLOCATIONS were originally conceived to resolve the large discrepency between the theoretical and real strength of solids. The idea that slip propagates by the movement of dislocations is now well confirmed both by electron transmission and etch pit studies. But this by itself is not sufficient to explain the low yield strength of crystals for there is still the need to understand where slip dislocations originally come from. Theoretical estimates place the stress to generate dislocations homogeneously in the lattice at approximately 1/30 of the shear modulus,' a value 104 to 105 times greater than the stress at which the very first manifestations of plastic deformation have been observed. Only an special cases can the theoretical strength be approached; in crystals of high perfection such as whiskers2 where dislocation sources do not preexist and in covalent crystals where the dislocations present at room temperature are almost completely immobilized by the bond character of the solid.3,4 For the most part it is necessary to assume that the yield strength of ionic and metallic solids corresponds to the motivation and multiplication of dislocation sources present beforehand. The question as to their origin appeared to be answered by the suggestion of Frank and Read5 that dislocations forming part of the grown-in structure could operate as a mill for the large scale production of dislocations. The Frank-Read mechanism is still widely accepted as the source of dislocations but a number of observations have been reported which are in serious disagreement with it. One of the most intriguing of these is that under normal testing conditions dislocations of the grown-in network appear to play no role in the plastic deformation of rock salt structure ionic solids. This was first reported in the etch pit studies on lithium fluoride by Gilman and Johnston6 and is true also for magnesium oxide. To explain the comparatively low yield stress of lithium fluoride it was proposed by a number of authors7,9 that small unresolved prismatic loops formed by vacancy condensation were acting either directly or indirectly as the dislocation sources. This proposal led Gilman10 to perform a series of detailed and careful experiments on lithium fluoride to try to identify the sources responsible for the initiation of slip. He concluded that prismatic loops played no general role and that other sources were more important. Dislocation sources in ionic crystals can be divided into two general categories. First, there

Jan 1, 1962

By L. Zwell, H. A. Wriedt

X-ray Lattice parameter and bulk density measurements were made at room temperature on solid solutions of nitrogen in purified a, iron, containing from 0 to 0.053 wt pct N. When nitrogen is dissolved in a, iron, the fractional increase in unit cell volume (X-ray diffraction) and the fractional increase in volume per gram of iron (bulk density measurement) are the same within experimental error. The two sets of results when averaged show that the unit cell edge of a, iron increases linearly by 3.2 X 10-2 A per wt pct N dissolved and that the partial gram-atomic volume of nitrogen at infinite dilution in a, iron is the same as it is in nitrogen-martensite, that is, 5.90 cm3. RECENT reviews17' of literature dealing with the lattice parameter of ferritic iron-nitrogen alloys indicate that the dilating effect of dissolved nitrogen on the bcc unit cell of a iron is not known with confidence. Five investigations3-7 either revealed no effect of nitrogen or were inconclusive. Among other investigations, where quantitative data were obtained, the results of Osawa and Iwaizumi8 indicate too large an effect, and those of Eisenhut and Kaupp9 show the lattice parameter of ferrite varying with the nitrogen content at concentrations far beyond the known solubility limit. It is not clear in Burns'10 data what value should be used for the lattice parameter of nitrogen-free ferrite in calculating the dilation. Burdese11 shares with Burns the shortcoming that the iron-nitrogen alloys were solution-treated and quenched with undissolved nitride present. The consequence is that the un- certainties in the solubility limit1 are added to those in the lattice parameter measurements when the variation of lattice parameter with nitrogen content is computed. For a system of such widespread interest, we felt that a new investigation was merited. Both X-ray diffraction and bulk density measurements were used to determine the dilation of the , a iron lattice by dissolved nitrogen. EXPERIMENTAL PROCEDURE Material. The bulk density and X-ray diffraction experiments were both made with specimens of a purified iron (denoted as "B iron")- from Battelle Memorial Institute. The impurity contents were as follows: As, C, Cu and Pb—50 ppm; Ag, Al, Co, Ga, 0, Ti-11 to 50 ppm; B, Be, Ca, Cd, Cr, Mg, Mn, Mo, N, Ni, S, Sb, Si, Sn, V, W-10 ppm or less. The vacuum-cast ingot was hot-forged and annealed. Pieces of the forged stock were machined and cold-rolled to give strip stock 0.08 and 0.002 in. thick for density and for X-ray measurements, respectively. Preparation of Specimens. Starting with a piece of the cold-rolled iron stock, the general sequence of operations, after an initial recrystallizing anneal, was to measure the density or lattice parameter, nitrogenize, remeasure the property, age or denitrogenize, and again measure the property. Duplicate analyses for nitrogen were made by a modified Kjeldahl method on portions of the actual density specimens and on pieces nitrogenized to equilibrium alongside the X-ray specimens. Annealing of the density specimens was performed by sealing the pieces with the as-rolled surfaces removed by filing into evacuated "Vycor" capsules and treating for 1 hr at 750°C followed by furnace cooling. (TO check the effect, if any, of annealing procedure, a specimen also was

Jan 1, 1962

By I. Fatt, D. N. Saraf

A method is described for measuring two- and three-phase relative permeabilities in sandstones or sand packs using a nuclear magnetic resonance (NMR) technique to determine fluid saturations. Two- and three-phase relative permeabilities have been determined on Boise sandstone using the NMR technique of saturation measurement. Three-phase relative permeability to water was found to depend only on the water saturation, whereas three-phase permeability to oil depended on both the water and oil saturations. Relative permeability to gas in three-phase flow was found to depend only on the total liquid saturation. INTRODUCTION Three-phase relative permeabilities are extremely useful in calculating field performance for reservoirs being produced by simultaneous water and gas drives. Three-phase relative permeability data are also needed for analyzing solution gas-drive reservoirs which are partially depleted and are being produced by water drive. Some thermal recovery processes involve three-phase flow which require three-phase relative permeability data for predicting reservoir behavior. Unfortunately, three-phase relative permeability measurements have rarely been made. Also, because of the scarcity of three-phase data, it has not been possible to date to relate other measured rock characteristics to the relative permeabilities with a great certainty. Leverett and Lewis,l Reid2 and Snell3 have reported three-phase relative permeability data on unconsolidated sands. Leverett and Lewis used ring electrodes spaced along the length of the sand sample to measure the resistivity of the sample which was assumed to be monotonically related to brine saturation. Gas saturation was determined from pressure-volume measurements. Oil saturation was obtained by material balance on the cell containing the sand sample. This method is involved and time consuming. Another difficulty arises from the fact that the resistivity of the sand is a function not only of saturation of brine but also of the distribution and saturation history of the brine in the pore spaces. Reid2 used a gamma ray absorption technique for measuring liquid saturation. This method has the disadvantage that total liquid saturation rather than oil or brine saturation is all that can be measured and still another method is required to determine the saturations of individual components. snel13 used a neutron bombardment method which also required a separate determination of the individual component saturations. Caudle et al.4 measured three-phase relative permeability on consolidated sandstones using vacuum distillation for determining fluid saturations. Distillation after each reading makes this technique very lengthy and time consuming. Corey et a1. 5 and Naar and Wygal 6 measured three-phase relative permeability on sandstones by the capillary-pressure method. Semipermeable diaphragm assemblies were used at each end of the core specimen to keep the water phase in the core. Gravimetric methods were used to determine fluid saturations. Sarem7 recently reported an unsteady-state method for measuring three-phase relative permeability on sandstones. This method is an extension of Welge's method8 for measuring two-phase relative permeability. Although Sarem's method is simple and comparatively fast, the assumptions involved may oversimplify the problem. Sarem's assumption, that in all rocks relative permeability to each fluid will depend only on the saturation of that fluid, seems to be rather unrealistic. Neglecting capillary effects at the end of the core is also a weak assumption. Donaldson and dean9 measured three-phase relative permeability using a method similar to Sarem's.

By A. R. Orban, R. B. Engdahl, J. D. Hummell

The initial phase of a research program on smoke abatement from Bessemer converters is described. In work sponsored by the American Iron and Steel Institute, a 300-lb experimental Bessemer converter was assembled to simulate blowing conditions in a commercial vessel. Measurements of smoke and dust were also made in the field on a 30-ton commercial vessel. During normal blows the dust loading from the laboratory converter averaged 0.51 lb per 1000 lb of exhaust gas. This was similar to the exhaust-gas loading of a commercial vessel. The addition of hydrogen to the blast gas of the laboratory converter caused a decided decrease in smoke density. Smoke was also reduced markedly when methane or ammonia was added instead of hydrogen. The research is continuing on a bench-scale investigation of the mechanism of smoke formation in the converter process. DURING the past 2 years, on behalf of the American Iron and Steel Institute, Battelle has been conducting a research program on the control of emissions from pneumatic steelmaking processes. The objective of the research program is to discover a practical method for reducing to an unobjectionable level the emission of smoke and dust from Bessemer converters. PRELIMINARY INVESTIGATION Although conceivably some new collecting technique may be devised which would be economically practicable for cleaning Bessemer gases, no such system based on presently known principles seems feasible because of the extremely large volume of high-temperature gases involved. Hence, the research is being directed toward prevention of smoke formation at the source. A thorough review was first made of former work to determine the present status of the cleaning of converter gases. No published work was found on work done in the United States on collecting smoke or on preventing its formation in the bottom-blown, acid-Bessemer converter. In Europe, however, a number of investigations have been made on the basic-Bessemer converter. Kosmider, Neuhaus, and Kratzenstein1 conducted tests on a 20-ton converter to obtain characteristic data for dust removal and the utilization of waste heat. They concluded that because of the submicron size of the dust, special equipment would be necessary to clean the exhaust gases. Dehne2 conducted a large number of smoke-abatement experiments at Duisburg-Huckingen in a 36-ton Thomas converter discharging into a stack. A number of wet-scrubbing and dry collectors were tried unsuccessfully. A waste-heat boiler and electrostatic collector with necessary gas precleaners was felt to be the best solution for this particular plant. Meldau and Laufhutte3 determined that the particle size was all below 1 µ in the waste gas of a bottom-blown converter. Sel'kin and zadalya4 describe the use of oxygen-water mixtures injected into a molten bath in refining open-hearth steel. They claim that with use of oxygen-water mixtures the amount of dust formed was reduced between 33.3 and 20 pct of its previous level, and emission of brown smoke almost ceased. Pepperhoff and passov5 attempted unsuccessfully to find some correlation between the optical absorption of the smoke, the flame emission, and the composition of the metal in a Thomas converter in order to determine automatically the metallurgical state in the melt. In a recent U. S. Patent (NO. 2,831,762)' issued to two Austrian inventors, Kemmetmuller and Rinesch, the inventors claim a process for treating the exhaust gases from a converter. By their method the inventors claim that the exhaust gases from the converter are cooled immediately after leaving the converter to a degree that oxidation of the metal vapors and metal particles to form Fe2O3 is inhibited in the presence of surplus oxygen. Gledhill, Carnall, and sargent7 report on cleaning the gases from oxygen lancing of pig iron in the ladle. They claim the Pease-Anthony Venturi scrubber removed 99.5 + pct of the smoke, thereby reducing the concentration to 0.1 to 0.2 grain per cu ft, which resulted in a colorless stack gas after the evaporation of water. Fischer and wahlster8 developed a small basic converter and compared the metallurgical behavior of the blow with that of a large converter. Later work by Kosmider, Neuhaus, and Hardt9 on the use of steam for reduction of smoke from an oxygen-enriched converter confirmed that the cooling effect of steam is detrimental to production. From review of all of the published information on the subject, it was concluded that a practical solution to the smoke-elimination problem had not been found. Accordingly, it was deemed desirable to investigate the feasibility of preventing the initial formation of smoke in the converter.

Jan 1, 1961

By R. Shuttleworth, R. Smith

A Knudsen effusion tnethod I~as been used lo measure the vapor pressure of pure iron in the temperature range 1000° to 1500°C. Neutron-irradiated , natural iron was used and the Mn'~proclzdced by the (n, p) reaction removed by evaporation at high temperature. The results can be represented by the equation: where pM - 1.088 x 107 atm and T, = 20,890°K. A value of 100.2 kcal per g- atom was obtained for AH;. THE vapor pressure of pure iron in the temperature range 1000" to 1500°C has been measured. Radioactive iron and a Knudsen cell technique were used and the Mn' produced by an (n, p) reaction removed by evaporation at high temperature. From the variation of vapor pressure with temperature values of the enthalpy and entropy of solid iron have been found. Previous workers2 used a Lang-muir method and measurements were made over a smaller temperature range than that in this work. EXPERIMENTAL The apparatus used was similar to that of Pyle and Shuttleworth, and McLellan and Shuttle worth. However, because of the higher temperatures the Knudsen cell was machined from tungsten bar and the flanged furnace tube was beryllia. Heating was by passing a high current (70 amp at 7 v for 1500°K) through a strip of tantalum foil laid across the top of the cell and through a turn of molybdenum wire around the furnace tube. This method of heating ensured that the top of the cell was slightly hotter than the base and prevented condensation and re-evaporation from the orifice. The temperature was measured by means of a pt/Pt 13 pct Rh thermocouple spot-welded to the base of the crucible. To ensure accurate temperature measurement the iron was in the form of a thin disc (0.75 cm diam by 0.075 cm) which lay on the base of the cell. The high-purity iron was irradiated in the Harwell pile for a week at a neutron flux of 1.2 X 10" neutrons per sq cm per sec. The isotopes fe'~ and Fe" are produced by (n! y) reactions but only Fe", half-life 45.1 days, is a emitter; Mn which is also a y emitter, half-life 300 days, is produced simultaneously by an (n,p) reaction.' Immediately after irradiation of natural iron the ratio of ~e" to Mn y activity was 100:l. However, manganese is very much more volatile than iron and almost all the y activity of the condensate is due to Mn'~. Thus it was essential to eliminate all the manganeses before any measurement of the vapor pressure of iron was made and this was done by preliminary heating for 20 hr at 1400°C. For each determination the iron was dissolved from the target with acid and the y activity compared to a known weight of iron. By means of a y-ray spectrometer the y-activity measurements were made at the 1.09-mev peak of the 17e5' spectrum where the background was of the order of 3 cpm. Despite the low specific activity of ~e" a mass of 10- " g of iron could be determined corresponding to a vapor pressure of about l0-'' atm. RESULTS The vapor pressures were calculated from the equation: Where m is the mass of iron effusing in a time t through an orifice of area a2, r is the radius of the target, Z is the distance from the orifice to the

Jan 1, 1965

By D. R. Parrish, W. E. Lamoreaux, W. W. Owens

Several methods are now being used by the industry for determining the gas-oil flow characteristics of reservoir rock samples. Most of the laboratory experirnerltal rlzethods can be classified either as steady-state, unsteady-state, or Hassler-type tests. Although the validity of the results obtained by any specific method is not questiorzed, in general, the complexity of these methods leaves much to be desired. This investigation dealt primarily with the development of a simplified unsteady-state (gas drive) laboratory test method for measuring kg/ko re1ationships of small core samples. A procedure for selecting uniform and representative sandstone rock samples was developetl since it was observed that the reliability of the test resu1ts was dependent upon having a sample which was uniform in porosity and permeability. The importance of factors known to influence the results of this type test, such as oil viscosity, gas expansion, and pressure differential were eva/uated. The method of calculating the test results was found to give valid data over a wide range of gas expansion. The limits of pressure differential and oil viscosity which would insure reliable results were defined. In cornparisorz with other presently used testing methods, the gar drive method requires considerably less apparatus, is less time consuming, and is more readily adaptable to a routine type core test. INTRODUCTION The detcrmination of the gas-oil flow characteristics of reservoir rocks has been given concentrated study by the oil industry for the past decade. Both analytical and experimental methods have been considered. The analytical methods have generally relied on a simplified characterization of porous materials in order that the fundamental laws of fluid flow and capillarity could be utilized. More direct experimental methods have been proposed by numerous production research laboratories with the primary goal being a simple and inexpensive, yet reliable method for measuring the gas-oil flow characteristics of reservoir rock samples. The experimental methods which have been reported in the literature generally can be grouped into one of the following classifications: 1. Steady state1,2,3,4 in which a fixed ratio of flowing fluids is forced through the test sample until equilibrium conditions of saturation and pressure gradient are established. 2. Hassler or stationary liquid method5,6,7 in which a uniform liquid saturation is attained, usually through capillary desaturation, then gas or oil is flowed through the sample at a pressure drop insufficient to disturb the pre-established saturation. :. Non-steady state method1,8,9,10 In which only the gas phase is injected into the sample, causing displacement of the oil phase and resulting in a system of continually changing average saturation and saturation gradient. The steady-state and Hassler methods have been most popular because, no doubt, of the simplicity of the actual relative permeability calculations. The problems involved in these methods were limited to apparatus design and measurement techniques. In the steady-state method, for instance, a constant flowing fluid ratio is established which, at equilibrium, results in an essentially uniform saturation over the entire length of the test sample. Therefore, the basic flow characteristics could be obtained by correlating the average saturation of the test sample with the kg/ko determined at various flowing gas-oil ratios.

Jan 1, 1957

By R. G. Weavind, R. S. Young, I. Wolf

ONE of the most important fields of investigation at the Diamond Research Laboratory in Johannesburg is concerned with improvements in metallurgical practices for the diamond mining companies, with particular reference to increased recoveries of the smaller industrial stones. Considerable work has been done on the possible application of flotation processes to the diamond industry. From the viewpoint of recovery processes, diamonds in their natural state may be grouped into two classes, the water-repellent diamonds, which adhere to a grease surface, and the water-avid diamonds, which, because of their wettability, will not adhere to a grease surface and must be recovered by means other than the grease tables used for water-repellent diamonds. Experiments in the flotation of small diamonds from both kimberlite and alluvial deposits indicate the following conclusions: Water-repellent diamonds: Satisfactory flotation of —16 mesh diamonds, which are naturally water-repellent, may be accomplished using either Aero-float 25 together with cresylic acid, or Du Pont B23 as frother together with kerosine as auxiliary oily conditioner or froth stiffener. The quantities of reagents required are of the order of 0.15 lb per ton Aerofloat and 0.18 lb per ton cresylic acid. The use of acid circuits is detrimental, and for best results a pH between 7 and 9 should be maintained. R. G. WEAVIND and I. WOLF are with the Diamond Research Laboratory, Johannesburg, South Africa, and R. S. YOUNG, Member AIME, is Director of Research, Diamond Research Laboratory. TN 76B. Manuscript, March 23, 1951. A flotation period of 5 to 10 min is necessary to insure that all floatable diamonds are removed. Diamonds larger than 16 mesh cannot be recovered satisfactorily by flotation. Xanthates do not act as collectors for diamonds, and this is probably associated with their inability to impart a water-repellent surface to this mineral. Water-repellent diamonds smaller than 28 mesh can be floated quite well by the addition of a frother alone, such as pine oil or Du Pont B23. Water-avid diamonds: Partial flotation of the smaller sizes of wettable diamonds can be achieved by preconditioning with fatty acid soaps, cationic amines, and similar reagents, which will impart a water-repellent film to diamonds. Washing to remove excess reagent, followed by flotation, will result in a fair recovery, but the latter is much lower than for water-repellent diamonds. Crushed boart: Recovery of crushed boart from the waste products of industrial uses is best accomplished by first conditioning the diamonds present in the mixture with fatty acids, cationic amines, etc., removing the conditioning agent by washing, and floating in a cell of the pneumatic type. Flotation reagents found to be most suitable are Du Pont B23, and Aerofloat 25 together with cresylic acid. The optimum quantities are 1.2 g Du Pont B23, and 0.55 g Aerofloat plus 1.4 g cresylic acid, per liter of pulp in the cell. A solids-to-water ratio of 1 to 4 is found to be the most suitable, and alkaline circuits are necessary for best results. Diamonds larger than 28 mesh are not recovered satisfactorily by this procedure, but for finer sizes flotation offers an excellent procedure for the reclamation of this strategic industrial material.

Jan 1, 1952

By C. O. Burgess, A. B. Kinzel

Although vanadium is an important constituent of almost every brand of high-speed steel manufactured today, little is known as to its role in this series of alloys. The now standard 18 per cent tungsten and 4 per cent chromium constituents were the result of developments and improvements before 1903. In that year, vanadium was added to the steel by Dr. J. A. Mathews. This proved to be an outstanding contribution, so that the standard high-speed steel of today is generally referred to as the 18-4-1 type—18 per cent W, 4 per cent Cr and 1 per cent V. Various modifications have been attempted since then, but with the exception of the introduction of cobalt, no striking improvements have occurred. Vanadium has been increased to 2 per cent in many of the common brands, and at least one brand contains 5 per cent V in addition to the usual tungsten and chromium. The carbon has been gradually increased so that it is not uncommon to find 0.80 per cent in the standard grade, although the carbon in the 5 per cent vanadium steel mentioned above is approximately 1 per cent, and even 1.2 per cent has been made experimentally. The role of vanadium has never been well understood, and although vanadium has been increased to 2.5 and even 5 per cent in certain high speed steels, it has not been generally established that the higher vanadium contents result in superior cutting properties. However, in all of the investigations, of which the writers are aware, the interrelation of the vanadium and carbon contents was not considered as a prime factor. The carbon content was held at 1.2 per cent or less—generally at the usual 0.65 to 0.75 per cent. Theoretical Aspects Although the role of vanadium is not understood, there are theoretical considerations which indicate definite reasons for the improved cutting effciency due to vanadium. Refinement of the secondary grain is one distinct possibility. The well-known action of vanadium in limiting grain size might well be expected to operate in high-speed steels, and even though its action were not evident in the parent austenite grain.

Jan 1, 1932

By John M. Lovejoy

CURRENT production of petroleum on such a vast scale presents many interesting problems- the solutions of which are important not only to those directly interested in the business, but to the nation as a whole. The industry is relatively young. Until the discovers of the Lucas gusher at Spindletop in 1901 petroleum production had not exceeded 60,000,000 bbl. per year compared with 1,100,000,000 bbl. in 1936. In 36 years then, the modern oil business, production, transportation, refining, and marketing has developed. I will first present a brief history. of oil production as a background for consideration of the present situation.

Jan 1, 1937

By B. D. Lichter

The lattice parameters of zirconium and zirconium-oxygen solid solutions (hcp) were determined from measurements of back-reflection X-ray photograms obtained at 29°C using a symmetrical focussing camera. The following linear equations between parameters (c,a) in angstrom units (10-8 cm) and atom ratio (m) of oxygen to zirconium were obtained: c = 5.14764 + 0.2077m a =3.23168 + 0.1099m. The linear equations given are valid over the range 0 to 5 at. Pct 0. The accuracy of individual parameter measurements approaches the limiting accuracy determined by the spectral broadening of the incident characteristic radiation, and exceeds the accuracy of previously reported values. THE present work was undertaken in order to determine the lattice parameters of zirconium-oxygen solid solutions with an accuracy that allows quantitative determination of oxygen in zirconium. The results indicate that this is possible if very careful measurements are made, since the parameter change is only a few hundredths of a percent per at. pct 0.1, 2 In the present investigation the desired accuracy was achieved with large-grained samples using a back-reflection focussing camera and maintaining good temperature control during exposure. In addition a digital computer was used for calculation of the parameters by means of an analytical extrapolation.37 Suitable diffraction photograms were obtained from large-grained samples by using a modification of the technique described by Graf and Monteil.5 This consists of simultaneous rotation and oscillation of the specimen about two mutually perpendicular axes during exposure. Whereas, normally the upper limit of grain size is about 50 µ for useable diffraction photograms, this technique allows extending the upper limit of grain-size to exposure of a single crystal. EXPERIMENTAL Preparation of Alloys for X-ray Diffraction—Zir-conium, designated as hafnium-free, Westinghouse "Grade 1," was swaged from l/2-in.-diam crystal bar to 3/8-in.-diam rods. Substantially all of the hydrogen was removed from the zirconium by annealing at 1200°C in a high dynamic vacuum. The rods were then swaged to 0.2 in. diam without intermediate annealing, and 2 in. lengths were cut for alloying with oxygen. Samples for chemical analysis were taken from portions of the rods between each 2 in. length. Chemical analysis of the dehydroge-nated zirconium is given in Table I. Commercial tank oxygen (99.5 pct 0) was condensed in a liquid nitrogen-cooled trap, and part of the condensate was slowly reevaporated into 5-liter storage flasks. Nitrogen remained as a reactive impurity, and the calculated maximum increase in nitrogen content after a 5 at. pct 0 addition to zirconium was 50 ppm by weight. However, chemical analyses of several of the prepared alloys indicated that the maximum increase in nitrogen content was 10 ppm. The storage flasks, a Sieverts-type gas burette and manometer, and associated traps, pumps, and pressure gauges were connected through a glass high-vacuum manifold to comprise the gas addition system. A fused silica tube, connected to the mani-

Jan 1, 1961

By W. G. Oldham

By monitoring the capacitance of abrupt p-n junctions it is possible to follow the motion of substitu-tional impurities. A p-n junction is formed by growth of silicon from an Al-Si alloy on an n-type silicon sutstrate at a temperature in the range 650" to 750°C. The diodes are etched and sorted for consistent V-I and capacitance behavior and separated into groups. After irradiation, each set with an unirradiated control set is annealed to various temperatltres for 10 mm and the capacitance remeasnred. For very heavily doped diodes (-1019 per cm3) observable capacitance changes occur at neutron fluences of >1015 per cm 3. The results may be interpreted in seceral ways, the simplest of which is to assume simple vacancy diffiision with small impurity -racancy interaction (at the diffiision, i.e. annealing temperature of 700°C). In this interpretation it is found that a typical vacancy makes about 1024 jumps and travels about 10-5 cm before disappearing. The required effective annihilation center density is about 1016per cm3 . Estimates of the vacancy-impurity interaction can be made and the above numbers correctecl, but for arty reasonable assumptions the number of vacancy sinks connot be much reduced. ThE complete annealing of radiation induced defects requires that the vacancies and interstitials either recombine, travel to the surface of the crystal, or travel to an annihilation center, e.g., a dislocation or a precipitate. If the interstitial is ignored except as a possible vacancy annihilation center at low temperatures,* the motion of vacancies may be followed by monitoring the corresponding motion of substitutional impurities. pfister2 has measured the enhanced diffusion of impurities in an asymmetric shallow diffused silicon structure by optically monitoring the junction movement. In these experiments we monitor instead the capacitance of a heavily-doped deep symmetric p-n junction. The sensitivity for this method is several orders of magnitude higher than in Pfister's technique, mainly for two reasons: 1) the junction capacitance of a heavily-doped junction is sensitive to impurity movements in the Angstrom range* com- and 2) the junction may be far from the surface which is a major annihilation center for vacancies. THE EXPERIMENT A p-n junction is formed by the epitaxial growth of silicon from an A1-Si alloy on a silicon substrate at a temperature in the range 650° to 750°C. The technique used is the transport of an aluminum melt through a temperature gradient.4 A 10-mil thick aluminum disc is sandwiched between two silicon wafers and the assembly raised to about 650° C with a temperature gradient normal to the sandwich. After about 8 hr the upper (hotter) wafer has been entirely transported and deposited epitaxially on the substrate wafer. The substrate and overgrowth resistivity are measured with a 4-point probe. The as-grown structure is lapped until the wafer is about 1/2 mm thick with the junction in the center. Contacts consisting of electroless nickel covered by electroplated rhodium are applied to both the p and n sides. The wafer is diced into square dice 1/2 to 1 mm on a side and the dice are etched sufficiently to remove approximately 1 mil of silicon. The following results are all for aluminum (p-side) and antimony (n-side) doped specimens with NA =3x 1018 per cm3, ND = 2-8 x 101A per cm3. The diodes are sorted for consistent V-I and capacitance behavior and separated into groups. After irradiation, each set with an unirradiated control set is annealed and the capacitance remeasured. A special capacitance measurement method is used to insure a low sensitivity to shunt resistance. The diode is voltage driven and the current monitored by a phase lock amplifier. It is possible to adjust the detector phase to a point where shunt resistances as low as 100 O have no effect on the reading. The diodes in this study have a capacitance in the range 1000 to 5000 picofarads and a shunt resistance in the range 100 to l06 O depending on the stage of the anneal. THEORY The theoretical problem is twofold: 1) The computation of the amount of impurity diffusion and hence the impurity profile resulting from a given amount of vacancy motion, and 2) the computation of the capacitance from the impurity profile. A comparison of the theoretical and experimental capacitance (in particular the changes) yields the amount of vacancy motion. Vacancy Motion. A convenient parameter to measure the total amount of vacancy motion is Jv the total number of vacancy jumps per unit volume. Although this parameter varies with position in the crystal, owing to vacancy annihilation at the surfaces, it is approximately independent of position far from the surfaces, i.e. in the junction region. In terms of the number of vacancies per unit volume Nv and the vacancy diffusivity given by

Jan 1, 1970

By J. Ostachowicz, B. Holynska, M. Lankosz

The paper presents an analyzer and the method for the continuous determination of weight percentage of ore grains with diameter smaller than 75 µm in mineral slurries. The method is based upon the measurement of characteristic x-rays of copper excited by primary radiation of two different energies 16.5 keV and 60 keV from Pu238 and Am241 sources respectively. Additionally the backscattered primary radiation is measured in order to correct the variations of the solids content in the slurry. Since the particle size distribution of slurry can be described by the Rosin-Rammler formula, some calculations have been carried out in order to evaluate the influence of distribution parameters upon the results of the measurements of weight percentage U75 of particles smaller than 75 µm. The influence of solids content and of the copper concentration variation on the results has been also evaluated.1 It resulted from the calculations that the ratio rl/rz, where rl and r2 are the relative intensities of copper characteristic x-rays excited with 16.5 keV and 60 keV photons respectively does not depend on the copper content within the range 1 % to 4% of copper and is slightly dependent on the solids weight fraction and its chemical composition. The change of the dispersion parameter of the Rosin- Rammler distribution from 0.5 to 0.9 results in a change of value of U75 of approximately 3.0%. The results of calculations have been confirmed by the results of laboratory experiments. Therefore, a prototype of industrial analyzer for continuous determination of weight percentage of particles smaller than 75 µm has been designed and made. Its schematic drawing is shown in [Fig. 1]. Slurry is flowing down through steel flow-cell of the length equal to approx. 2 m. In the center, two XRF measuring heads (1) and (2) are located. Each of the heads comprises a rigid waterproof cover (3) with the mylar window (4), in which a proportional counter of resolution 15% for 6.4 keV is mounted with a preamplifier (5). The low- energy isotope source (6) is centrally located above the detector

Jan 1, 1980

By William B. Plank

A NEW record-a quarter million students in the engineering schools of the United States and Canada-has resulted from the great demand for engineers following World War II. The figures released by the American Society for Engineering Education and which appeared in detail in the Journal of Engineering Education for January 1948, show that, on Nov. 1, 1947, 252,250 students were studying engineering in 149 engineering schools of both countries. There are 244,390 in the 143 schools canvassed in the United States, and 7860 in six schools in Canada. These figures include both undergraduate and graduate students and are therefore comparable with the figures in previous presentations on this subject. This unprecedented engineering student body

Jan 1, 1948

By J. David Lowell

On a low desert ridge six miles south of Cairo lie the remains of the world's earliest known mining town, Maadi of predynastic Egypt. Copper artifacts, including ingots and an ax head which was spoiled in casting, indicate that copper ore was smelted in Maadi, and radio- carbon dating has placed the activity at least as early as 3300 B.C. This is the oldest documented date for the use of smelted copper, the first industrial metal used by man. Copper was mined and smelted almost as early in Asia Minor and on the island of Cyprus, but the greatest development of the budding copper industry was in Egypt, where specific historical records show that about 10,000 tons of copper metal were produced in the period from 1850-1580 B.C. Contrast this production of 35 tons per year with the present world production of about 7 million tpy.

Jan 1, 1970

By H. W. McCue, Henry Rogatz

Oil.—During the year 1939, there were 365 oil wells drilled in the Texas Panhandle, with a total daily initial production of 130,968 bb1.— that is, 69 fewer oil wells drilled than in the previous year, with a decrease. in total daily initial production of 61,738 bbl. The total daily potential of the field on Dec. 5, 1939, as determined by the Texas Railroad Commission, was 1,344,677 bbl., an increase of 94,032 bbl. over the previous year. On Dee. 5, 1939, a daily allowable of 130,527 bbl., which was an

Jan 1, 1940