Search Documents

By A. E. Martin, Gerhard Derge

IE the molecular constitution of molten slags were better known, the nature of chemical reactions in slags and between slags and metals could be better understood and as a consequence might be better controlled. Constitutional information can be obtained by studies on either the molten or the solidified slags. Valuable as the studies on solidified slags admittedly are for many purposes, especially as control methods in steelmaking, they are always of questionable value in giving information on the molecular constitution of liquid slags. However, the characteristics of molten slags such as viscosity, rates of dilfusion, and electrica1 conductivity can be determined experimentally and interpreted along with other knowledge on slag-metal and slag-gas reactions so as to provide direct information on liquid slags. Metallurgists are accustomed to regard reactions in molten slags as involving only neutral molecules, whereas it is quite possible that ionic constituents are actually involved. For example, the dissociation of calcium silicate usually is represented us Ca2SiO4 = 2CaO + SiO2 although a reasonable alternative would be to write Ca2SiO4 = 2Ca+2 + Si04-4 Such ionic dissociation has been suggested frequently without adequate experimental proof. This paper deals especially with electrical conductivity measurements on slags oi the blast-furnace type. These measurements were made to determine whether or not slags are ionized and, if so, to provide a qualitative estimate of the extent of ionization. Electrolysis experiments that indicate the identity of the ions present are also reported. Since the presence of ions has not been considered carefully in modern slag studies, the relevant literature will be reviewed. Review of Literature In 1906 Aikenl obtained a patent for a continuous process of producing iron electrolytically by passing a direct currenl through a bath of FeO.SiO2 to which iron oxide was added periodically to maintain a uniform concentration. The patent also included the addition of CaO and MgO to the bath to lower its melting point. The silicate melts involved were thus in the same system as basic open-hearth slags but with higher FeO and lower CaO contents. Electrical conductivity measurements were made on some molten silicates by Doelter2 in 1907. Natural silicates, such as

Jan 1, 1943

By A. E. Martin, Gerhard Derge

IF the molecular constitution of molten slags were better known, the nature of chemical reactions in slags and between slags and metals could be better understood and as a consequence might be better controlled. Constitutional information can be obtained by studies on either the molten or the solidified slags. Valuable as the studies on solidified slags admittedly are for many purposes, especially as control methods in steelmaking, they are always of questionable value in giving information on the molecular constitution of liquid slags. However, the characteristics of molten slags such as viscosity, rates of diffusion, and electrical conductivity can be determined experimentally and interpreted along with other knowledge on slag-metal and slag-gas reactions so as to provide direct information on liquid slags. Metallurgists are accustomed to regard reactions in molten slags as involving only neutral molecules, whereas it is quite possible that ionic constituents are actually involved. For example, the dissociation of calcium silicate usually is represented as Ca2SiO4 = 2CaO + SiO2 although a reasonable alternative would be to write Ca2SiO4 = 2Ca+2 + Si04-4 Such ionic dissociation has been suggested frequently without adequate experimental proof. This paper deals especially with electrical conductivity measurements on slags of the blast-furnace type. These measurements were made to determine whether or not slags are ionized and, if so, to provide a qualitative estimate of the extent of ionization. Electrolysis experiments that indicate the identity of the ions present are also reported. Since the presence of ions has not been considered carefully in modern slag studies, the relevant literature will be reviewed. REVIEW of LITERATURE In 1906 Aiken1 obtained a patent for a continuous process of producing iron electrolytically by passing a direct current through a bath of FeO-SiO2 to which iron oxide was added periodically to maintain a uniform concentration. The patent also included the addition of CaO and MgO to the bath to lower its melting point. The silicate melts involved were thus in the same system as basic open-hearth slags but with higher FeO and lower CaO contents. Electrical conductivity measurements were made on some molten silicates by Doelter2 in 1907. Natural silicates, such as

Jan 1, 1943

By N. S. Stoloff, J. N. Mushovic

Age hardening response of a Mg-Th-Zr alloy has been studied at temperatures in the range 60° to 450°C. Transmission microscopy revealed clustering of thorium atoms at low aging temperatures, supporting a previous report of GP zone formation. Peak strengthening, which is observed at 325°C, is due to the formation of a coherent, ordered, DO19 type superlattice structure, of Hobable composition Mg3Th, as plates parallel to the matrix prism planes. These plates later reveal a Laves phase structure of composition Mg2Th. The equilibrium Mg4Th phase begins to precipitate in two different forms at an early stage, competitively with the Mg2Th plates. RECENT work on the Mg-Th system indicated that, unlike most magnesium-base alloys, complex precipitation phenomena may be occurring. The partial phase diagram of the Mg-Th system indicates that an equilibrium phase, Mg5Th, is the sole intermediate phase.' sturkey,' however, has reported, using X-ray and electron diffraction techniques, that a metastable fcc Laves phase, Mg2Th, precedes the formation of the equilibrium compound, which he identified as closer in composition to Mg4Th. Murakami et al.3 reported that the equilibrium phase precipitates preferentially on grain boundaries and dislocations in a Mg-1.7 wt pct Th alloy; Kent and Kelly4 aged a more dilute alloy, Mg-0.5 wt pct Th, for 4 days at 220°C and found similar results. In addition, they reported that a platelike phase with a structure close to that of the magnesium matrix forms perpendicular to the basal plane and is probably ordered. Research on a Mg-4 wt pct Th alloy by electrical resistance measurements and transmission electron microscopy has suggested that GP zones may form at low aging temperatures.3 However, the electron micrographs purporting to show this phenomenon were not conclusive. In view of the fragmentary evidence concerning the nature of the precipitation processes in the various Mg-Th alloys, an aging study was undertaken to clarify the characteristics of the various precipitates which form and to correlate the mechanical properties of the system with the direct precipitate-dislocation interactions. The latter results are presented elsewhere.' The purpose of this paper is, therefore, to discuss the precipitation sequence in this system. EXPERIMENTAL PROCEDURE Sheet stock (0.060 and 0.010 in. thick) of a commercial Mg-3.93 wt pct Th-0.42 wt pct Zr alloy (designated HK3lA) similar to that studied by sturkey2 was supplied through the courtesy of Dr. S. L. Couling of Dow Metal Products Co. Zirconium does not enter into any precipitation reactions,' but is present primarily as a grain refiner. The alloy was chill cast, warm rolled to 0.090 in. thick stock, and then finally reduced by a combination of hot and cold rolling. The alloy chemistry is given in Table I. This material was solution treated at 580°C for 4 hr in a dry CO2 atmosphere, and then water quenched. Material in this condition was fairly clear of precipitate particles and was fully recrystallized. Aging at temperatures less than 200°C was accomplished by immersing the alloy in a silicone oil bath; for higher temperatures, aging was done in a salt pot. Age hardening treatments were conducted at 60°, 80°, 105°, 135°, 160°, 250°, 325°, 350°, and 450°C for times ranging from 5 min to 400 hr. Hardness tests were performed on chemically polished 0.060-in.-thick blanks of solution treated material which were aged at the various temperatures for increasing lengths of time. For aging temperatures above 150°C the Rockwell Superficial 30T scale was employed, while samples hardened at temperatures below 150°C were monitored with the 45T scale. Each data point consists of at least three separate readings. Yield stresses also were measured at room temperature on both 0.060 and 0.010 in. sheet specimens aged at 325°C. The aged foils were thinned by the window method in a solution of 80 pct absolute alcohol and 20 pct concentrated perchloric acid (70 pct) maintained at 0°C. A stainless steel cathode was used and the applied voltage was 10 to 15 v. Thinned samples were rinsed in distilled water and pure methanol. After the me-thanol rinse the thin foils were quickly dried between filter paper. Foils prepared by the above method were examined in a Hitachi HU11B electron microscope operating at 100 kv. RESULTS A) Hardness. The hardness data are depicted in Figs. 1 and 2. Peak strengthening occurs at 325°C after aging about 6 min, see Fig. 1. Significant strengthening is achieved also at 350°C, but aging at 450°C produces only softening. The stepped curve at 250°C indicates that a complicated precipitation process may be occurring at that temperature. Fig. 2 suggests that at least two hardening mechanisms exist since the lowest temperature hardness peaks are displaced to the left of the peaks obtained at 135° and 105°C. A great deal of scatter is observed at long times in all cases due to magnesium surface degradation caused by the silicone oil bath. B) Identification of the Strengthening Precipitates. The structure formed atlowagingtemperatures (c10O°C) was not clearly resolvable by transmission microscopy. The only bright-field evidence for a change in structure was a mottled appearance which could be observed at extinction contours, as shown in Fig. 3(a), and the disappearance of this effect when dislocations produced under the influence of the electron beam passed through the matrix, as noted in

Jan 1, 1970

By F. H. Daniels

IN this paper it is my intention to call your attention to a few of the many producers using blast, now in common use in Sweden, and also those constructed by the Washburn & Moèn Manufacturing Company at their Quinsigamond Works. During a prolonged stay in Sweden the writer had an opportunity

Jan 1, 1881

By Reed S. C. Rogers, Robin P. Gardner, Kuruvilla Verghese

The development and use of short-lived radioactive tracer methods for the onstream determination of residence time distributions in large-scale ball mills is described. Tests are reported on a pilot-plant ball mill with 0.43 m diameter and 0.86 m length and on an industrial mill with 1.83 m diameter and 2.74 m length. Tests with different tracer feed sizes indicate that the residence time distributions on both mills are independent of charge particle size. Similar tests are planned for a large ball mill of 4.57 m diameter and 9.30 m length. No safety problems were encountered in these tests and none are anticipated in tests of the larger mill.

Jan 1, 1981

[ ]

Jan 1, 1938

By Ta M. Li

Recent economic and environmental setbacks have not slowed Occidental Oil Shale, Inc.'s program aimed at the commercialization of oil shale. In fact, the firm expects to have a 795 MI (500C) bbl) per day production unit working by the end of 1976. The key to Occidental's ambitious program is an in situ method that extracts the valuable oil by retorting the shale in place. The process will require practically no water and will leave the spent shale in place underground. Additionally, all plant operations are to be located within the mine. These factors thus serve to make the operation attractive from an environmental viewpoint, in contrast to proposed conventional schemes which call for extensive underground mining, crushing and grinding at the surface, and construction of a massive surface retorting facility.

Jan 12, 1976

By R. A. Pasternak, B. Evans

In an ultrahigh-vacuum study of the sorption of nitrogen by niobium* resistivity data for this metal have been obtained as function of temperature and of low nitrogen concentrations. The ultrahigh-vacuum system in which base pressures of about 5 x l0-10

Jan 1, 1965

AN intermetallic compound, Ni3A1, has an ordered fcc structure of type Ll2, and shows peculiar dependence of the yield stress upon temperature; i.e., the yield stress increases by a factor of six upon raising the temperature from 77" to 900K1, 2 This compound is technologically important, since many nickel-base superalloys owe their high-temperature strength to the peculiar yield stress behavior of Ni3Al. The only study of the elastic behavior of this compound was made by Davies and Stoloff,1 who determined Young's modulus of poly crystalline Ni3A1 between 300" and 730°K. The determination of single-crystal elastic constants of Ni3A1 is therefore of interest in connection with dislocation dynamics and is reported in this paper. A single-crystal specimen, 1 by 1 by 3 cm, was cut from an ingot generously supplied by Dr. B. H. Kear of Pratt & Whitney Aircraft. Following initial machining with a Servomet and a surface grinder, the specimen was etched and annealed at 1100°C for 5 hr in vacuum followed by furnace cooling. Two parallel faces were oriented normal to within ±l deg of a [I101 crystallographic axis by the back-reflection Laue technique. The parallel faces were hand-lapped, etched, and polished by the usual metallographic procedures. Final thickness along the [I101 axis was (0.9325 * 0.0005) cm. Chemical analysis gave an average composition of 87.35 pct Ni. Total impurity content is esimated to be no more than 0.1 pct. The elastic constants were calculated from measurements of ultrasonic waves which were propagated along the [110] axis. A longitudinal wave and two shear waves whose displacements are aligned along the [ 110], [li~], and [001] directions, respectively, are necessary in order to completely specify the three elastic constants. Two 3/6-in. quartz transducers were bonded to the parallel faces of the sample with ~ac-seal.3 Although this bond was sensitive to thermal shock, it performed satisfactorily over the entire temperature range for both longitudinal and shear wave propagation. A frequency of 5 mHz was employed in the method of Williams and Lamb4 in order to measure the absolute value of the ultrasonic velocity. The pulse-overlap technique of Mcskimin5 was also used at this frequency in order to determine the shift in the ultrasonic velocity

Jan 1, 1970

By W. Rostoker

A STUDY of the titanium-oxygen system' involved an associated series of measurements of the lattice parameters of the a and TiO phases. The results permit some interesting deductions which are herein reported. A comprehensive survey of the physical PI-operties of the phases in this alloy system has been made by Ehrlich.2 However, only impure titanium was available at that time, so that some revision of his measurements is to be expected. The lattice parameters were calculated from the high angle lines of Debye-Scherrer patterns taken in a 14 cm camera and using filtered CuKa radiation. The specimens were prepared largely by crushing and screening of lump samples which had been quenched from elevated temperatures. Only in the case of low oxygen contents was it necessary to resort to filing and annealing. The results of the lattice parameter studies are graphically presented in Figs. 1 and 2. It will be seen that oxygen produces a pronounced distortion of the c parameter of the a phase (hexagonal close-packed). The trend is in general agreement with Ehrlich's work, although the divergence of actual parameter values strongly suggests that his titanium was very impure. It will be noted that the a phase of titanium can tolerate the unusually high saturation solubility of about 34 atomic pct 0. By virtue of this unique effect, it is possible to make a calculation of the effective atomic diameter of oxygen when dissolved in a lattice with metallic bonding. This has not been possible before. Ehrlich's2 density measurements demonstrated that oxygen occupies interstitial positions in the a lattice and the trend of the lattice parameters would certainly support this. In a hexagonal close-packed unit cell the largest interstitial positions lie at (2/3, 1/3, 1/4) and (2/3, 1/3, 3/4). Accordingly, if both of these positions were occupied, the ratio of titanium to oxygen would be 1:1. The extrapolated c parameter may be taken as between 4.93 and 4.99?. The a parameter appears to reach a constant value of 2.955? at low oxygen contents. The distance of the center of a titanium atom site from the [vc2/16+a2/3-1.448] Then the atomic diameter of the oxygen atom is represented by the function: where the radius of the titanium atom is 1.448A,

Jan 1, 1953

By Alan J. Strauss

The Group IV elements germanium, tin, and lead form nine 1:1 compounds with the Group VI elements sulfur, selenium, and tellurium. This paper reviews the properties of the pseudobinary solid solutions formed by these compounds, including the extent of mutual solid solubility, temperature-composition phase diagrams, transport properties, deviations from stoichiometry, optical properties, and energy band structure. Particular emphasis is placed on the Pbl-xSnxTe and Pb1-xSn,Se alloys with rocksalt structure, because of current interest in these malerials for generating and detecting infrared ,radiation. ThE Group IV elements germanium, tin, and lead form nine 1:1 compounds with the Group VI elements sulfur, selenium, and tellurium. Some of the physical and electronic properties of these compounds, including their melting points1-8 and energy gaps,4'9-12 are listed in Table I. Four compounds (SnTe, PbS, PbSe, and PbTe) have the cubic rocksalt (Bl) structure. At room temperature GeTe has a rhombohedra1 structure closely related to the B1 structure, into which it is transformed at about 400°C. Four compounds (GeS, GeSe, SnS, and SnSe) have the orthorhombic B29 structure. In samples which have not been intentionally doped with impurities, the electrical conductivity is due primarily to electrons or holes produced by the ionization of donor or acceptor lattice defects associated with deviations from stoichiometry. Undoped samples of PbS, PbSe, and PbTe may be either n type or p type, depending on whether they contain excess lead or an excess of the Group VI element, respectively, but only p-type samples of the other compounds have been reported. This paper will review the properties of the pseudo-binary solid solutions formed by the nine 1:l compounds. The topics to be considered include the extent of mutual solid solubility, temperature-composition phase diagrams, transport properties, deviations from stoichiometry, optical properties, and band structure. Particular emphasis will be placed on the Pb]-xSnxTe and Pbl-xSnxSe alloys with B1 structure, which are promising materials for generating and detecting infrared radiation in the 8 to 14 µm atmospheric window and beyond. MUTUAL SOLID SOLUBILITY The extent of mutual solid solubility in the pseudo-binary systems has been investigated for fourteen of the eighteen ternary systems (in which the two terminal compounds have a common element) and for nine of the eighteen quaternary systems. In most cases, X-ray diffraction measurements made at room temperature were used to determine the structure and lattice parameter(s) of the phase(s) present in samples of various compositions prepared by freezing from the melt. In many investigations, including the extensive studies of Krebs and co-workers,13'14 the samples were annealed at elevated temperatures before X-ray measurements were made. In some cases, metallographic examination and thermal analysis have also been employed. The results for the ternary and quaternary systems are summarized in Tables II and III, respectively. (The original references should be consulted for the annealing temperatures.) The solubility of one compound in the other is at least 5 mol pct in all cases, and is often much larger. Complete solid solubility has been observed in all systems so far investigated in which the terminal compounds have the same structure, although in the PbS-PbTe system complete solubility is limited to elevated temperatures. Thus complete solid solubility occurs in five systems where both compounds have the B1 structure (SnTe-PbTe, PbS-PbSe, PbS-PbTe at temperatures above 805°C, PbSe-PbTe, and SnTe-PbSe) and in three where both compounds have the B29 structure (GeS-SnS. GeSe-~n~e-, and SnS-SnSe), as well as in two involving GeTe and a compound with B1 structure (GeTe-SnTe and GeTe-PbTe). On the basis of thermal analysis data, complete solid solubility at sufficiently high temperatures has also been reported for the GeSe-GeTe2 and SnS- pbS22 systems. This seems unlikely, however,

Jan 1, 1969

By R. E. Hook, H. J. Garrett, A. M. Adair

X-ray diffraction and metallographic techniques were employed to examine the impurity phases occurring in as-swaged and recrystallized chromium produced fvom high-purity iodide chromium crystals. Chromium oxides are found to form in a consistent manner associated with the temperature of recrystallization. Microscopically observable second phase particles of Cr203 are observed to form intergranulurly beginning at 1300T. Beginning at 1500°C. Cr30, is formed intergvanulurly, atzd at 1600°C and above Cr30, is also formed in association with migrating grain boundaries. Geometrical traces formed by particles of this high temperature oxide uithin the grains rez)eal the histmy of grain boundary motion. X-ray evidence is presented which suggests the existence of a high temperature form of Cr203. Other impurity phases in addition to the oxides of chromium are also present. THE partitioning Of impurity elements between grain boundary aid lattice sires, either as solutes in solution or as second phases, may exercise an important influence on the mechanical behavior of metals and alloy systems. This partitioning of impurities could have a direct bearing on the iecrys-

Jan 1, 1963

By E. J. Hall

(Butte Meeting, August, 1913.) THE iron-nail method of assaying has been used for a number of years, but has not met with the approval of all assayers. The method possesses advantages which may be given as follows : (1) no preliminary treatment is required ; (2) a lead button of proper size can be obtained (3) it is economical. On, the other hand, it has its disadvantages, which may be summed up as follows: (1) it is not applicable to ores containing large amounts of impurities other than sulphur, as practically all the base metals will contaminate the lead button ; (2) the slag is unsatisfactory in the larger number of fusions; (3) the method was known to give low silver results under certain conditions and the gold results were questionable. It was with the idea of determining the extent of this latter disadvantage that the following investigation was undertaken. It is well known that the fusion obtained in the lend assay is far more satisfactory than that in the " nails method " for gold and silver. The principal difference in the charges as a class is the presence of considerable reducing agent in the lead charge, and a limited oxidizing action in the nails charge, due to PbO. The possibility of improving the nails fusion by simulating the lead charge was the reason for using argol in some tests, even though there were reasons for expecting this would have -au objectionable effect on the results.

Jan 6, 1913

Jan 1, 1934

By W. G. Fischer, S. R. Felde

Trona ore at the Westvaco, Wyo., mine of FMC Corp. has been obtained by room-and-pillar methods since the mine began operation. The flat- lying, 10-ft thick trona (Na2CO3.NaHCO3.2H2O) is covered by 1500 ft of weak shale and sandstone, and extraction of pillars on the retreat quite often throws large amounts of weight onto development workings. Weak shales in the roof and floor fail rapidly, and the mine ribs slough to such an extent that mining often becomes very difficult. When this occurs, efficiency goes down, costs go up, and the risk to men and machinery increases greatly. Difficult mining conditions in the early '60s forced a re-evaluation of all presently known mining techniques in bedded deposits. Many room-and-pillar mining plans were compared with the system in use at that time, but none of them offered a better solution to the roof control problem. Longwall techniques were also seriously considered, but machinery was not available that would cut the hard trona seam and still maintain the productivity obtained from room-and-pillar sections. However, since roof control in the longwall methods appeared to be more satisfactory than that found in room-and-pillar techniques it was believed that a new technique using the longwall principle and based on rock mechanics should be tried rather than previously known pillaring methods.

Jan 4, 1966

By N. A. D. Parlee, I. D. Shah

THIS communication reports the results of some work done on the effect of gold, palladium, and platinum on the liquid-gas-solid equilibrium in the Ag-O system,1,2 see Fig. 1. Recently several investigators3, 4, 5 have reported the effects of gold, palladium, platinum, and copper on the solubility of oxygen in liquid silver. This communication represents only a portion of the work done here on the solubility of oxygen in liquid silver and liquid Ag-Au, Ag-Pd, and Ag-Pt alloyss—the greater part having already been reprted. The apparatus, materials, and procedures used were similar to those of earlier work.' l The main precautions observed in obtaining these freezing points at constant temperature and PO2 = 1 atm were as follows: 1) The points were approached very slowly from higher temperatures. 2) In the very near vicinity of the L-G-S equilibrium point precautions were taken to see that the melt was in equilibrium with oxygen at one atm. Equilibrium was considered to have been attained when no more absorption of oxygen was observed in the last 15 min at a fixed temperature. 3) In the case of these alloys, the freezing point of the melt at 1 atm of oxygen and the equilibrium amount of oxygen absorbed by the liquid "infinitesimally" above this point were determined by lowering the temperature in very, very small steps, equilibrating at

Jan 1, 1969

F. E. BASH, Philadelphia, Pa.-In order to make a definite check on the emissivity of crucible steel under works conditions, a test was planned and executed by the plant of the Midvale Steel Co., by a Sub-committee, as follows: Five crucibles were put in a crucible furnace with-the normal charge and were treated in the same manner as a number of others that were charged at the same time; the only difference was that the five cur-cibles had lids with.2-in. holes in the center. It was thought that after the crucibles were removed from the furnace a reading could be made through the hole in the lid with the optical pyrometer and that such a reading would give the true temperature of the steel as black-body con-ditions should prevail inside the crucible. If after obtaining the true temperature, the crucible lid were removed and the steel poured into the ladle, the apparent temperature could be taken by sighting on the steel stream and the emissivity obtained from the two temperature values. Such a test was carried out with five crucibles. About a third of the crucibles charged into the furnace with the five experimental ones were first drawn from the furnace and poured into the ladle. The experimental crucibles were then drawn and readings of the true temperature were made

Jan 12, 1919

By Pol Duwez

IN the course of an investigation of the V-CO system, two intermediate phases were found. One of these phases corresponds approximately to the stoichiometric composition VCo and is isomorphous with the sigma phase in the Fe-Cr system.' The second phase has the composition V3Co; its crystal structure is described in the present note. The alloys were prepared by mixing the two metals in the powder form, pressing a small disk weighing about 5 g at 80,000 psi, and arc melting this disk on a water-cooled copper plate in an atmosphere of pure helium. The details of this technique have been described.' The vanadium powder was obtained from Westinghouse Electric Corp., Bloomfield, N. J. This powder is probably of very high purity, since when it is properly sintered or melted in the above-mentioned arc furnace, ductile specimens are obtained. The cobalt powder, from Charles Hardy, Inc., New York, contained 0.5 pct Ni, 0.1 pct Cr, and traces of Si and Fe. After melting, the V,Co samples were sealed in evacuated quartz tubes and homogenized for ten days at 800°C. Powder diffraction patterns were obtained with a 14.32 cm diam camera, using Ka copper radiation. The patterns were readily indexed on the basis of a primitive cubic lattice with a parameter equal to 4.675A. The density, determined by the immersion method, was 6.71 g per cu cm; hence the number of molecules per unit cell is approximately 1.95; i.e., 2. At this point, the possibility that the structure might be that of beta tungstena became apparent. The beta tungsten structure is described as follows: Space group 03,, — Pm3n 2 Co in (a) : 000; ?4lhYZ (hhl) reflection present only if 1 = 2n. Assuming this structure to be the correct one, intensities were computed by means of the usual eauation: 1 + cos220 I oc p F sin 0 cos 6 where F is the structure factor, 0 the Bragg angle, and p the multiplicity factor. The observed and calculated values of sin 0 and the intensities are given in Table I. The agreement between the observed and the calculated sin 0 is good and there are no flagrant discrepancies between the calculated intensities and those estimated visually. The (hhl) reflections for which 1 is odd are not observed, as required by the space group. In addition, the (410), (430), and (531) reflections are missing as expected, because of the special (a) and (c) positions in0%. However, six reflections—(llo), (220), (310), (411), (422), and (510)—which have very weak computed intensities were not observed. For these reflections, the structure factor is proportional to the difference between the scattering factors of the two atoms in the structure. Since the scattering factors of vanadium and cobalt are not very different, these reflections are weak. However, by using Ka chromium radiation, whose wavelength is just above the absorption edge of vanadium, the effective scattering factor of vanadium may be decreased by one or two units; consequently the difference between the cobalt and vanadium scattering factors is increased. It was, indeed, found that in a powder pattern taken with chromium Ka radiation, the three reflections (110), (220), and (310) were actually present. The three other reflections (411), (422), and (510), with spacings smaller than half the wavelength of chromium Ka, were obviously not obtainable with chromium radiation. All the experimental results appear to confirm the beta tungsten structure for V,Co. In this structure, each cobalt atom is surrounded by twelve vanadium atoms at 2.61A; each vanadium atom is surrounded by two vanadium atoms at 2.34A, four cobalt atoms at 2.61 A, and eight vanadium atoms at 2.86A. Acknowledgment This work was done at the Jet Propulsion Laboratory, California Institute of Technology, under contract number W-04-200-ORD-455 with the Army Ordnance Department, Washington, D. C. The author wishes to thank this agency for the permission to publish the results of this investigation. References 'P. Duwez and S. R. Baen: X-Ray Study of the Sigma Phase in Various Alloy Systems. Symposium on the Nature, Occurrence, and Effect of Sigma Phase. ASTM Special Tech. Pub. No. 110, pp. 48-54. Philadelphia, 1951. 2 C. H. Schramm, P. Gordon, and A. R. Kaufmann: The Alloy Systems Uranium-Tungsten, Uranium-Tantalum, and Tungsten-Tantalum. Trans. AIME (1950) 188, pp. 195-204; Journal of Metals (January 1950). 3 M. C. Neuburger: The Crystal Structure and Lattice Constants of Alpha and Beta Tungsten. Ztsch. fiir Krist. (1933) 85, pp. 232-237.

Jan 1, 1952

By J. J. Arps

This paper is a study of the effect of temperature on the electrical resistivity of sodium chloride solutions based on the published resistivity and density data in the International Critical Tables. This temperature effect is of considerable importance in quantitative interpretation of electric logs, where it is frequently necessary to correct mud resistivities measured under surface conditions to temperatures existing at the bottom of the bore hole. An empirical approximation formula was developed for this conversion which has proved to be very useful and seems to provide results well within the range of accuracy of the data involved. This approximation formula states: sistivities of sodium chloride solutions at temperatures of t and t degrees Fahrenheit, respectively. INTRODUCTION Research by various investigators during the past 20 years has clarified the physical principles of the phenomena which cause the natural or spontaneous electric potential in rotary drilled bore holes. The basic relationship which is most commonly used reads: in which the SP deflection, as measured from the shale base line, is expressed in millivolts. K is a constant, which appears to vary between 50 and 110; the low value applying to shaly sands, whereas the higher values are more common in carbonate rocks. A good average value for K = 70. for which value there is considerable theoretical justification." In order to calculate the resistivity of the connate water R and to estimate its "equivalent salinity" (as NaCl) from an electric log by means of this SP relationship from a knowledge of the static self potential and of the resistiv- ity of the mud filtrate R it is necessary to first correct the resistivity of the mud filtrate measured under surface conditions to the resistivity of this same mud filtrate in the well bore at a different temperature. In order to make this temperature conversion for the mud filtrate the variation of the electrical resistivity of sodium chloride solutions with temperature is commonly used. Since some discrepancies were found in the charts ordinarily used for this purpose, it was felt desirable to make a new study of this relationship based on the published measurement data. Because of the fundamental nature of these relationships and as an aid to other workers in this field, an attempt has been made in this study to show every step in the calculations. CONDUCTIVITY VS MOL CONCENTRATION The most complete published reference on the temperature relationship of sodium chloride solutions of different concentrations is provided in the International Critical Tables.' The basic measurement data on the electrical conductivity of aqueous sodium chloride solutions, at different temperatures, as given in these tables, are reproduced in Table 1. The electrical conductivity values in this Table 1 are expressed as 10' times the specific conductivity k in ohm-'cm'l per unit of concentration in milligram mols per liter of solution C, or: RESISTIVITY VS MOL CONCENTRATION These conductivity values from Table 1 were first converted to the corresponding electrical resistivity values (R) , expressed in ohm-meters, as is conven-

Jan 1, 1953

By O. B. Buchlen, J. W. Smith

The Coal Research Bureau of the School of Mines at West Virginia University, using an experimental flotation cell designated an airlift-cyclone was able to obtain a clean coal product containing 7.64% ash with 94% yield and 97% coal recovery. This favorable performance was obtained with the experimental flotation cell operating as a simulated three-stage unit on slurry taken from the fine coal circuit of a coal preparation plant. This experimental device, consisting of a sheet metal cyclone-like unit mounted on a U-shaped uplift pipe, uses a combined flotation and cyclone action to beneficiate the minus 14 mesh partially cleaned feed product. In addition to providing comparable analytical results, the airlift-cyclone possesses other attractive features among them being a low capital expenditure, utilization of moderate plant floor space, efficient operation on high density feed slurry, and absence of moving parts. The primary shortcoming of the experimental cell is its limited capacity. The Coal Research Bureau presently has under construction a larger unit which, it is hoped, will provide the capacity and quality to establish the airlift-cyclone as a commercially feasible unit. Froth flotation of fine coal is a practice which has only recently gained wide acceptance in this country. Various explanations can be put forth for this delayed acceptance of a very selective and efficient system of coal preparation. Among these reasons would be the advent of continuous mining machines resulting in the increased production of coal fines, the change in market patterns from domestic and rail consumers who did not want fines to a predominantly utility market which normally consumes fines, and also the imposition of legal restrictions in regard to stream pollution. However, the major detriment is probably the high cost involved both in installation and operation of the flo- tation unit and auxiliary systems. These facts assume greater emphasis when considering that froth flotation installations normally process a low quality feed product. A recent estimate' of installation costs including dryers, filters, and other auxiliary equipment for a flotation system was $5000 to $7000 per ton of capacity while the operating costs, exclusive of auxiliary equipment, were estimated at 10 to 306 per ton of feed. The Coal Research Bureau of the School of Mines at West Virginia University is currently developing a simplified froth flotation cell, designated an airlift-cyclone, which may provide considerable savings in capital and operating costs without sacrificing product quality or recovery. This experimental cell consists of three primary components: 1) a vertically mounted U-shaped pipe; 2) an air injector device; and 3) an integrally mounted cyclone-like unit (Fig. 1). A feed slurry is introduced at the top of one leg of the U-pipe while compressed air is injected near the base of the other leg. The air serves both to aerate the pulp and to cause it to flow upward into the base of the cyclone unit where the floated clean coal is separated from the reject material and unfloated coal which remains in slurry. The Coal Research Bureau's experimental airlift-cyclone is somewhat similar in principle to a flotation device developed by Russian engineers in the late 1950's. In tests upon a two-stage pilot-size device, the Russians obtained very favorable cleaning efficiencies.' However, later experience with production models demonstrated that rated capacities and acceptable product quality could not always be maintained.3 Because of these limitations, Russian engineers subsequently recommended that conventional, mechanical cells be used when cleaning difficult to float slurries. Engineers at the Coal Research Bureau felt that such a device utilizing the combined actions of a cyclone and a froth flotation machine offered numerous attractive features and merited investigation. Accordingly, a small capacity experimental airlift-cyclone was designed and, with the permission of the Christopher Coal Company Div. of Consolidation Coal Co., installed in Christopher's Humphrey preparation plant near Morgantown, West Virginia.

Jan 1, 1964