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Jan 1, 1958

CARACAS PETROLEUM Established February 24, 1957 Meets second Tuesday monthly W F Shelton, Chairman Homer N Mead, First Vice-Chairman Jose G Paez, Second Vice-Chairman T A Moore, Treasurer E A Moore, Secretary Cia Shell de Venezuela Apartado 809 Caracas. Venezuela

Jan 1, 1958

By C. S. Brooks

Several of the commonly used methods for deter-mination of effective grain densities of minerals have been evaluated for accuracy and precision, and their applicability to various types of petroleum reservoir minerals tested. Consideration was given to the effect of consolidation, swelling clay, and wettability on these grain-density determinations. Procedures with helium displacement, a modified low-pressure Boyle's law porosimeter, and liquid displacement (water, n-decane, and n-octanol) were tested. The helium-displacement procedure was used primarily as an independent reference for which the effects of fluid-solid interaction, e.g., adsorption and wettability, were negligible. The procedures with the Boyle's law porosimeter and with liquid displacement are the methods in common use. Minerals investigated included calcite, West Texas limestone core samples, California sandstone core samples, and Wyoming bentonite. The number of samples tested, while not large, was adequate to permit application of statistical methods. Grain-density measurements on calcite (Iceland spar) provided a basis of comparison for the accuracy and precision of the procedures under investigation for a material with a high degree of chemical and physical homogeneity and for which fluid-solid interactions were at a minimum. Liquid-displacement procedures (water or n-decane) provided the greatest reliability and precision for measurement of the grain densities of the limestone tested. Gas-displacement procedures (helium or Boyle's law porosimeter) provided the greatest reliability and experimental convenience, if not the greatest precision, for the measurement of the grain densities of the swell- ing clay, Wyoming bentonite, and the shah sandstones which -contained appreciable amounts of swelling, in-terstitial clays. These experiments were designed to evaluate the applicability of the grain-density procedures in common we to some of the less tractable minerals—tight limestones, shaly sandstones, and swelling clays. The results should provide a useful basis for a selection of the method most suitable for application to the various petroleum reservoir minerals encountered and especially for use in the estimation of formation porosity. INTRODUCTION These experiments were undertaken to evaluate the accuracy and precision of several commonly used methods for determination of effective grain densities of minerals, and to test their applicability to various types of petroleum reservoir minerals. Consideration was also given to the effect of consolidation, clay, and wettability on these grain-density determinations. Procedures used included measurements with helium displacement, with a modified low-pressure Boyle's law porosimeter, and with liquid displacement (water, n-decane, and n-octanol). The minerals investigated included calcite, West Texas limestone core samples, California sandstone core samples, and Wyoming bentonite. The accurate determination of the porosity of petroleum reservoir formations, in particular those of low porosity, has received much attention. Both bulk-volume and grain-volume measurements necessary in the evaluation of porosity have been examined by many investigators with the objectives of improving both the accuracy and the precision of these determinations. In this investigation statistical criteria for selection of the most reliable and suitable procedure for use with a given type of mineral are demonstrated. The grain-volume measurement procedures appear to be the most susceptible to improvement.

Jan 1, 1958

By J. L. Dumanoir, Maurice Martin

The induction-electrical log is a combination of a SP curve, a short normal curve, and an induction log; all three logs being recorded simultaneously in a single run. The spacing of the short normal is 16 in. The induction log is designated as 5FF40, which means that the sonde involves five coils and a focusing system, and that the distance between the main coils is 40 in. Examples of induction-electrical logs are shown in Figs. 13 and 15. The right-hand track contains the induction conductivity curve. The scale of this curve is linear with the units of conductivity, i.e., mhos/m or millimhos/m (mmhos/m), increasing from right to left. The same curve can be read in the reverse direction as a resistivity log, with a hyperbolic scale. In the middle track, the solid curve represents the short normal. (An amplified short normal is also shown in Fig. 15). The dotted curve is the resistivity curve of the induction log, i.e., the reciprocal of the conductivity curve, recorded with the same linear scale as the short normal. The SP is in the left-hand track. In this combination, the SP curve and the 16-in. normal are the essential correlation curves, as in the conventional electrical log. The induction log provides a more accurate and detailed record of formation boundaries than the conventional log, especially in hard rock territories. Furthermore, the induction-electrical log makes possible the determination of fluid content, particularly in thin beds—at least qualitatively and very often quantitatively. In such thin beds, because of the adverse effect of the adjacent formations, the responses of the conventional devices are generally doubtful and/or incom-plete. Another advantage of the new combination is that the induction log is little affected by the presence of thin hard streaks interbedded within the permeable sections, whereas such occurrences are the cause of serious distortions of the long normal and lateral curves. The evaluation of saturation from any resistivity log implies the knowledge of the true resistivity R, of the bed and of the resistivity R.. of the flushed zone, or at least of the ratio Rxo/Rc. With the induction-electrical log run in fresh mud, the 16-in. nor-mal has a smaller radius of investigation than the induction log, so that the former reads closer to R.. and the latter closer to Rt. Thus, it has been observed that the ratio of the 16-in. normal to the induction log readings can be used as a basis for the interpretation in terms of saturation, with the help of appropriate charts. The purpose of the present paper is essentially to explain this procedure and to provide the corresponding charts. On the other hand, when a formation is deeply invaded, the response of any log (in particular the induction log) depends upon the radial distribution of formation resistivities behind the wall of the hole, which itself is a function of the arrangement of the fluids saturating the formation pore spaces. This paper, accordingly, will begin with a schematic description of the distribution of fluids and resistivities in the invaded zone. Next, some essential characteristics of the induction log will be reviewed. Finally, the determination of the interpretation charts and their application will be explained. The discussion will be confined to the case of fresh muds, i.e., muds whose resistivity is at least five times as great as that of the formation waters. With the present equipment the induction log is not well adapted for logging in salty mud. The Laterolog and guard electrode log are at their best under conditions of low resistivity mud. Accordingly, when these tools were introduced a few years ago, the use of salty mud was recommended. Now, with the introduction of induction logging, spe-

Jan 1, 1958

By A. Schild

The effect of heating a producing well on the rate of oil recovery has been analyzed in the simple case of a well producing oil by a radial drive and in the steady state. Differences of production rates with and without borehole heating have been calculated and plotted; these measure some of the benefits of the thermal recovery process. A striking feature is that the production increase tends rapidly to a constant value for large production rates. Some concrete examples, including a rough comparison with field data. are discussed. Heating requirements have been calculated and plotted on the assumption that the heaters used are 100 per cent efficient. Heating has been thought of as applying only to low volume wells producing heavy oils. However, the calculations suggest that the thermal process considered might be profitable even for some wells producing large quantities of light oil, especially in unconsolidated formations where fracturing is not possible. In the case of wells producing other fluids with the oil or of wells producing partly or wholly by gravity drainage, the theory developed does not apply in detail. It can be expected, however, that any general qualitative be-havior will remain valid. Under normal temperature conditions, high viscosity emulsions sometimes form around the wellbore, lowering the permeability in the vicinity of the well and impeding the production of oil. Borehole heating often prevents such emulsification. This important effect is not easily amenable to mathematical analysis and has not been included in the theory presented here. It should therefore be kept in mind that the benefits due to borehole heating may in fact exceed the values given by the following calculations. INTRODUCTION The recovery of viscous, low gravity oils can often be stimulated by applying heat to the production zone. The higher temperature lowers the viscosity of the oil, increasing its mobility, and therefore its rate of production. One thermal method of recovery 1,2,3,4. consists in operating a heater inside a producing well and, at the same time, producing oil from the well. In this paper a simple theoretical model is analyzed to study the effect of such heating on the recovery of oil. The reservoir mechanics of the process is the only aspect of the problem which is considered here. The details of the heating system are ignored, and it is simply assumed that the heater raises the temperature in the immediate vicinity of the producing well to a pre-assigned temperature T w. Although heating requirements are calculated, these refer only to the heat supplied to the formation and to the oil being produced; they do not include heat losses due to the inefficiency of the heater. A short outline of the theory follows: The heat supplied to the producing well flows out into the formation by means of thermal conduction. At the same time, the flow of oil carries heat by convection from the formation towards the producing well. After sufficient time has elapsed, a steady-state is reached where the temperature, the velocity of the oil, etc., no longer vary with time but are functions of position only. In the steady state the temperature decays like an inverse power from the high value Tw at the wellbore to the original reservoir temperature T. at some distance away from the well. The effect of the high temperature and low oil viscosity near the producing well is the same as if the oil were produced at reservoir temperature To but through a producing well of a larger radius. From this point of view, the energy and money being expended to provide heat

Jan 1, 1958

By Kichizo Niwa, Toshio Yokokawa, Mitsuo Shimoji, Yoshihiko Watanabe, Satoshi Kado

A LTHOUGH a systematic research on diffusion in liquid metals has not been carried out, partial studies have been developed by various workers in several systems. A few recent papers among them have shown that this line of approach is quite useful for understanding the structure of the liquid state. Furthermore, it has been found in kinetic

Jan 1, 1958

University of Alabama-University, Alabama, Mining and Metallurgical Society, William L Mason University of Alaska-College, Alaska, Mining Society of the University of Alaska, Doug¬las W Huber University of Arizona-Tucson, Arizona, Miners Society, S L Smith University of California-Berkeley, California, Mineral Technology Association, Jack Washburn Carnegie Institute of Technology-Pittsburgh, Pennsylvania, The Metals Club, Gerhard Derge Case Institute of Technology-Cleveland, Ohio, Case Metallurgical Engineering Society, Robert F Hehemann

Jan 1, 1958

Jan 1, 1958

By L. D. Mullins, H. B. Bradley

Numerous articles have appeared in the literature citing the application of the potentiometric analyzer to cycling operations. Specific information obtainable by a potentiometric analysis, as noted by various investigators, includes: 1. Pattern sweep efficiency for various injection and production rate programs. 2. Injected fluid breakthrough time at production wells. 3. Optimum production and injection rates. 4. Prediction of injection and/or production well locations. 5. History of advance of the in-jected-produced fluid interface. 6. Ultimate life of the reservoir. 7. Ultimate reservoir production. This note describes a procedure for predicting pressure distribution in a gas-condensate reservoir by using the potentiometric analyzer to obtain potential distribution data on an analog model of the reservoir and then applying Muskat's' equations. The method relates the volumetric weighted average datum pressure to the mean potential in the model.

Jan 1, 1958

Jan 1, 1958

By E. J. Whittenberger

OVER the past two decades, the Cr-Ni stainless steels, popularly termed 18-8 steels, have been used in ever increasing amounts in the aircraft, automotive, chemical, transportation, and building industries.' The contribution of nickel to these steels is associated with its strong austenite forming tendencies which assure good hot and cold forming characteristics, and with its beneficial influence upon corrosion resistance, especially in oxidizing acids. The adjustment of the chromium and nickel contents has been used advantageously in controlling the rollability and the response of the mechanical properties of these steels to cold reduction. With the advent of the jet age and the government stockpiling of nickel, considerable emphasis has been placed upon the development of satisfactory low nickel or nickel-free substitute austenitic stainless steels, especially for nonmilitary applications.2 Fer-ritic 17 pct Cr (AISI Type 430) stainless steel has been effectively substituted for the austenitic grades in applications with mildly corrosive exposure. However, the limited formability and ferromagnetic behavior of this grade do not permit its satisfactory use for many applications. To achieve better formability in a nenmagnetic steel and conserve nickel, a number of low nickel substitute austenitic grades of stainless steel have been developed in recent years. In most of these steels, manganese and nitrogen have been substituted for a portion of the nickel content, for example, 17 pct Cr-4 pct Ni-6 pct Mn (AISI Type 201), 18 pct Cr-5 pct Ni-8 pct Mn (AISI Type 202), and 16 pct Cr-1 pct Ni-17 pct Mn, all of which contain approximately 0.15 pct N.1 The precipitation of ferrite when large ingots of these Cr-Ni-Mn-N steels are heated to temperatures high enough for conversion to slabs on conventional universal slabbing mills has seriously affected the hot workability of these steels. This has been especially true in the case of the 16 pct Cr-1 pct Ni-17 pct Mn (sometimes referred to as 15 pct Cr-1 pct Ni-15 pct Mn) composition." Because it is possible that little, if any, nickel will be available for nonmilitary stainless steel applications in the event of a national emergency, a need has existed for a nickel-free austenitic stainless steel containing hot and cold forming characteristics similar to 18-8 steels and corrosion resistance at least comparable to the 17 pct Cr ferritic steel. The aforementioned deleterious effect of ferrite upon the hot working characteristics of the 16 pct Cr-1 pct Ni-17 pct Mn, steel indicates the importance of establishing the austenite-austenite plus ferrite phase boundaries as the first step in the development of nickel-free or low nickel substitute steels. This paper presents the data collected in an elevated temperature constitutional study of the Cr-Ni-Mn-N system at the South Works of the United States Steel Corp. Experimental Procedure The 300 compositions used in the investigation were melted in a 26 Ib induction furnace and cast in 3 14 in. diam by 18 in tall hot-tcpped ingot mo1ds.

Jan 1, 1958

By P. D. Southgate

VIBRATION, both ultrasonic and sonic, can affect the course of a variety of metallurgical processes. Reports of work on this subject have appeared at intervals over the last twenty years and a thorough review has been made by Hiedemann,' who gives a full list of references. It has been established that both refinement of structure and outgassing of the melt can be produced in most metals with sufficiently intense vibration. Many of the experiments in this field have been carried out using alloys of direct commercial interest in production- type casting equipment. Here a different approach is adopted, and simple binary alloys which exhibit different types of structure are used to facilitate examination of the effects produced under well-controlled conditions. Results from this kind of experiment should enable the basis of larger scale experiments with similar types of materials to be better substantiated. The alloys selected for this work are: 1) aluminum of 99.2 pct purity, the principal impurity being iron, near 0.4 pct; 2) A1-1.8 pct Fe, which is near eutectic composition; 3) A1-4 pct Fe—the second phase, of composition FeAl3, forms distinct acicular crystals; and 4) A1-12 pct Si—although this is of eutectic composition, the silicon normally appears in the form of large plates. Experimental Method There are three practicable methods by which acoustic vibration can be transferred to liquid metals: a) vibration of the whole of the container; b) electromagnetic induction; and c) insertion of a vibrating probe into the liquid. Method c is chosen here, and a frequency of 8 kc per sec is used. The end of the probe is electrically heated so that the metal near it will be the last to solidify. This ensures that vibration is transmitted directly to the liquid metal without passing through any solidifying and pasty intermediate region, which would attenuate acoustic waves severely. In addition, the heating prevents solid metal adhering to the probe, with consequent detuning. The transducer assembly is shown in Fig. 1. A stack of Permendur laminations 30 cm long acts as a half-wave vibrator and a winding along its length carries polarizing and energizing currents. It is joined by a half-wave coupling bar to a mild steel exponential horn, which tapers from 3.8 to 1.1 cm diam. A stainless steel stub 3 cm in length is welded on the free end. The assembly is supported by a plate located at the node of the coupling bar. Acoustic radiation losses are minimized by allowing the free end of the transducer to protrude above the surface of the cooling water. The exponential horn serves the function of matching the acoustic output impedance of the transducer to the radiation resistance of the probe into the melt. Electrical drive is provided by a 1 kw generator. Measurements of probe vibration amplitude during melt treatment are obtained from a gramophone pick-up with the needle attached to the wide end of the horn. This device is calibrated with a microscope before use. Liquid aluminum is very actively erosive and solution of materials with which the molten metal comes into contactcauses difficulties. Erosion of the probes in particular can be severe since it is greatly accelerated by the vibration. Tests of various acous-

Jan 1, 1958

By R. W. Braund

THE Tracy mine is within the corporate limits of Negaunee, Mich. The tract of land comprising the Tracy group lies on the east end of the Marquette Iron Range between adjoining mined-out properties on the north and south. Since acquiring the Tracy lands in 1921, Jones & Laughlin Steel Corp. has completed about 115,- 000 ft of surface diamond drilling, partially outlining five orebodies. Now that mining has started, one or more underground drills are in constant operation to obtain information that will aid mine development planning. Some 20,000 ft of underground drilling have been completed to date.

Jan 1, 1958

ALASKA Established November 19, 1947 Meets fourth Monday monthly except June through August Term of office ends October Peter O Sandvik, Chairman Denny G Breaid, Vice-Chairman Douglas W Huber, Secretary-Treasurer School of Mines University of Alaska P O Box 337 College, Alaska

Jan 1, 1958

By Edward B. Walker, Michel Grosmangin

The geological and economic conditions peculiar to the Greater Oficina area are presented to demonstrate the necessity of a low-cost, well-site method of distinguishing gas-bearing formations. The method of gas detection with the neutron log is briefly discussed and its limitations are explained. A new method is described which consists in running a second neutron log with a larger source-to-detector spacing. Field data indicate that under favorable conditions the larger spacing response is proportionately more influenced by the virgin gas zone than is the shorter spacing response. One important condition is that the gas sands be invaded, with a diameter of invasion equal to about two to three times the hole diameter. The calibration of the longer spacing log is made so that the two logs read the same deflection in shale and in a known water or oil sand. Under such conditions, gas is indicated by a positive separation, i.e., the curve for the longer device is displaced to the right of the curve for the shorter device. Because of the non-linearity of the long spacing response, low porosity formations also show positive separations. In sands with large porosity variations, the gas sands can no longer he located visually. They can be detected on a plot of shorter spacing vs longer spac-ing deflections. INTRODUCTION In the Greater Oficina area of Eastern Venezuela, the rapid and accurate detection of gas from well logs is of primary importance because of a combination of economic, geologic, and operational conditions. Briefly, these conditions are: economic—there is no market for gas at the present time; geologic—a single well may contain as many as 30 or more oil or gas sands for which intervals -to be tested must be selected; opera-tional—first, once opened to the casing through perforations, gas sands are extremely difficult and expensive to squeeze off, and second, gas detection must be rapid because the geologist must decide immediately, at the well, which sand to perforate. During the early period of exploitation in Greater Ofi-cina, when clay base muds were used, sidewall samples, together with electric logs, gave fairly good distinction between oil and gas sands. When exploitation became concentrated on deep fields of poorer sidewall sample recovery, and after the advent of oil emulsion muds, now the standard drilling fluid in Greater Oficina, the regular neutron log became the most reliable indicator of gas. In 1953, R. Norelius devised the dual-spacing neutron technique for gas detection. The dual-spacing neutron log has proved to be highly successful in detecting gas and has been adopted as a regular survey by all of the oil companies of the area. Several hundred dual-spacing neutron logs have been run in Eastern Venezuela and several tests per well are available for positive evaluation of the logs. The findings outlined below are based upon this extensive field experience. GEOLOGICAL CONDITIONS OF THE GREATER OFICINA AREA The Greater Oficina area lies on the south flank of the Eastern Venezuela Basin (Fig. 1). Nearly all accumulations of oil and gas in the area are trapped, in whole or in part, against normal faults. All known oil and gas reservoirs in Greater Oficina occur in the Ofi-cina formation (Miocene-Oligocene) or in the "U" sands. The U sands are the lithologic equivalent of the Merecure group (Otigocene-Eocene), which contains oil in many fields north of Greater Oficina. Most of the petroleum produced in Eastern Venezuela is from the Oficina formation.

Jan 1, 1958

By T. G. Richardson, F. M. Perkins

In the recent paper of Richardson and Perkins entitled "A Laboratory Investigation of the Effect of Rate on Recovery of Oil by Water Flooding,"' the authors found very little appzrent effect on oil recovery of having free gas saturation present prior to water flooding in unconsolidated sands. We agree that the effect in this particular system was small but do not feel that the data presented should be regarded as disproving work of others which has shown an appreciable effect. The authors do not make such a claim, but neither do they advance an explanation of the difference. In our experience the following factors must be carefully considered when studying the relation between residual oil saturation after water flooding and initial free gas saturation: (1) the magnitude of the inherent residual oil saturation, i.e., the residual oil saturation with no free gas; (2) the increase in oil-water viscosity ratio with pressure lowering if the gas saturation is obtained by solution gas drive; and (3) the oil shrinkage which occurs with pressure lowering and gas evolution. The system studied by Richardson and Perkins gave residual oil saturations as low as 20 per cent without free gas present, and one should perhaps not expect much further lowering. As an illustration of the magnitude of the effect when the residual oil saturation is inherently higher we submit the accompanying figure. These data were obtained on an unconsolidated sand under elevated pressure in a system similar to the one described by Richardson and Perkins. Gas saturation was established by gas drive before water flooding. The viscosity ratio was 600:1 under the conditions of the displacement. Here the gas was extremely effective in reducing residual oil saturation. This fact was also indicated by Kyte, et al.2 Their plots of residual oil saturation vs initial gas saturation show trends of greater free gas effect with higher oil viscosities. The pressure-dependent effects were not discussed by Richardson and Perkins. They should be separated from the free gas effect if the objective of the study is a correlation of residual oil saturation vs initial free gas saturation. The increase in oil viscosity when gas is released from solution tends to increase residual oil saturation. This effect is rather small in the viscosity range of kerosene. A Buckley-Leverett calculation, assuming an increase in viscosity ratio from 1.2 to 1.8, indicates an increase in residual oil saturation of about 1 per cent of pore volume. Thus, one would expect this system, if operated at constant viscosity ratio, to show a slightly greater free gas effect. As Dyes- as shown, oil shrinkage can offset the beneficial effect of free gas on waterflood oil recovery, if the gas saturation is established by depletion. Since

Jan 1, 1958

Jan 1, 1958

By W. C. Lilliendahl, G. Meister

Uranium metal with a purity of about 99.9 pct was produced on a large scale by fused salt electrolysis with a material efficiency of about 90 pct. The material efficiency depends mainly on bath composition, electrolysis temperature, electrode smothering, and elutriation during washing of the powder. RESEARCH and development work on fused salt electrolysis carried on by the Westinghouse Lamp Div. Bloomfield, N. J., was done under the Manhattan District Corps of Engineers and later under the Atomic Energy Commission for the commercialization of uranium production for the first atomic pile at the University of Chicago in 1942. From the conception of the atomic bomb project it was recognized that metals with impurity levels having little metallurgical significance would be required. Permissible impurity levels were based on neutron absorption. Of particular significance was boron, which could not be present in amounts exceeding 1 ppm. The electrolytic method as developed in 1930 by Driggs and Lilliendahl,1,2 and later improved, yielded uranium of very low boron and other deleterious impurity content. No other method was capable at that time of producing uranium metal of the required purity.' The low boron content of uranium produced by the electrolytic process resulted from the availability of the reactants which were low in boron content, and from the inherent elimination of boron in the fused salt bath. Since the heart of any electrolytic process is the electrolysis cell, this paper will deal with the development of the original bath composition for the efficient production of uranium from a batch process to one of continuous operation. Emphasis also will be placed on other factors which will affect the material efficiency of the process. With the laboratory cell the material efficiency of uranium powder recovery in the early electrolysis was relatively low, about 35 pct based on the ratio of uranium recovered to uranium added. This early process also had other defects. The electro- lytic bath could not be used continuously. After three runs from a freshly charged crucible, the deposit showed a tendency to slip off the electrode as it was raised from the bath. This condition necessitated pouring the charge every fourth run and preparing a new bath. It was assumed at that time that this condition was caused by the increasing fluoride concentration with each addition of uranium salt, which adected the mobility of the uranium ions. Experimental The electrolysis cells differed in size only. They were of the floating cathode type. The laboratory cells were 21/2 in. ID and 6 in. deep and operated at 30 amp and 5 volts. Production was about 150 g metal powder per 8 hr. The plant cells (5 units) were 9 in. ID x 21 in. deep and operated at 1800 amp at 12 volts. The total production unit was designed to produce 250 lb of uranium powder per 8 hr day. Because of the tendency of uranium fines toward spontaneous combustion, material efficiencies were based only on the recovery of useful coarser metal which could be safely handled. The reported efficiencies are of particular significance only as related to the same group of experimental procedures. At the start of the project no changes were contemplated until previous data could be definitely confirmed. Therefore, the first experiments were with the 50 pct CaCl2-50 pct NaCl mixture. The material efficiency of uranium deposition as a function of the number of electrolyses is shown in Table I. In Table I, the decrease in efficiency at 800°C with number of runs is apparent and confirmed the earlier data. Operating at 900°C enabled the number of runs to be doubled, but before pouring the charge the efficiency of recovery became poor. This test indicated that the improved efficiency might have been caused by an increase in the fluidity of the bath.

Jan 1, 1958

By R. P. Carreker

THE experiments described in this report were conducted as a part of a general program designed to document the deformation behavior of pure metals over a wide range of temperature. Material The silver used in this investigation was obtained from the Handy and Harmon Co. as 99.97+ pct pure. It is from the same length of wire as that designated H-H silver by Hoffman and Turnbull in their investigation of self-diffusion in silver.' The silver was drawn at room temperature from 0.060-in. diam to 0.020-in. diam wire without intermediate annealing. Seven-inch lengths of cold-drawn wire were annealed in groups of ten by placing them in individual quartz tubes spaced circumferentially about and near the vertical furnace axis. Dry nitrogen was passed through the furnace to lower the partial pressure of oxygen. The three annealing temperatures used were 700°, 800°, and 900°C, producing grain sizes of 0.017, 0.040, and 0.250 mm diam after 30 min at temperature. Testing Procedure The details of the testing procedure have been described in the reporting of results of a similar investigation of Copper. Annealed specimens of 5-in. gage length were gripped between grooved plates. Tests were performed using an Instron tensile-test-

Jan 1, 1958

By Tormod Forland

FROM equilibrium measurements on the system NaF-Na 3A l Fo-A 1 2 O 3-Na CO 3-CO 2 with high contents of NaF, Forland, Storegraven, and Urnesl concluded that complexes are formed containing two oxygen, three aluminum, and a less defined number of fluorine per complex. The same number of oxygen atoms per complex was also found by cryoscopic measurements for mixtures high in NaALF 6. In a recent paper by Stokes: some other complex ions, Al2O2F42- and AlOF2-, have been suggested. Here an additional argument in favor of the complex ALO2F. suggested by Forland, Storegraven, and Urnes will be given. When fused Na3AlF6 containing some A12O3, is cooled slowly, the solid phase will consist of the two components as separate phases. The melting point and the heat of fusion of Al2O3 are so high that this component will form the stable solid phase even though in the liquid state the complex may have a high stability. If, however, the fused mixture is quenched, the decomposition of the oxygen-containing complex and the formation of solid Al2O3 does not proceed fast enough, and a solid solution of A12O3 in Na3AlF6 is obtained. Zintel and Morawietz3 obtained cryolite containing 10 pct AL2O3 in this way. The density and the lattice parameters of the A12O3 containing cryolite were also measured, and from this it was concluded that the Al2O3 enters the cryolite lattice as Al3AlO0 groups replacing Na3AlF6 groups. However, the experimental data could as well be explained by assuming that one Na+ ion and two of its neighboring F- ions are replaced by one Al3+ ion and two O2- ions. This may be pictured schematically as: F F F F F F F Al F Na F Al F ,-Na+ + Al8+ F Al 0 A1 0 A1 F F F F —2 F- + 2O2- F F F solid cryolite cryolite-alumina solid solution This means that the complex in the solid solution, derived from X-ray and density measurements, is the same as that which Forland, Storegraven, and Urnes derived from equilibrium measurements in the liquid state. References IT. Forland, H. Storegraven, and S. Urnes: Ztsch. fur anorgan-ische und allgemeine Chemie, 1955, vol. 279, p. 205. 2J. J. Stokes: AIME Trans. To be pubhshed. s E. Zintel and W. Morawietz: Ztsch. pubhshed.fur anorganische und allgemeine Chemie, 1939, vol. 240, p. 145.

Jan 1, 1958