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Jan 1, 1948

By George G. Binder Jr., James W. Lacey, Arthur L. Draper

An experimental investigation of miscible fluid displacement has been made in linear porous media under highly adverse mobility ratio conditions. Various refined oils were displaced at field rates by liquid propane in both horizontal and vertical models 9 to 36 ft in length. In horizontal tests, mixed zones or transition zones form between the two liquids early in the displace-lents. Initially, the zones grow rapidly. III 2-in. diameter models, the mixed regions become nearly stable zones from 6- to 20-ft long. From then on these quasi-stable zones apparently grow only by molecular diffusion. The lenghts of the quasi-stable zones appear to be almost independent of the core material in which displacement;; are made and increase with increasing rates of injection and oil/solvent viscosity ratios. The lengths of the quasi-stable zones. measured in 2-in. diameter models at viscosity ratios and injection rates anticipated in the field indicate that essentially piston-like displacements of oil by solvent would occur. However, the mixed zone lengths increase markedly as the model diameter increases. In vertical displacements controlled by gravity drainage, only short trans-sition zones form. The entire lenghts of these zones can be accounted for by molecular diffusion. Therefore, in reservoirs having characteristics allowing a high degree of gravity drainage, nearly complete oil recovery should be attainable by miscible fluid displacement. INTRODUCTION The oil industry is faced with an ever increasing cost for finding new oil reservoirs. This, coupled with the fact that conventional methods of oil recovery usually leave from 1 to 3 bbl of oil in the ground for every barrel produced, has aroused considerable interest in developing more efficient methods. An integral part of the mechanism of many of these new methods of recovery is a miscible fluid displacement in which oil is displaced by a much less viscous materiai such as liquid propane. A numher of irlvestigators have explored the mechanics of miscible fluid displace-ment,'.2.1.'."." but in the experiments reported many of the important factors have been varied only over a limited range far removed from norma1 oilfield values. This paper presents the results of an experimental study of oil displacement by liquid propane at field rates from linear, natural-sandstone models of various sizes. Both horizontal and vertical flow tests were made. EXPERIMENTAL APPARATUS AND PROCEDURE Refined oils with viscosities varying over a wide range were displaced at several rates by liquid Propane from both horizontal and vertical flow systems. The behavior of the displacement was observed by propane-oil analyses of the effluent and, when possible, by differential pressure measurements along the cores. A schematic flow diagram of the apParatus used to conduct the experirents is shown in Fig. 1. The cores used in the tests were 9-ft lengths cut from natural consolidated sandstone and turned to the desired diameter. These were cast in steel tubing with a low melting point (160°F) alloy which expands on solidification. Flanges welded to the ends of the steel pipes permitted sealing the ends or butting one core to another. Pressure seals were maintained with O-rings. The cores were cleaned by flushing

By H. Colijn

Belt scales are frequently used in the mining industry because of the ability to handle large tonnages without interrupting the material flow, fitting easily into all types of bulk handling systems and being relatively inexpensive. Although manufacturers claim weighing accuracies better than Y2%, many operators experience, in practice, much larger errors and they have become apprehensive about the use of belt scales. However, in spite of these disappointing instances, a belt scale is one of the most valuable tools for process and inventory control. Since it is a measuring device, care should be given to the design and installation of belt scales. The basic components of a belt scale are: (1) conveyor belt, (2) scale suspension, (3) sensing device, (4) integrating and recording. The first component of this system is of great importance to the overall accuracy and has been thoroughly discussed in earlier papers. This paper will review primarily the various scale hardware designs currently available, and will be confined to the last three components of the system.

Jan 1, 1973

By AIME

TITANIUM-RICH ilmenite deposits, situated in the Allard Lake area in Quebec some 400 miles down the St. Lawrence River from Quebec City and 28 miles north of Havre St. Pierre on the north shore of the Gulf of St. Lawrence, are undergoing an intensive development program by the joint efforts of the Kennecott Copper Corp. and The New Jersey Zinc Co. Easily accessible ore, amounting to about 125 million long tons and carrying from thirty to forty per cent titanium oxide, has been delimited. Plans are being made for construction of an electric smelter at Sorel, on the south bank of the St. Lawrence midway beween Montreal and Three Rivers, which will produce 650 long tons of high-grade titanium slag and 500 long tons of iron per day from 1500 long tons of ore. Occurrence of ilmenite ore in this area has been known since J. A. Retty reported his geological work in the lower Romaine River area for the Quebec Bureau of Mines in 1941. In this report Dr. Retty mentions the presence of anorthosite rocks, some of which were rich in ilmenite. Claims were staked by several interests but the small showings and complex metallurgy were too formidable for any organization not adequately equipped with capital, metallurgical knowhow, and market outlets. However, Kennecott became interested and through a newly formed Canadian subsidiary, Kennco Explorations Ltd., options were taken up under the direction of A. H. Robertson. An area of 300 square miles was traversed in the summers of 1945 and 1946. During 1946 and 1947 geophysical and diamond-drill prospecting disclosed a num-

Jan 1, 1948

By James A. Beck

Phosphorus is essential to all life processes and therefore to the existence of man. In this role, there are no substitutes for phosphorus. In a commercial sense, phosphorus and its compounds are important to our entire economy, both in agricultural and in nonagricultural applications. The world's phosphate requirements are met by mining phosphate rock. Two general types of phosphate ore deposits are commercially important-igneous and sedimentary. Igneous deposits generally are more difficult and more expensive to mine than sedimentary deposits and are of importance mainly in the USSR, North Vietnam, and South Africa. Approximately 15% of current world production comes from these deposits. Over 80% of world production is from the pellet sedimentary deposits of Florida, North Africa, and elsewhere. Guano, the second type of sedimentary deposit, is produced in South America but is declining in world importance. Production Production of phosphate rock was reported in 31 countries during 1972. However, about 80% of world output is produced in three countries: the United States, the USSR, and Morocco (Table 15.2A.1). Throughout the past 20 years, between 75% and 80% of world output has been produced by these three leading countries. Between 1948 and 1972 world production increased at an average rate of 10% per year, from 21.5 to 103.9 million tons. Growth was quite steady at 6% per year through 1963, but in the 5 years from 1963 to 1968 production increased 11 1/2% per year. Since 1968 production has increased about 91/2 % annually. Since 1948 several new phosphate mining ventures have been developed in Senegal, Togo, Israel, and North Vietnam. In the same period, only one important phosphate deposit, on Makatea Island, has been mined out and closed. A number of other phosphate mining ventures are in various stages of planning and development. The most important new venture in phosphate mining is in the Spanish Sahara. New mining capacity is expected also in Syria, and serious investigation is in progress in Peru, India, Turkey, and Australia. Major expansion of existing operations is expected in Morocco, Russia, Tunisia, Israel, and Jordan. Consumption Historical data on world consumption of phosphate rock are not available in detail, but world consumption of phosphate has closely paralleled world production in the past two decades. The United States is the world's largest user of phosphate rock, accounting for 30%

Jan 1, 1976

By Leonard B. Gulbransen, John R. Lewis, W. Martin Fassell, J. Hugh Hamilton

A simple reproducible method was developed for determining the ignition temperatures of magnesium and magnesium alloys and by this method magnesium and over 100 magnesium alloys were measured. The ignition temperature of magnesium was determined in O2-SO2, O2-N2 mixtures and in O2 from 0.166 to 10 atm pressure. The ignition temperature of magnesium is generally lowered by alloying and increased by an increase in oxygen pressure. WITH the expanded use of magnesium alloys in industry, ignition temperatures are of considerable importance, especially in heat treating and for service at elevated temperatures. Magnesium alloys exhibit a relatively slow linear oxidation rate up to temperatures near the melting point.' At some critical temperature the rate of oxidation becomes extremely rapid. This high rate of oxidation is accompanied by the emission of light and additional characteristics suggesting a flame. The literature concerning the ignition temperatures of magnesium and magnesium alloys is relatively incomplete and the values reported by various authors are not in agreement. The most probable reasons for this are: 1—The absence of a suitable definition of ignition, and 2—the need of a standardized method of determining the ignition temperatures of inflammable metals and alloys. The exact date of the discovery of the fact that magnesium will ignite and burn is unknown. It is likely that H. Davey encountered this property of the metal during its preparation in 1808. The first reference in the literature specifically on ignition of magnesium is by Lenze, Metz, and Rubens.' They investigated the inflammability of certain magnesium alloys. Brown3-' reported that magnesium ribbon will ignite in air at 507 °C by what was called the rising temperature method. Hartman, Nagy, and Brown" reported that magnesium powder ignites from 475" to 560°C depending on particle size. According to Guise, Mars, and Wilson prolonged heating in air at 427°C of common casting magnesium alloy causes it to ignite. Samples of magnesium alloys were placed directly in the flame of a torch by Carapella and Shaw.' These investigators obtained some evidence of melting prior to ignition. For commercial magnesium, they reported an ignition temperature of 650°C. Their values varied from 450" to 800°C for magnesium alloys. Willmore and Peterson" studied the effect of air velocity, humidity, rate of heating, and foreign metal contact on the ignition temperature of magnesium. They conclude that melting is not a prerequisite for ignition and that the conditions which influence ignition are complex and difficult to analyze. The only quantitative theoretical treatment of the ignition temperatures of magnesium and magnesium

Jan 1, 1952

By W. A. Anderson, R. F. Mehl

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

Jan 1, 1945

By Frank H. Macpherson

When it became apparent early in 1941 that the United States might be drawn into the war, studies were made of the bauxite situation in Arkansas, principally because 9.5 pct of the known bauxite reserves of the country were located in that State. Bauxite mining was then geared for maximum production to supply ore to meet this country's war requirements and, if necessary, to supply the needs of Canada as well. In view of the comparatively small bauxite reserves, Congress appropriated funds for an extensive exploratory drilling program to be carried out by the Bureau of Mines in cooperation with the Geological Survey. An alumina plant was erected near Bauxite and an aluminum plant near Hot Springs, Ark., by the Defence Plant Corp. The Metals Reserve Co. established a schedule of prices, arranged for stockpile sites and a buying agency. Operators cooperated to step up production and new ones came into the field. Production Record Prior to 1941, the greatest annual production in Arkansas was 562,892 long tons, dry basis in 1918. During the single month of August 1943, 693,596 long tons were mined—130,704 tons more than for the entire year of 1918. In general the Arkansas bauxite deposits are relatively small, irregular in thickness, somewhat scattered and, compared to coal, iron or open-pit copper deposits, are ill-adapted to an expansion in output. Commercial deposits range in horizontal extent from less than an acre to about 40 acres and are usually very irregular in outline. The average thickness of all known workable deposits is between 12 and 15 ft. with a maximum of about 60 ft. The ore bodies are usually somewhat undulating and nearly horizontal although locally some deposits dip as much as IS°. Types of Bauxite Three physical types of bauxite may be recognized: pisolitic, granitic and amorphous. Pisolitic ore is the most common type. It consists of small pebble-like nodules, ranging from the size of a pin head up to several inches in diameter, all set in a fine grained matrix. Transported bauxite is usually- pisolitic. Most residual bauxite is granitic. It is believed not to have moved appreciably from the location where it originally was formed. This is indicated by the fact that it appears to grade into unaltered nephelite syenite, which it overlies. Amorphous ore is the least abundant. It is nonpisolitic and resembles clay, has no characteristic texture, and can be identified definitely only by chemical analysis. Uses of Bauxite Bauxite is chiefly used for, and at the present time is substantially the only

Jan 1, 1948

By Frank H. Macpherson

When it became apparent early in 1941 that the United States might be drawn into the war, studies were made of the bauxite situation in Arkansas, principally because 9.5 pct of the known bauxite reserves of the country were located in that State. Bauxite mining was then geared for maximum production to supply ore to meet this country's war requirements and, if necessary, to supply the needs of Canada as well. In view of the comparatively small bauxite reserves, Congress appropriated funds for an extensive exploratory drilling program to be carried out by the Bureau of Mines in cooperation with the Geological Survey. An alumina plant was erected near Bauxite and an aluminum plant near Hot Springs, Ark., by the Defence Plant Corp. The Metals Reserve Co. established a schedule of prices, arranged for stockpile sites and a buying agency. Operators cooperated to step up production and new ones came into the field. Production Record Prior to 1941, the greatest annual production in Arkansas was 562,892 long tons, dry basis in 1918. During the single month of August 1943, 693,596 long tons were mined—130,704 tons more than for the entire year of 1918. In general the Arkansas bauxite deposits are relatively small, irregular in thickness, somewhat scattered and, compared to coal, iron or open-pit copper deposits, are ill-adapted to an expansion in output. Commercial deposits range in horizontal extent from less than an acre to about 40 acres and are usually very irregular in outline. The average thickness of all known workable deposits is between 12 and 15 ft. with a maximum of about 60 ft. The ore bodies are usually somewhat undulating and nearly horizontal although locally some deposits dip as much as IS°. Types of Bauxite Three physical types of bauxite may be recognized: pisolitic, granitic and amorphous. Pisolitic ore is the most common type. It consists of small pebble-like nodules, ranging from the size of a pin head up to several inches in diameter, all set in a fine grained matrix. Transported bauxite is usually- pisolitic. Most residual bauxite is granitic. It is believed not to have moved appreciably from the location where it originally was formed. This is indicated by the fact that it appears to grade into unaltered nephelite syenite, which it overlies. Amorphous ore is the least abundant. It is nonpisolitic and resembles clay, has no characteristic texture, and can be identified definitely only by chemical analysis. Uses of Bauxite Bauxite is chiefly used for, and at the present time is substantially the only

Jan 1, 1948

By Hamilton Wingate

In his paper on the hydraulic mining of a low-grade gravel in California,* Mr. W. H. Radford expresses the hope that other members of the Institute will contribute, for the benefit of all, their experience in similar lines. In these notes 1 shall describe the conditions and results of the operation of the Gold Bug Mining Co., of Cleveland, O., at Georgetown, Eldorado county, Cal.

Jan 1, 1903

By Enrique Hauser

FIRE-DAMP is a mixture of methane with other inert gases or combustible gases. The inert gases in question are carbonic acid, water vapor, nitrogen, etc. The combustible gases are hydrogen, ethane, etc. The study of the properties of fire-damp, therefore, becomes a study of the properties of methane and the influence on its properties of the different gases we have mentioned. Characteristic Properties of Methane 1. Respirability.-Methane being a paraffin is characterized by its weak chemical affinities. From the physiological, point of view one could substitute it for nitrogen of the air at least momentarily, without experiencing any difficulty in breathing the mixture consisting of 21 per cent. 02 + 79 per cent. CH4. I .have tried this on myself, making the gas exhaled -from the lungs burn subsequently in a Bunsen burner.1 From the chemical point of view, this weak affinity permits the gas to be burned in certain circumstances with hydrogen and oxide of carbon in an oxygenated mixture, with the result that the last two gases achieve only a fractional combustion. This practice has been utilized with success in the methods of analysis which I have perfected and which I describe later in this paper. 2. Retardation of Flashing Point.-A characteristic property of methane is its retardation of flashing point, noted by Davy in 1816 and studied by Mallard and Le Chatelier in 1883.2 Taffanel and Le Floch have recently confirmed these results.3 Let us recall the nature of this retardation:

Jan 2, 1916

By M. E. Grimes

Rio Algom Mines Ltd. owns eight uranium mines and mills in the Elliot Lake district of Ontario, seven of which were producing before 1960. At present only one mine is operating and meeting current contract requirements. Under present economic conditions, it is not feasible to mine ore of less than 2.0 lb per ton U3O8, although there are very large reserves below this grade, Rio Algom is interested in preconcentration for three possible applications: to extend ore reserves by permitting use of lower grade ore, to reduce costs on processing of present grade ore, and to reduce capital investment in expanding production to meet future production goals. Rio Algom has been investigating various applicable preconcentration processes since the early 1950s to date, on laboratory and pilot-plant scale. Methods investigated include gravity concentration by sink-float, high intensity wet magnetic separation, flotation of uranium, flotation of acid consumers, and a number of electronic sorting methods including radiometric, photometric, and conductimetric. No method tested has yet been satisfactory under Rio Algom's criteria of uranium recovery and cost, principally because uranium loss has been too high for a useful weight rejection. Metallurgical results of the preconcentration test work and the economic assessment therefrom are reviewed.

Jan 1, 1974

By Earl C. Herkenhoff

Publication of the article "The Flotation Behavior of Digested Asphalt Ridge Tar Sands" by R.J. Smith and J.D. Miller has confirmed and again spotlighted a most significant and important development in the field of tar sand and heavy oil mining. This is the ability to recover 95% of the bitumen in dry tar sands by a hot water process. The initial investigation by Miller and Sepulveda in early 1978. "Separation of Bitumen from Dry Tar Sands," was the first blockbuster. It is disappointing that there has been so little scientific and industry ackowledgement that the authors laid to rest the long entrenched belief that the sand grains had to be "water wetted" for a hot water process to be applicable. Dr. Miller and his researchers at the University of Utah used slightly different mineral dressing terminology in describing their process but it is essentially the old, established technique of high &lids attrition scrubbing at elevated temperatures with a conditioner or modifier, followed by dilution and froth flotation. Similar techniques were described in detail for other nonmetallic minerals in the mid-1940s by Stuart Falconer of American Cyanamid Co. The authors used a 15-minute "scrub" period (or in their terminology "digester step") at 73% solids and 95OC (203°F) in a 0.3 m solution of sodium carbonate-about 4 kg/t (8 lb per st) of tar sand. Flotation was at 10% solids. Obviously, the scrub is an expensive step with respect to energy input but the high recovery of bitumen appears to justify it. Two basic questions then arise: What are the effects of shorter scrubbing time, lower temperature, and less sodium carbonate? Would a two-stage approach be advantageous? That is, could you get the major proportion of the bitumen with a mild scrub and apply the high power and temperature only to the refractory portion? These variables should be evaluated. Apparently, all results were only for rougher flotation. What would the grade and recovery of bitumen be if multiple cleaner flotation steps were employed? We must concede that a 60.62% grade of bitumen leaves considerable room for upgrading. Finally, it should be noted by all executives who approve funds for heavy oil recovery schemes, most of which are variations of in-situ methods, that mining can yield a 95% recovery of bitumen. That is correct, 95%. Imagine what that does to the total barrels recovered from a heavy oil resource compared with the scrawny 30-35% maximum recovery we are getting now. The conclusion-let's mine heavy oil and tar sands.

Jan 1, 1983

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 H. D. Colson, Robert A. Rapp

When a binary alloy is oxidized to form simultaneously an internal oxidation zone and an external scale which grows at a constant rate, the oxidation should reach a condition of steady shale, in which the internal oxidation zone is maintained at a time-independent thickness. Assuming an ideal model for the steady-state oxidation, the diffusion equation is solved for the steudy-state concentration profiles for oxygen and alloying- element in the metal. A theoretical prediction of' the steady-state thickness of the internal oxidation zone is made in terms of the experimental parameters. FOR the oxidation of binary alloys, Rhines, Johnson, and Anderson,1 as well as Mask: have derived equations describing the kinetics for the simultaneous formation of an internal oxidation zone and an external scale which was assumed to mow according to a parabolic rate law. Experimental determinations of internal oxidation zone thicknesses beneath a Cu2O scale for Cu-Be and Cu-A1 alloys3,4 have shown some deviation from Maak's theoretical expressions, because the ideal model assumed for the calculation is not met experimentally. Some pure metals, such as columbium and tantalum oxidize at elevated temperatures and high oxygen pressures to form nonprotec-tive external scales which thicken at a constant rate. If such a base metal is alloyed with a solute element which may form a more stable oxide than the solvent oxide, then internal oxidation of solute may occur beneath the growing external scale. A review of the internal oxidation of alloys has been published recently.5 The purpose of this paper is to analyze theoretically for a binary alloy the kinetics for the simultaneous formation of an internal oxidation zone and an external scale which grows at a constant rate. Consider an alloy A-B in which A is the more-noble solvent and B is the less-noble solute. The solute oxide is assumed to precipitate in internal oxidation as stoichiometric particles of BO, which are assumed to have a negligible solubility product in the A matrix. It is further assumed that the diffusion of oxygen through the zone of internal oxidation is not impeded by previously precipitated BO, particles. The specimen is assumed to be sufficiently thick so that the solute content in the center of the specimen does not change. For consistency: the following notation of Maak2 has been used:

Jan 1, 1967

By D. L. Wood

INTERNAL oxidation of alloys has been investigated by Rhinesl,2 and by Meijering and Druy-vesteyn. Rhines showed that dilute Cu-A1 alloys can be internally oxidized without forming an external scale by annealing in an oxygen partial pressure equal to the decomposition pressure of Cu2O. The oxygen is supplied at the outside surface at a rate sufficient to maintain saturation of the surface with respect to oxygen. Oxygen diffuses inward and, at the interface between the subscale and the alloy, oxygen meets the solute and reacts to precipitate its

Jan 1, 1957

By M. Yokoi, K. Yoshida, T. Ishihara

The solubility of aluminum in cryolite melts has been determined by measuring the weight loss of aluminum submerged in melts contained in closed silicon nitride crucibles. The solubility in pure cryolite has also been checked with radioactive isotopes. The solubility decreases with increasing A1203 concentration, decreasing temperature, and decreasing cryolite ratio. The change of aluminum solubility in pure cryolite with the activity controlled by using Al-Ag and A2-Cu alloys supported the assumption that aluminum would dissolve in the form of monovalent ions according to the reaction 2AI + A1' —3 A1'. DURING the electrolytic production of aluminum, the electrodeposited metal redissolves in the bath in some form and is subsequently oxidized back to the former ionic state. This dissolution is believed to cause a decrease in current efficiency. Reported data on the solubility of aluminum in cryolite melts are scattered. The mechanism of the dissolution has not yet been determined, although certain tentative interpretations have been proposed. Many previous studies were performed under different test conditions. Studies were performed in open Systems and closed systems,'o and some were apparently not given sufficient time to Saturate." The solubility can be determined either analytically or gravimetrically. The analytical determination involves measurement of hydrogen gas evolved when frozen cryolite bath saturated with aluminum is treated with sodium hydroxide or hydrochloric acid. The gravimetric determination, adopted by many investigators,'-37'3>14 involves measurement of weight loss of the metal after equilibration with a known amount of salt. It appears that the former technique yields much smaller values of solubility than the latter technique. This large difference in results strongly suggests that the dissolved metal in the cryolite melt is no longer in the metallic state. In the present study, the solubility was determined by the gravimetric technique at various activities of aluminum using A1-Ag and Al-Cu alloys. An attempt was also made to determine the ionic (or atomic) state of the dissolved metal from the solubility data. 1) EXPERIMENTAL Apparatus. Preliminary tests demonstrated that silicon nitride was suitable as a container material since it is compatible to both the fluoride melts and molten aluminum. Crucibles were made from silicon powder nitrided with Nz gas at 1600°C. The good compatibility between crucible and melts is due to the near perfect nitrogenation of silicon. Only small amounts of silicon were found in the aluminum metal after the experiments. The crucible dimensions were 90 mm inside height, 38 mm ID, 105 mm outside height, and 50 mm OD. Close-fitting lids made of silicon nitride were also prepared. The crucible was placed in a close-fitting graphite crucible heated by a vertical Kanthal furnace, Fig. l. The lid and crucible are fastened tightly together by the condensation of vaporized bath in the narrow gap between them. The temperature was measured in the wall of the graphite crucible and controlled within * 5°C. The temperature difference between the measuring point and the interior of the melts was initially determined. Materials. The materials used were: Greenland cryolite (impurities CaF,, 0.5 pct; AlzO3, 0.2 pct; high-purity aluminum metal (purity 99.99 pct); A1203 and AlF, (provided by Nippon Light Metal Co., Ltd); reagent-grade NaF and CaF2; and 99.9+ pct Ag and Cu. Powdered reagents were carefully dried before use. A1-Ag and A1-Cu alloys were prepared before the experiments; their composition was checked by analysis

Jan 1, 1969

By M. B. Bever, A. K. Jena

In the investigation reported here, calorimetric measurements have been made to determine the heat of formation of the compound AuSb2 and the partial gram-atomic enthalpies of antimony and gold in dilute solution in liquid tin and their enthalpy interaction coefficients. In order to interpret the behavior of antimony and gold in dilute solution in tin, nonzero values are assigned to the energies of bonds between like solute atoms relative to the pure solute state. Sa.mples of the compound AuSb2 were prepared by melting stoichiometric amounts of antimony and gold (99.999 pct pure) in evacuated and sealed Vycor tubes, which were shaken vigorously and quenched in water. The ingots were annealed in evacuated and sealed tubes at approximately 700°K for 2 weeks. Metallo-graphic and X-ray examinations gave no indication of second phases or microsegregation. The samples were added from 273°K to tin-rich solutions in a solution calorimeter1 maintained at 623°K. The calorimeter was calibrated with tin; the heat content of tin, H623°K- H273°K, was taken as 4.08 kcal per g-atom.2 In each calorimetric run at least four additions were made. The total concentration of solutes in the bath at the end of any run did not exceed 1 at. pct. The measured heat effect of an addition was plotted against the average of the atom fractions x of Sb + Au in solution before and after that addition. From this plot the heat effect at infinite dilution h,,, and the composition dependence of the heat effect dh/dx in the composition range 0 < x < 0.01 were obtained. The results for the additions of antimony, mixtures of antimony and gold, and the compound AuSb2 are listed in Table I. The heat effect h on addition of a sample of the compound AuSb2 or a mechanical mixture of antimony and gold at 273°K to a tin-rich solution at 623°K can be expressed as:

Jan 1, 1969

By D. H. Baldwin, R. E. Reed-Hill

DURING the course of experiments involving oxygen equilibrations with a high-purity Pd-5 at. pct Rh alloy, the appearance of a subscale was noted. Most of the heat treatments in a pure oxygen atmosphere were performed at 900°C. The presence of the subscale was noted when the oxygen partial pressure was in excess of approximately 95 mm, up to 1 atm, the highest pressure used. According to available thermodynamic information&apos; on the free energy of formation of Rh2O3 (the only reliably reported solid oxide of rhodium), this oxide should not be stable under these conditions, nor, of course, any oxide of palladium. Extraction of the subscale from the matrix was affected by treatment with aqua regia, and the resulting X-ray diffraction powder pattern is shown in Table I. This pattern is not that of Rh2O3, nor that of any known rhodium or palladium oxide. It can be indexed on a hexagonal lattice with a. = 5.22Å and co = 6.0Å. In addition to this unknown material, there was a weak Rh2O3 pattern. An X-ray fluorescence analysis of the powder gave 3214 palladium counts per sec and 5381 rhodium counts per sec, thus indicating the likelihood of a double oxide of palladium and rhodium. In view of the fact that the above result was obtained on a single sample, it is perhaps best not to insist upon the above ratio of about 0.6, but possibly to tentatively assume 0.5 or 1/1. The small amount of Rh2O3 in the X-ray pattern might have occurred on cooling, and it seems possible that the double oxide, below some temperature level, is not as stable as Rh2O3. To examine this point, some of the extracted double oxide was heated on a sheet of pure palladium in air at 900°C, and allowed to furnace-cool over a period of several hours. The X-ray diffraction pattern of the powder showed approximately the same intensity of Rh2O3 and the "hexagonal" oxide as before, but, in addition, a rather faint pattern of another crystalline species made its appearance. This finding again suggests partial transformation of the major (double) oxide to other oxides on cooling from 900°C. Application of the phase rule shows that only one equilibrium oxide (subscale) could have been present at temperature. Vacuum-fusion, oxygen analysis of the extracted subscale showed 7.7 ± 0.7 pct O. Combining this information with that of the X-ray fluorescence analysis suggests the formula PdRhO. This compound should have an oxygen content of 7.07 pct, which is within the range of error of the oxygen analysis. However, until a more careful stoichiometric study is made, it is suggested that the formula be written

Jan 1, 1965

By R. J. Wasilewski

The resistivity of single crystal and of polycrystalline metal has been determined between 77° and 1500°K. At comparable purity, the resistivity of the poly crystalline metal differs from that calculated from the axial resistivity values. The observed anisotropy is briefly discussed. A zone refined titanium rod was obtained from F. J. Darnell.1 The hardness of this material varied between 52 and 64 Bhn, indicative of its high purity. Single-crystal specimens were cut out from a few large grains, elongated predominantly along <1120>. Resistance measurements were taken with specimens immersed in liquid nitrogen, solid CO,, and acetone, and at ice point, and then recorded continuously between room temperature and 1200" to 1250°C, throughout at least one full heating and cooling cycle at a rate of l° to 3°C per min. Four probe measurements were taken using spot-welded Pt wire 0.003 in. in diam as potential terminals, and the electromotive force drop was determined poten-tiometrically. A standard resistance, in series with the specimen, served to determine the dc current (generally about 80 ma) in the circuit. In order to eliminate spurious thermal electromotive forces, the circuit polarity was automatically reversed at 5-min intervals, and the mean of the two adjacent readings taken as the true electromotive force value. The discrepancy between the readings at reversed polarities was generally of the order of a few µ v, as all the spot-welded joints were contained within a volume of some 5 mm cube. The relative resistance (R T/R 273o) variation with temperature is tabulated below, and shown in Fig. 1, as measured during the first heating run. The discontinuous drop in resistance, corresponding to the a — ß transformation, started for both initial orientations at 1170°K; i.e., some 15°K above the accepted value of 882°C (1155°K). Judging by the temperature ranse of transformation—some 30°K for the single crystal and 20°K for the polycrystal-line specimen—this difference is believed caused by the solution of the oxygen present initially on the surface of the specimens. The general trend of the resistance vs temperature shown in Fi,;. 1 is in qualitative agreement with that previously reported for polycrystalline titanium metal. 2,3 Significant anisotropy is, however, indicated by the crossing over of the curves for <1120> and <0001> orientations at 273°, 650°, and 1000°K. This difference is most startlingly shown in Fig. 2, where instantaneous temperature coefficients (l/R273 x dR /dT) are plotted for both the first heat-

Jan 1, 1962