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By J. E. Strassner

Oilfield emulsions are stabilized primarily by film-forming asphaltenes and resins containing organic acids and bases. Adding inorganic acids and bases radically changes the physical properties of these films and their emulsion-stabilizing properties. Interfacial films show one of three different physical characteristics when retracted in pendent drop tests. These compressed films have rigid, soap-type or minimum film properties depending on the quantity of asphaltenes and resins in the crude oil and on the pH and composition of the brine. There exists for each crude oil-brine system an optimum pH range over which the adsorbed film exhibits minimum contracted filtn properties. In this range, intmfacial tension is high — frequently near its maximum value — indicating the absence of highly surface-active specier; crude oil-brine emulsions generally show minimum stability; and surfactant requirements for breaking these emulsions are significantly reduced — sometimes no surfactant is needed. About two-thirds of the world's crude oil is produced as emulsions that must be treated (demulsified) to be marketed.' Approximately three-fourths of all domestic crude oil produced must be treated. The percentage of crude requiring treatment increases as fields become older and more water is produced. Demulsification most frequently is attained through use of surfactants, heat and electric treaters. It is estimated that over 75 percent of all oilfield emulsions are broken by chemicals generally containing alkylene oxide condensates. Although acids and bases are known to affect emulsion stability:-' they rarely are used in the oil field except in batch treatment of the most severe emulsions. Nevertheless, pH adjustment by using acids or bases in demulsification has some advantages over other methods. Mainly, it is cheaper. Acids and bases frequently are cheaper to use than surfactants, or can appreciably reduce the amount of surfactant required for demulsification. Secondary advantages are that less oil is lost by emulsi-fication into the aqueous phase, and that less corrosion is encountered when the optimum pH is basic. Limitations to the use of pH include (1) use in brines containing high concentrations of reactive ions, (2) closer supervision for pH control than is required for surfactants and (3) need for corrosion protection when the optimum pH is sufficiently acidic. These factors indicate that the economics of pH con trol in demulsification will be maximized when relatively large treating facilities are needed, when relatively large surfactant concentrations are required to break an emulsion, when a relatively low concentration of the aqueous phase is emulsified in the oil and when the emulsified aqueous phase contains relatively low concentrations of reactive ions. Because there are no broad guide lines for using pH control in breaking oillield emulsions (and because the limited guides available are highly specific and frequently contradictory), this paper will attempt to clarify the principles involved in using acids and bases to break emulsions. These principles also should be useful in refinery separations and in other oilfield applications where stable or unstable petroleum emulsions are involved. Principles of Emulsion Stability Oilfield emulsions generally occur as water droplets dispersed in oil (w/o) and occasionally as oil droplets in water (o/w). These emulsion droplets are usually in the 0.1- to 10-micron range. However, more coarsely dispersed water droplets frequently are present in the emulsion. Pure hydrocarbons and water will not form stable emulsii except in extreme dilutions where the large distance brtween droplets inhibits coalescence. An emulsion breaks because interfacial tension acts to minimize the surface area of the dispersed drops by coalescence. However, emulsions can be stablized for long periods of time by the presence of a third phase that adsorbs at the oil-water interface and inhibits coalescence of the dispersed phase."' Emulsions generally are stabilized by (1) repulsive charges on the surfaces of the dispersed phase and (2) adsorbed films that, being preferentially wetted by the continuous phase, act as a physical barrier to inhibit contact between the dispersed droplets. Both these factors generally are important in stabilizing and in breaking o/w emulsions. However, repulsive charges are less effective in stabilizing w/o emulsions which generally are stabilized by adsorbed films.V or this reason the nature and importance of these films at oil-water interfaces were examined closely; as will be shown, pH changes were found to affect the films significantly, and this work led to laboratory tests of pH- adjustment in emulsion breaking. This paper will present evidence to show that emulsions are stabilized primarily by films that form around droplets

Jan 1, 1969

By R. J. Schilthuis

In 1929, Coleman, Wilde, and Moore1 undertook an investigation of the theoretical decline in reservoir pressure as related to the production of oil and gas. The most important part of this work was presented in an equation defining the relationship between the reservoir pressure, the quantities of oil and gas produced, the oil and gas content of the reservoir, and the properties of the reservoir fluids. With this equation, it appeared that, with sufficient data, it would be possible to calculate the oil content of the reservoir and predict quantitatively the effect of gas-oil ratio on the decline of reservoir pressure. Needless to say, such an expression would be highly important in evaluating fields and in arriving at a choice of production methods to be used. Unfortunately, at the time these investigators published their work, there were not sufficient data available to permit application of the equation. The technique of measuring reservoir pressures had not been developed, gas measurements were uncommon, oil and water production records were in most cases inadequate, and little was known of the properties of the complex hydrocarbon mixtures making up the oil and gas in the reservoirs. For these reasons, little additional work of a similar nature could be done. However, during the past four years many data have been systematically accumulated on reservoir pressures and the properties of oil and gas, and it is now possible to use these data in furthering the studies on the behavior of oil and gas reservoirs. It is the purpose here: first, to present the derivation of a modified form of the equation given by Coleman, Wilde and Moore, which will permit the calculation of what later will be defined as the "active oil" content of a reservoir; second, to derive formulas for calculating the reservoir-energy changes that occur during the course of production, and finally, to discuss the limitations and application of the equations developed.

Jan 1, 1936

By R. J. Schilthuis

In 1929, Coleman, Wilde, and Moore1 undertook an investigation of the theoretical decline in reservoir pressure as related to the production of oil and gas. The most important part of this work was presented in an equation defining the relationship between the reservoir pressure, the quantities of oil and gas produced, the oil and gas content of the reservoir, and the properties of the reservoir fluids. With this equation, it appeared that, with sufficient data, it would be possible to calculate the oil content of the reservoir and predict quantitatively the effect of gas-oil ratio on the decline of reservoir pressure. Needless to say, such an expression would be highly important in evaluating fields and in arriving at a choice of production methods to be used. Unfortunately, at the time these investigators published their work, there were not sufficient data available to permit application of the equation. The technique of measuring reservoir pressures had not been developed, gas measurements were uncommon, oil and water production records were in most cases inadequate, and little was known of the properties of the complex hydrocarbon mixtures making up the oil and gas in the reservoirs. For these reasons, little additional work of a similar nature could be done. However, during the past four years many data have been systematically accumulated on reservoir pressures and the properties of oil and gas, and it is now possible to use these data in furthering the studies on the behavior of oil and gas reservoirs. It is the purpose here: first, to present the derivation of a modified form of the equation given by Coleman, Wilde and Moore, which will permit the calculation of what later will be defined as the "active oil" content of a reservoir; second, to derive formulas for calculating the reservoir-energy changes that occur during the course of production, and finally, to discuss the limitations and application of the equations developed.

Jan 1, 1936

By G. F. Jenkins

ASBESTOS is a general term embracing the fibrous varieties of a number of minerals. Of these, the hydrous magnesium silicate, chrysotile (H4Mg3Si209), a variety of serpentine, is the most abundant and useful to industry. All other types of asbestos belong to the amphibole group of minerals and are classified as: crocidolite, NaFe(SiO3), FeSiO3; anthophyllite, (MgFe)SiO3; amosite, also a ferromagnesium silicate but with iron content higher than that of anthophyllite; tremolite, CaMg3(SiO3)4; and, actinolite, Ca (MgFe)3(SiO3)4. PROPERTIES The commercial value of asbestos depends largely on the physical property that permits it to be readily separated into fine filaments of high tensile strength and flexibility, which, coupled with the fact that it has the quality of incombustibility of a mineral-in distinction to vegetable and animal fibers-makes it of unique usefulness for many purposes. To some extent, the value depends upon the length of the fiber, although extreme length is neither necessary nor desirable for most purposes. Chrysotile occurs as cross-fiber veins, in which the asbestos fibers are approximately' at right angles to the vein walls, with vein width- or fiber length-seldom exceeding 2 or 3 in.; also as slip-fiber, in which the fibers 'lie in the same plane as the vein or on slippage planes. A cleanly broken vein of cross-fiber has a pearly luster and may range from a deep green or brown color to light shades of yellowish green or cream. When of good quality, the fiber filaments forming the vein may be easily drawn away from their neighbors and exhibit a fine silkiness and pure white color. They may be twisted into a thread and when flexed between thumb and fingers are found to be strong and pliable. Chrysotile withstands comparatively high temperatures without breaking down completely or fusing but begins to lose water of crystalliza-

Jan 1, 1949

By Charles Bell

THE Telluride mining district of southwestern Colorado is defined by the 37° 45' and 38° parallels of latitude and 107° 45' and 108° meridians of longitude. Telluride was never a boom camp, but has had a steady growth. In recent years, notwithstanding the business depression of 1920, the business has been the same as in normal years. The first prospector is said to have appeared in 1875, in which year locations on the Smuggler vein were made. Shipments were made in 1877 and 1878, and in 1879 milling the ores was attempted. While the district produced high-grade ores, it did not become important until 1890, when the Rio Grande Southern R. R. was completed from Ridgway to Telluride. The railroad has since been extended to Durango. In the fall of 1896, 400 stamps were in operation, and the annual production was $3,000,000.00, two-thirds of which was gold. The total production from 1875 to 1923 was: Gold $58,274,527; silver 41,830,920 oz., valued at $31,016,893; copper 15,258,866 lb., valued at $2,533,291; lead 166,056,484 lb., valued at $8,324,910; zinc 18,141,182 lb. valued at $1,323,787; or a total production of $101,473,408. All: claims are held in fee. Most of them are 1500 by 300 ft. but claims located within the last few years are 1500 by 600 ft. General supplies are obtained at Telluride, Denver, and Salt Lake. The largest mines are within 6 miles of the town of Telluride. Denver is 422 miles and Salt Lake is 439 miles, by rail, from Telluride. One-half of the distance to Denver and one-sixth of the distance from Telluride to Salt Lake is by narrow-gage railroad. The labor is efficient. The best miners are Italians and Austrians, then Slavs, Greeks, and Mexicans follow in the order mentioned. There are no labor unions. There are no serious mine pumping problems, the drainage being through adits. The Tomboy and Smuggler companies pump water from their reservoirs, the former for, milling and domestic purposes and the latter for milling, power, and domestic purposes.

Jan 2, 1924

By R. H. Landshof, Reynold Q. Shotts, James A. Redding

GENERAL INTRODUCTION by R. Q. Shotts The sizing of coal particles is one of the most important beneficiation operations performed from the time coal is broken at the face until it is delivered to the customer. Indeed, in many cases it may be virtually the only such operation performed in that interval, although it is most often accompanied by some comminution. Sizing, as the term implies, is a separation of the broken coal particles into arbitrary groups, each group containing particles within restricted mass, volume or size limits. Size itself is not a rigidly defined property, but is actually determined more by the operating principles of the sizing device than by unique properties of the particles themselves. Particle size cannot be uniquely defined independently of particle shape. Taggart l says, "In fact, it is not possible to state the size of a single irregular body by means of a single dimension; such possibility exists only for regular polyhedra and their limit, the sphere." In view of the scarcity of regular polyhedra among coal particles, even though most appear to approximate a cube, we actually define size in terms of a surface opening through which the particle barely will or will not pass, or of two openings, the smaller of which retains all particles of the group under study and the larger of which passes all of them. Alternatively, size is expressed in terms of rate of settling of particles in a fluid under closely controlled conditions. Historical Sketch2-Taken from Coal Preparation, 2nd Ed. "Sizing is the process of separating mixed particles into groups of particles all of the same size or into groups in which all particles range between certain definite maximum and minimum sizes. In coal preparation, sizing is generally accomplished by passing the coal over screens. Separation by differential settling in air or water currents has been adapted to the special field of separating very fine sizes, and these processes are in commercial use to a relatively small extent in the coal industry. Separation with screens is a very old industrial practice. Agricola described the use of screens for ore treatment in the middle ages. In the literature of the British coal industry references were made to the screening of coal as early as 1589, but the practice of extensive sizing for the market did not become general until the last half of the nineteenth century. "In America, the practice of sizing developed first in the Pennsylvania anthracite region, beginning with the use of rakes in the mine working places to recover coarse coal. The mining procedure left the fines in the mine.

Jan 1, 1968

By J. R. Long, A. H. Roberson, T. R. Graham, R. S. Dean

Experimental work on the properties of high-purity alloys of the copper-man-ganese-zinc system has necessarily required extensive metallographic work to determine the equilibrium conditions in this system. Previous work on these alloys is fragmentary and, unfortunately, based on alloys made with impure grades of manganese, thus introducing significant amounts of iron, silicon, aluminum and carbon. Since these elements are known to affect equilibrium conditions, it became desirable to re-examine these alloys made from the pure metals. The alpha solid solution field was of particular interest and, therefore, was chosen for the initial work, which was outlined to determine the composition limits of this field. Previous Work Heuslerl conducted an extensive survey of the liquid-solid regions of this system and also made an estimate of the solid-phase boundaries at 340°C. The pertinent part of his diagram is given in Fig. I, but it is of limited usefulness, since it applied to a single temperature only and is based on impure alloys under admittedly nonequilib- rium conditions. Bauer and Hansen,2 likewise working with impure alloys, have determined the phase boundaries for alpha-beta brasses containing small amounts of manganese and indicate an increase in the extent of the alpha field with increasing manganese. This is not in accordance with Heusler or with data obtained on pure alloys.3 They also described a third constituent precipitating in the alpha plus beta field below 350' to 400°C. but did not identify this constituent. Guillet4 and Heike and Ledibur6 have also noted this precipitate. Each of these investigators recognized that impurities present in the manganese could and did have an effect on the structure and properties of their alloys. Corson6 in particular pointed out the hardening effects of silicon, aluminum, and carbon in copper-manganese alloys and Heusler reported that his alloys containing more than 25 per cent manganese were extremely brittle. In all probability this brittleness was due to the impurities present. This early work, therefore, should be taken as a general guide for preliminary studies only, and high-purity alloys may be expected to produce different results. The work of the Bureau of Mines laboratories with electrolytic manganese has been briefly summarized by Dean7 but includes only a short section on this system. Later work3 outlined a limited portion of the alpha field in the neighborhood of 65 per cent copper, 10 per cent manganese, and 25 per cent zinc. The present work was under-

Jan 1, 1945

By F. M. Lewis, J. F. Meyers

This second progress report of grinding presents comments regarding ball consumption and data pertaining to the hydroscillator, which is closed circuited with the tricone mill. A study and postulate of how balls function is presented. The paper summarizes cost reduction obtained by the method of "grinding for the tail race" rather than for "mesh tons." AT the Regional meeting in Columbus, Ohio, in September 1949, the authors presented a progress report of the first year's operation with a Hardinge tricone mill in closed circuit with a Dorr hydroscillator. The present report covers our findings on this grinding circuit to January, 1950. In order to clarify our position, the authors wish to state that no invention or discovery is claimed. The Tennessee grinding circuit is simply an engineered arrangement of known equipment arranged to incorporate all of the recognized efficiency factors of comminution as they are known today. As we concluded our first report, it was not clear how effective the Tennessee mode of operation would be on harder ores. The only information we had at that time was that the Bond grindability test at 48-mesh gave 6.04 g of undersize per revolution. A later test on the same sample at 100-mesh reduced this to 2.04 g, which is definitely in the harder ore class, and which makes the reported 8.80 kw-hr per ton of —200-mesh produced a very creditable figure. Hydroscillator Operation The machine as now developed has proved dependable and easy to operate. It starts easily under full load and responds quickly to operating adjustments. The hydraulic holes in the oscillating plate do not plug when shut down under full load. Absolutely clean hydraulic water is essential. An Elliott water screen or similar device should be an essential part of the machine to keep all scale and trash of all kinds from the hydraulic compartment. The shift operators have expressed approval of the machine. In table I we show a typical screen analysis of the hydroscillator rake sand as compared to conventional classifier rake sand on our ore. We have previously reported that of the 28.7 pct reduction in power, the hydroscillator contributed 6 pct, on a —200-mesh basis. This is a conservative figure. Some of our test runs indicated that the saving was as high as 10 pct. Laboratory studies by the Dorr Co. engineers indicate that still greater efficiency is possible. Nevertheless, the 10-ft plate is overflowing 2100 tons per day at 3 to 4 pct + 65-mesh, which is a very creditable performance by

Jan 1, 1951

By F. M. Lewis, J. F. Meyers

This second progress report of grinding presents comments regarding ball consumption and data pertaining to the hydroscillator, which is closed circuited with the tricone mill. A study and postulate of how balls function is presented. The paper summarizes cost reduction obtained by the method of "grinding for the tail race" rather than for "mesh tons." AT the Regional meeting in Columbus, Ohio, in September 1949, the authors presented a progress report of the first year's operation with a Hardinge tricone mill in closed circuit with a Dorr hydroscillator. The present report covers our findings on this grinding circuit to January, 1950. In order to clarify our position, the authors wish to state that no invention or discovery is claimed. The Tennessee grinding circuit is simply an engineered arrangement of known equipment arranged to incorporate all of the recognized efficiency factors of comminution as they are known today. As we concluded our first report, it was not clear how effective the Tennessee mode of operation would be on harder ores. The only information we had at that time was that the Bond grindability test at 48-mesh gave 6.04 g of undersize per revolution. A later test on the same sample at 100-mesh reduced this to 2.04 g, which is definitely in the harder ore class, and which makes the reported 8.80 kw-hr per ton of —200-mesh produced a very creditable figure. Hydroscillator Operation The machine as now developed has proved dependable and easy to operate. It starts easily under full load and responds quickly to operating adjustments. The hydraulic holes in the oscillating plate do not plug when shut down under full load. Absolutely clean hydraulic water is essential. An Elliott water screen or similar device should be an essential part of the machine to keep all scale and trash of all kinds from the hydraulic compartment. The shift operators have expressed approval of the machine. In table I we show a typical screen analysis of the hydroscillator rake sand as compared to conventional classifier rake sand on our ore. We have previously reported that of the 28.7 pct reduction in power, the hydroscillator contributed 6 pct, on a —200-mesh basis. This is a conservative figure. Some of our test runs indicated that the saving was as high as 10 pct. Laboratory studies by the Dorr Co. engineers indicate that still greater efficiency is possible. Nevertheless, the 10-ft plate is overflowing 2100 tons per day at 3 to 4 pct + 65-mesh, which is a very creditable performance by

Jan 1, 1951

By R. W. Ph. D. Raymond, Anton Filers, O. H. Hahn

THIS paper will treat of such works only as beneficiate ores directly in the mining districts. And when it is said that more than twenty furnaces exist in Utah, about as many in Nevada, five in Montana, and four in Cerro Gordo, Inyo County, California, it is obvious that a business so extended deserves attention. Wide apart as these different works are located, they have nevertheless to deal in nearly every case with the same or very similar circumstances and conditions, so that, with very few exceptions, virtually the same system of smelting is followed in all these establishments. This is the so-called method of reduction and precipitation in blast-furnaces. As the principal reasons for the employment of a blast-furnace process are to be considered : the low percentage of lead in the ores, the high price of the only available fuel, charcoal, and the exorbitant rates demanded for labor. The reasons why the reduction and precipitation process is preferred to a roasting, reduction, and precipitation process are the high prices of labor and materials, and the preponderance of oxidized ores over sulphurets, though in some cases the latter are quite abundant. The weight of these reasons will be better understood when the character of the ores to be treated and the object of the smelting are more minutely stated. The ores are in nearly all cases a preponderating mass of oxidized lead ores, such as cerussite, anglesite, and leadhillite, in which nests and nodules of undecomposed galena occur. Associated with these are : in Eureka, Nevada, arseniate of iron and arsenical pyrites, hydrated oxide of iron, quartz, and calcareous clay ; in Little Cottonwood Canyon and American Fork, Utah, iron oxide, and in some cases a combination of antimony, the nature of which I have not ascertained; also dolomite and quartz in widely varying proportions; in Bingham Canyon, Utah, only quartz and comparatively little oxide of iron, or iron sulphurets; in Cerro Gordo, California, oxide of iron, iron pyrites, antimonial compounds, copper ores, and, as gangue, carbonate of lime and quartz. In Argenta, Montana, occur, besides the above-named lead ores, pyromorphite, and molybdate of lead. The preponderating gangue of the Argenta ores is quartz, and there is here a larger proportion of galena than elsewhere in the West. In most of the localities named, the lead ores themselves contain sufficient silver to render its separation from the ore the main object of the smelting; but in some of the districts, and especially in Montana, the lead ores serve only to furnish the extracting agent for the silver of true quartzose silver ores, which at the same time contain a sufficient percentage of lead to make amalgamation impracticable. They are therefore beneficiated by smelting, although the lead itself has no market value.

Jan 1, 1873

By E. L. Tucker

IN THE metallurgy of precious metals, it has been standard practice for years to use cyanogen compounds, so it was but natural that early investigators in the field of flotation should consider these compounds as possible flotation reagents. In Australian Patent 9508, of 1913, alkali cyanides were described as suitable reagents for the separation of heavy sulfide minerals, the reagents being employed either in an alka-line or neutral circuit. In U. S. Patent 1236501, of 1917, to John M. Tibbet, the use of cyanide in conjunction with soda ash or lime is described. One of the claims of this patent reads, "An improvement in the cyanide process for the treatment of ores comprising, mixing the ore with cyanide solution and oil and alkali: emulsifying the oil in the presence of the ore, the alkali and the cyanide solution, floating a portion of the values in the pulp by producing gas bubbles in the mixture-and removing the values floated." More recently, Sheridan and Griswold, in U. S. Patents 1421585 and 1427235, describe a somewhat similar process and have, successfully introduced it in. the mill of the Timber Butte Milling Co. U. S. Patent 1429544, of 1922, to Stevens, describes the use of double cyanides of copper, zinc, and lead. The success of cyanide as a reagent in the differential flotation of lead and zinc sulfides in highly complex ores is proof that these patents have a solid foundation.. Although the technique of their application to particular ores has been worked out in many cases, no one, so far as is known, has attempted to describe the nature of the action of the cyanide or to determine the ideal conditions for its, application. It was the purpose of the present investigation to gather information on these points. Naturally this would have been an exceedingly ambitious.

Jan 8, 1925

By John S. Johnson, Thomas Fraser

SIZING is the process of separating mixed particles into groups of particles all of the same size, or into groups in which all particles range between certain definite maximum and minimum sizes. In coal preparation, sizing is generally accomplished by passing the coal over screens. Separation by differential settling in air or water currents has been adapted to the special field of separating very fine sizes, and these processes are in commercial use to a relatively small extent in the coal industry. Separation with screens is a very old industrial practice. Agricola described the use of screens for ore treatment in the middle ages. In the literature of the British coal industry references were made to the screening of coal as early as 1589, but the practice of extensive sizing for the market did not become general until the last half of the nineteenth century. In America, the practice of sizing developed first in the Pennsylvania anthracite region, beginning with the use of rakes' in the mine working places to recover coarse coal. This mining procedure left the fines in the mine. Preparation outside the mine started with the installation of station¬ary cast-iron plates with 4 to 6-in. square holes. The run-of-mine coal was dumped upon the platforms, the large pieces of rock were picked out by hand, and the large lumps of coal were broken with hammers. The term "breaker," which still applies to the anthracite-preparation plant, originated with this practice, but the term is no longer descriptive of the entire function of the plant. In 1884, the first power-operated anthracite coal breaker' was erected by Gideon Bart at his colliery at Wolf Creek near Minersville, Pa. This plant utilized a system of rolls for breaking the coal and revolving screens for sizing. The plant was driven by a steam engine. It 'could handle

Jan 1, 1943

By A. J. Boyer, T. R. Meadowcroft

An experimental determination has been made of the efject of surface diffusion on the vapor pressure obtained in a Kwudsen cell. The results show that a knife-edge orifice in a molybdenum lid may give erroneous results for the vapor pressure of silver. when a correction suggested by winterbottom and Hirth is made, the results become meaningful. Experimental work with cylindrical orifices in molyhdenz~m lids and knife-edge orifices in ceramic lids shows that good vapor-pressure results may he obtained when the orifice is designed so that ejfusion is the only significant source of weight loss. THE Knudsen effusion cell technique has been used by many investigators to study relative and absolute vapor pressures over metals and alloys at elevated temperatures. As a result of this interest, some theoretical studies have been made of geometric factors affecting effusion from the orifice of a Knudsen cell. A review of these studies has been made by Margrave.1 Recently, Winterbottom and Hirth2 have suggested that a physical effect, that of condensation, surface diffusion, and re-evaporation, may seriously affect Knudsen cell measurements, especially when a knife-edge orifice is used. Inasmuch as many of the present vapor-pressure data have been obtained using knife-edge orifices. it was felt that an experimental evaluation of the effect of surface diffusion on Knudsen cell measurements would be of value both in the design of the cell orifice and in establishing realistic estimates of the limits of error for existing data. The experimental program was in two sections. Firstly, measurements of the vapor pressure of silver were made in cells with cylindrical and conical orifices in which the surface-diffusion contribution to the weight loss should be negligible. These results were correlated with existing data to give a reliable measure of the real vapor pressure of silver. Secondly, measurements made using knife-edge orifices were corrected using the surface-diffusion theory of Winterbottom and Hirth2 and were then compared to the real values. The experimental arrangement is shown in Fig. 1. The balance was an Ainsworth RV-AU-1 automatic recording microbalance capable of measuring weight changes of ±0.02 mg on a total load of up to 100 g. The temperature was measured by an optical pyrometer signted on the bottom of the suspended crucible. The temperature readings were calibrated in a separate experiment in which pyrometer measurements were made while at the same time thermocouple readings were taken of the temperature at the inside top and bottom of the crucible. The range of reproducibility with this technique was ±4°C. A constant voltage source maintained a temperature of ±2°C at 1200°C over 10 hr. Silver of 99.99 pct purity was used in nonporous alumina crucibles. Lids of molybdenum, tantalum, or magnesia were cemented to the crucible using a sodium silicate cement. Table I shows the characteristics of the lids used. The vapor pressure is obtained using the basic Knudsen formula:

Jan 1, 1965

By W. S. Potter

The proportions of manganese and carbon in manganese steel are familiar to all…

Jan 1, 1915

By Frederick Laist

THE past year has witnessed no radical changes in methods for the reduction and refining of copper. The Carson litigation was finally brought to a close ant1 the copper smelter is again free to introduce charge into his reverberatory furnaces in whatever manner suits him best. This litigation naturally led to much experimentation with various methods of charging and with various types of bath. In some cases the charge was introduced more or less centrally on a relatively dry hearth and in other cases into a bath of greater or less depth. The results of these furnaces were meticulously compared with the results obtained in side-charger furnaces, and it was apparent that it made little, if any difference how a given furnace \\.as charged so long as care was taken that there was always something in the furnace for the flames to work on. So long as this requirement was complied with, consumption of fuel per ton of charge smelted and tonnage smelted per furnace day remained substantially the same regardless of the method of charging or the depth of bath employed. In some instances the center-charged deep-bath furnaces gave slightly better results than the side-charged particularly with respect to copper losses. The slags of the deep-bath furnaces are generally a little cleaner

Jan 1, 1930

By W. N. Miner, R. O. Elliott

Electrical-resistivity )measurments were made be-trueetz room temperatrive and 1.5 oK on five different stocks of cerium metal, and the results were correlated with the types, amounts, and distribution of the impurities present. Magnesium, which appeared to be distributed as a solute throughout the cerium matrix, was found to have a large effect on the residual resistivity, 1 at. pct Mg being sufficient to increase the residual resistivity by about 10 microhm-cm. The formation of ß by repeated thermal cycling between room temperature and liquid-helium temperature is attributed to the deformation and faulting that occurs during the ? D a transformation. In preparation for starting a proposed study of cerium-rich alloys, we examined samples from severa1 stocks of cerium metal in order to choose the purest stock for future use in making the alloys. Low-temperature electrical-resistivity data were used to gain initial information about the purities of the stocks. Additional information was subsequently obtained from chemical analyses, density measurements, optical metallography, and electron-micro-probe analyses. Cerium that has been annealed at high temperature and cooled to room temperature has the fee crystal structure (? phase) with a = 5.16Å. When cooled further, in the region between about 250" and 150°K, some of the fee phase transforms to the double hcp form (ß phase) with a = 3.68 and c = 11.92Å. The remainder of the room-temperature fee form (and perhaps some of the hexagonal phase) transforms electronically in the vicinity of 100° K to the more dense or "collapsed" fee form (a phase), a - 4.85A, by transferring about 0.5 electron per atom from the 4f level to the valence band. Very little work related specifically to the effects of impurities on the physical properties of cerium has been reported in the literature. Gaume-Mahn1, 2 has studied the effects of calcium, magnesium. iron, silicon, and tantalum on the electrical resistivity and magnetic susceptibility of cerium between 60o and 300°K. Gschneidner, Elliott, and McDonald3 have discussed the effects of total impurity content on the hysteresis of the a —? (reversible) transformation and on the formation of the 4 and "a-? intermediate" phases. Smith and Morrice* have reported the effect of total impurity content on the resistivity of cerium at 4 and 293°K. In none of these reports, however, is it apparent that the distributions of the impurities were determined, L.r., whether the impurities were present in inclusions or in solid solution in the matrix is not mentioned; nor does it appear that the phase purity of the cerium was always considered. In the present study, five different stocks of cerium were involved. One was represented by a single sample of electrowon cerium, which was all that had remained from a stock of high-purity material obtained from the U.S. Bureau of Mines, Reno, Nev., in 1959. The other four stocks were recently purchased from commercial sources and were specified to be 99.9 wt pct pure. EXPERIMENTAL Cerium stocks designated as #1, #2, #4, and #5 were obtained from commercial suppliers for the specific purpose of finding a reliable source of high-purity cerium. Although the purity level of the cerium was specified to be 99.9 pet, the specifications did not include limits as to the amounts of various impurities that would be acceptable. Consequently the chemical analyses of the different stocks varied widely. Stock #3, which had been obtained from the U.S. Bureau of Mines and which was the purest on the basis of chemical analyses, consisted of a single specimen of electrowon cerium. It was included in the examination for purposes of comparison. Table I contains the chemical and spectrographic-

Jan 1, 1968

By W. F. Hergert, L. H. Banning

Experimental production of Al-Si alloys, containing from 33 to 55 pct Al, by direct reduction of aluminum silicates in a three-phase arc furnace is described. Advantages of a smelting technique utilizing hogged wood waste as part of the reductant and for temperature control are discussed. WORK on the problem of producing aluminum by smelting has been in progress since the middle of the eighteenth century. Early work met with little success and in 1782 Lavoisier, an eminent French chemist, expressed the belief that alumina could not be reduced by carbon. It was almost a century later when the Cowles brothers developed a process for the production of aluminum alloys by reducing alumina coincident with the reduction of other metal oxides. In practice, the other metal oxide was usually copper. In 1907 it was first shown that alumina alone could be reduced by carbon at a temperature of 2200°C. The metal produced was volatilized and lost or recombined with the oxides of carbon formed in the reaction.' For a number of years after the Cowles brothers abandoned production of Cu-A1 alloys because their product was not commercially competitive with the aluminum produced by the Hall process, there was little interest in thermal reduction processes. After World War I interest in such processes was renewed and a number of patents were issued on processes for the production of A1-Si alloys.' , "he function of the silicon in these processes was the same as the function of the copper in the Cowles brothers process, namely, to prevent the reduced aluminum from recombining with the oxides of carbon and to promote absorption of the aluminum vapors set free at the high temperature required for the reduction reaction. The advantage of using silicon in place of copper for this function is that silicon has a higher boiling point (2600"C) than copper (2310"C) and its oxides, combined with aluminum oxides, occur in nature in almost unlimited quantities. No A1-Si alloys have been produced commercially in the United States, as far as is known. However, considerable experimental smelting of aluminum silicate materials has been done by the TVA at Wilson Dam, Ala.' The most extensive development and commercialization of the electrothermal production of A1-Si alloys took place in Germany before and during World War II.V he furnaces used in the

Jan 1, 1956

By George J. Clark

One of the major problems of operation in the anthracite industry is the disposal and handling of refuse—not because of its complexity but because of the quantity and type of material involved. It is the purpose of this paper to describe the kinds of refuse, methods of disposal, quantities of material to be handled and equipment used, together with present day application at specific operations in the Northern, Eastern Middle, Western Middle and Southern anthracite fields. For the purpose of this paper, refuse is considered to be any material that has no present or foreseeable future value and that must be handled and disposed of in the process of mining and preparing anthracite for market. Included in this classification are tunnel rock, mine rock, cleaner plant refuse, breaker refuse, old timber, ashes and silt. Disposal Methods Old timber is disposed of either by burning or by depositing on the refuse bank. Burning is preferred because timber on the refuse bank is a potential fire hazard. Ashes are deposited on a separate bank, mixed with other refuse, or flushed into old mine workings. In many places, the latter practice has caused considerable difficulty in preparation of coal mined from these areas. In depositing ashes on the surface, it is wise to refrain from mixing them with material containing coal as such contamination may prevent reclamation of the coal in future years. Tunnel work, mine rock, cleaner plant and breaker refuse compose the bulk of the material to be disposed of and handled, and are referred to collectively as "refuse" in this paper. Waste material in or adjacent to the coal beds may be removed at the working face wherever possible. This can be done in flat or lightly pitching beds, and in the Northern field represents a sizable percentage of this type of refuse handled. In the other three coal fields, this method of disposal cannot often be used. Refuse not removed at the working face is taken to the surface and generally is deposited on banks; occasionally it is crushed and flushed into old mine workings. Breaker refuse often is used for constructing berms for silt-retention basins. Disposal Problems The problem of handling refuse is different for each operation, owing to topographical conditions, quantity of material to be handled, anticipated requirements and types of equipment in use elsewhere at the operation. Preparation plants with limited refuse-disposal areas, excessive grades to reach the required elevation and long hauls to disposal areas not readily accessible require the selection of equipment to best meet the conditions. The quantity of refuse to be handled from a given amount of raw material varies considerably throughout the four fields. In mine coal, this varies from a low

Jan 1, 1949

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 J. B. Newkirk, W. G. Martin

Oxidized cobalt powder is known to have a magnetic hysteresis loop which is asymmetric with respect to the magnetization axis. The experiment described herein shows that the orientation relationship between the basal plane of hexagonal cobalt and the oxide which forms upon it at 400°C is {111}ux//{100.1 }co <110>ux//<11.O> This orientation relationship allows a magnetic interaction between the antiferromagnetic oxide and the ferromagnetic substrate which could account for the offset hysteresis loop. Oxidized nickel powder has a symmetrical hysteresis loop and so is apparently not influenced by any magnetic interaction between metal and oxide. The orientation of the oxide (cubic) was found to be identical with that of the nickel substrate when the oxide forms on a polished surface parallel with {111} Ni. IN 1956 W. H. Meiklejohn and C. P. Bean discovered that fine particles of cobalt which had been prepared in a certain way have a magnetic hysteresis loop which in a strong field is asymmetric relative to the magnetization axis.&apos; The cobalt powder exhibited this unusual magnetic property only after it had been oxidized in air or oxygen; it lost the shifted hysteresis loop when the oxide was reduced in hydrogen. X-ray and neutron diffraction&apos; experiments showed the presence of cobaltous oxide (COO) and hexagonal cobalt in samples exhibiting the biased hysteresis loop and specifically showed no indication of any other compound with the exception of mercuric oxide.* The magnetic hysteresis loop becomes symmetrical above the Nee1 temperature (paramagnetic state) of COO. Therefore, it was concluded that the anomalous magnetic behavior is associated with the influence of cobaltous oxide upon the metallic cobalt. It has been proposed that crystallographic coherency may exist between the cobalt and a plane of some antiferromagnetic material which has unbalanced spin distribution and sufficient magnetic anisotropy to hold its spin in the direction which existed when the specimen was cooled. COO has these properties. Therefore, Roth&apos; has suggested that cobaltous oxide may form with a {111} plane parallel and coherent with the basal plane of the hexagonal cobalt metal and proposed that, as consequence of the antiferromagnetic interaction between COO and the underlying cobalt, the magnetization direction in oxidized fine Co particles may be ro-lated from the easy c-direction.2 Such a relationship, he proposed, would explain the observed magnetic effect in oxidized cobalt powder. The main purpose of this study was to determine the orientation relationship, if any, between the basal plane of cobalt and the oxide which forms upon it. Attempts to produce a film of COO which was strong enough to be handled were not successful. However we did succeed in making a film of CoCo2O, which was strong enough to be removed from the cobalt substrate and mounted on an electron-microscope grid. Because of the close structural similarity of COO and CoCo2O, we believe the orientation relation found for CoCo2O, on cobalt probably also holds for COO on cobalt. The epitaxial relationship of NiO and Ni also was investigated. To date no shifted hysteresis loop has been observed with nickel powder. However, the similarity of atomic array in cobalt and nickel leads to the prediction that a {111} of NiO may be parallel with a (111} of nickel. Experimental Method Cobalt-Cobalt Oxide—A coarse-grained specimen of a (hexagonal) cobalt was prepared by allowing a large crystal of fee cobalt to transform slowly at 400°C. The crystal was then cut to expose a surface parallel with the basal plane. A back reflection Laue X-ray photograph showed that the 00.1 plane was within 2" of the cut surface. The surface was mechanically polished and then electro polished in 85 pet orthophosphoric acid after which the crystal was held for 30 min at 400°C in air. During this heat-treatment the surface darkened slightly due to the oxide film which formed. The film was not thick enough to give an X-ray diffraction pattern, even by a glancing-angle technique. Glancing-angle electron diffraction was not possible either, owing to the interference of the electron beam with the high magnetic fields which exist at the 00.1 surface of the cobalt. However, it was possible to make an electron-diffraction photograph of the oxide film by stripping it from the cobalt substrate using the method described later. By maintaining reference marks carefully, it was possible to preserve the orientation relationship between the stripped film and the substrate on which it was formed. The oxidized surface of the crystal was first covered with a 1 pet solution of collodion (cellulose nitrate) in amyl acetate. When the film was dry, small rectangles were scored on the surface with a needle point. The specimen was then repolished

Jan 1, 1959