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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 Arthur Phillips

THE normal method of preparing metallic alloys for commercial use involves the preparation of a melt containing the given components in the chosen proportions and allowing the homogeneous liquid mass to solidify in a mold of the desired form. The solidification is frequently accompanied by a segregation of the alloying elements in different parts of the casting. When the segregation is occasioned primarily by marked differences in density of the solid and liquid phases, it is termed "gravity" segregation. When the segregation conforms to a. selective freezing in harmony with the teachings of the equilibrium diagram of the alloy system-i.e., the lower melting phases are concentrated in the regions of the casting last to freeze-it is often referred to as " normal" segrega-tion. However, in many cases the lower-melting part of the system is concentrated in the parts of the casting first to freeze and the result in this case is termed "inverse" segregation. To complete the. terminology of the subject, normal segregation in a single phase is usually called "coring" and the word will be used in that sense in this paper. Inverse segregation, particularly when the liquid phase is exuded or sweated out on the surface of the casting, is sometimes called "location." Unfortunately, some ambiguity has arisen from the use of this term and it is perhaps advisable to confine its use to the dictionary definition; namely, "The separation of two phases by heat sufficient to melt one but not the other." The gravity and normal types of segregation are both well understood and to some extent are controllable by taking advantage of the most favorable cooling rate for a given casting condition. Inverse segregation has received considerable attention from several investigators- but none of the theories offered seem to account in a convincing way for the many examples of this type. The observations made in the present work on segregation in single crystals, and in some other castings, tend to support one theory of the mechanism of inverse segregation and definitely to

Jan 1, 1937

By C. W. Dunham

FOR discharging and diffusing the gases from the reverberatory furnaces and converters the Morenci Reduction Works has been provided with one of the largest reinforced concrete chimneys ever built. It is 612 ft. high from the bottom of the foundation to the cap at the top, and has a minimum diameter of 24 ft. inside the lining near the top and 38 ft. 10 in. at the bottom. Its estimated capacity, at the elevation of 4338 ft. above sea level, is about 1,000,000 cu.ft. of gas per minute at a temperature of 500° F. and an atmospheric temperature of 90°. Under these conditions the draft will be at least 3 in. of water at the flue inlet. The gases enter the chimney through a steel balloon flue 33 ft. high and 15 ft. wide, the bottom of which is 19 ft. above the ground.

Jan 1, 1942

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 K. E. Brown, A. R. Hagedorn

A 1,500-ft experimental well was used to study the pressure gradients occurring during continuous, vertical, two-phase flow through 1-in., 1 1/4-in. and 1 1/3-in. nominal size tubing. The test well was equipped with two gas-lijt valves and four Mathak electronic pressure transmitters as well as with instruments to measure the liquid production rate, air injection rate, temperatures and surface pressures. Tests were conducted for widely varying liquid flow, rates, gas-liquid ratios and liquid viscosities. From these data, an accucrate pressure-depth traverse was construcred for each test in each of the three tubing sizes. From the results of these tests, correlations have beer] developed which allow the accurate prediction of flowing pressure gradients for a wide variety of tubing sizes, flow conditions, and liquid properties. Also. the correlations and equations which are developed satisfy the necessary condition that they reduce to the relationships approprate to single-phase flow when the flow rate of either the gas or the liqutid phase becomes zero. All the correlations involve only dimensionless groups. which is a condition usually Sought for in similarity analysis but not always achieved. The correlations developed in this study have been used to calculate pressure gradients for pipes of larger diameter than those upon which the correlations are based. Comparisons of these calcuclaed gradients with experimetally determined gradients for the same flow conditions obtained from the literature indicate that extrapolation to these larger pipe sizes is possible with a degree of accuracy sufficient for engineering calculations. The extent of this extrapolation can only he determined with additional data from larger pipe diameters. INTRODUCTION The accurate prediction of the pressure drop expected to occur during the multiphase flow of fluids in the flow string of a well is a wideiy recognized problem in the petroleum industry. The problem has been brought even more into prominence with the advent of tubingless or slim-hole completions which use small-diameter tubing. Many of the correlations which give reasonably accurale results in the lager tubing sizes are greatly in error when applied to small-diameter conduits. Small-diameter conduits are defined as 1 1/2-in. nominal size tubing or smaller. The study of the pressure gradients which occur during multiphase flow of fluids in pipes is exceedingly complex because of the large number of variables involved. Further difficulties relate to the possibility of numerous flow regimes of widely varying geometry and mechanism and the instabilities of the fluid interfaces involved. Consequently, a solution to the problem by the approach normally used in classical fluid dynamics based on the formulation and solution of the Navier-Stokes equation has not been forthcoming. This is primarily the result of the nonlincarities involved and the difficulty of adequately describing the boundary conditions. As a result of the foregoing, most investigators have chosen semi-empirical or purely empirical approaches in an efford to obtain a practical solution to the problem. Much of the previous work in this area was done in short-tube models in the laboratory. A number of problems arise, however, when attempts are made to extrapolate these laboratory results to oilfield conditions where a much longer tube is encountered. In those few studies where data taken in long tubes were utilized, the data covered only a limited range of the variables, and as a result inaccuracies are introduced when the correlations are extended outside the range of the original data. Also, as a consequence of the limited amount of data available for these studies, the effects of several important variables were overlooked. The problem of predicting the pressure drop which occurs in multiphase flow differs from that of single-phase flow in that another source of pressure loss is introduced, namely, those pressure losses arising from slippage between the phases. This slippage is a result of the difference between the integrated average linear velocities of the two phases, which in turn is due to the physical properties of the fluids involved. In contrast to single-phase flow. the pressure losses in multiphase flow do not always increase with a decrease in the size of the conduit or an increase in production rate. This is attributed to the presence of the gas phase which tends to slip by the liquid phase without actually contributing to its lift. Many investigators have attempted to correlate both the slippage losses and the friction losses by means of a single energy-loss factor analogous to the one used in the single-phase flow problem. In an approach of this type, hourever, many of the important variables, such as

Jan 1, 1966

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 G. V. Raymor, James T. Waber, I. Rex Harris

The lattice parameters of a series of fcc alloys of cerium and thorium were measured at 93 " and 298OK. Lattice parameters were also estimated for 171OK. Substantial deviations, y, from Vegard's law were observed. Although y was negative at the two higher temperatures, it was positive and large at the lowest temperature. A variety of models, which have been proposed in the past, were considered, and the calculated values of y were compared with the observed values. The best agreement was achieved with values computed with Friedel's equation. THE purpose of this investigation was to determine the effect of temperature on the lattice parameter and on deviations from Vegard's law of Ce-Th alloys. A large negative deviation from Vegard's law was first observed independently by Weiner, Freeth, and Raynor' and Van vucht2 in the room-temperature lattice parameters of Ce-Th alloys that form a continuous series of solid solutions. This observation was confirmed by Evans and Raynor. The allotropy of unalloyed cerium was reviewed recently by Gschneidner, Elliott, and McDonald. In two subsequent papers,5" these authors reported the influence of various alloying additions on the y= transformation, which occurs below room temperature. Although other rare earths tend to stabilize the double-hexagonal phase, thorium, plutonium, and scandium as solutes tend to stabilize the normal fcc phase. With addition of sufficient thorium as a solute, there is evidence that the formation of is suppressed and it becomes possible to pass continuously with decreasing temperature from the room-temperature phase to the fcc a phase. Thus there is a closed loop which is similar in many ways to the y loop well-known in ferrous alloys. A closed field also occurs in the pressure-temperature "equilibrium" diagram of unalloyed cerium. Because of interest in the effect of thorium additions and their influence on the a and phases, lattice-parameter measurements were made at low temperatures on the fcc phase for a series of alloys ranging from 10 to 90 at. pct Th. The results obtained at three temperatures are shown in Fig. 1. Evans and Raynors analyzed the deviations from Vegard's law in Ce-Th alloys in terms of changes in the occupancy of the 4f electron level in cerium,

Jan 1, 1964

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 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 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 O. B. Bucklen, P. G. Meikle

INTRODUCTION The trend in the coal industry for many years has been to make every- thing "bigger and faster." This also held true for loading and storage facilities. Where once a million ton per year mine was rare, three to five million ton per year mines are not uncommon today in the bituminous industry. This greatly increased production, made possible through mechanization, required greatly improved loading facilities just to get the coal away from the mine. Also, there is a trend toward combining production from more than one mine and cleaning it in a single preparation plant. In addition to increased loading capacity, this frequently necessitates raw coal storage and blending facilities. The development of the unit train with its attendant economics, more than any other factor, has contributed to the widespread construction of storage and high-speed loading facilities. In the export market, the construction of ever larger coal colliers has contributed to a need for faster and larger loading facilities. In this climate of rapidly changing technology, any written account is faced with the possibility of obsolescence before its appearance. Thus, this chapter seeks to define the common and current practice in coal loading and storage facilities with the full knowledge that this practice is an ever-moving target. FUNDAMENTALS OF COAL STORAGE Storage of coal is becoming an increasingly important part of coal handling systems at mines, particularly since the advent of the unit train concept in transportation. In order to take advantage of reduced transportation rates on trainload shipments of coal offered by unit train movement, operators have found that storage is an economic necessity. In unit train practice large predetermined quantities must be loaded in relatively short periods of time as opposed to conventional practice where coal is loaded at a speed dependent on the production capacity of the mine and/or the cleaning capacity of the preparation plant. Two surveys of storage practices at mines reveal several objectives for storage.1, 2 Raw and/or clean coal storage is generally practiced in order to accomplish one, or a combination, of the following objectives: 1. To improve plant efficiency by distributing plant feed over the entire operating time, or to allow a preparation rate different from the production rate. 2. To limit interruptions of supply, ie, allow mine and plant to function independently with delays in one not affecting the operation of the other.

Jan 1, 1968

By Y. G. Shiau, J. E. Burke

Several attempts have been made to account for the fact that grains in a fully recrystallized metal will coarsen on annealmg. Two fundamentally different hypotheses have been advanced, with several variations of each. One school considers that the cause of grain growth is the surface energy of the grain boundary. The theory of Jeffriesl that grain size and grain size contrast control growth is an example. The second school considers the primary cause to be a difference in the lattice energy on either side of the grain boundary. The more perfect grains are considered to grow at the expense of their less perfect neighbors, with a decrease in free energy, and a consequent increase in the stability of the system. Burgers2 presents the case for the strain or lattice imperfection theory of grain growth quite completely. The latter theory is attractive, since there is no doubt that differences in lattice energy or lattice perfection can cause grain boundary migration. A recrystallization nucleus grows for this reason as was beautifully demonstrated by van Arkel and Ploos van Amstel.³ Although it is generally stated that grain growth does not precede recrystallization, several workers4-5 have shown that small strains may induce a single crystal in an aggregate to grow, or at least may cause some grain boundary migration. The origin and nature of the imperfections that are considered to be responsible for normal grain growth have never been clearly described, but it is generally agreed that they are a consequence of the difficulty of atomic reorientation in the solid state, and that they do not seriously differ from the type of imperfection that can be introduced by mechanical deformation. An object of the present work was to determine whether the introduction of mechanical deformation would cause grain growth in a specimen which would not otherwise show it under the conditions used. It was also planned to determine the effect of such deformation on the rate of growth in a specimen which would show growth in the unstrained condition. Recently Maddigan and Blank6 have indicated that slightly strained specimens of alpha brass can undergo considerable growth prior to recrystallization if annealed at low temperatures. French7 has reported that at deformations less than 17 pet it is very difficult to detect the beginning of recrystallization in the same material. It was therefore planned to broaden this work to include a complete study of the microscopic behavior of alpha brass under condition~ of temperature, time, grain size and deformation such that recrystallization would not occur or would occur to only a Small extent. Experimental Procedure The brass was prepared by melting cathode copper and commercially pure zinc

Jan 1, 1949

By J. E. Burke, Y. G. Shiau

Several attempts have been made to account for the fact that grains in a fully recrystallized metal will coarsen on annealmg. Two fundamentally different hypotheses have been advanced, with several variations of each. One school considers that the cause of grain growth is the surface energy of the grain boundary. The theory of Jeffriesl that grain size and grain size contrast control growth is an example. The second school considers the primary cause to be a difference in the lattice energy on either side of the grain boundary. The more perfect grains are considered to grow at the expense of their less perfect neighbors, with a decrease in free energy, and a consequent increase in the stability of the system. Burgers2 presents the case for the strain or lattice imperfection theory of grain growth quite completely. The latter theory is attractive, since there is no doubt that differences in lattice energy or lattice perfection can cause grain boundary migration. A recrystallization nucleus grows for this reason as was beautifully demonstrated by van Arkel and Ploos van Amstel.³ Although it is generally stated that grain growth does not precede recrystallization, several workers4-5 have shown that small strains may induce a single crystal in an aggregate to grow, or at least may cause some grain boundary migration. The origin and nature of the imperfections that are considered to be responsible for normal grain growth have never been clearly described, but it is generally agreed that they are a consequence of the difficulty of atomic reorientation in the solid state, and that they do not seriously differ from the type of imperfection that can be introduced by mechanical deformation. An object of the present work was to determine whether the introduction of mechanical deformation would cause grain growth in a specimen which would not otherwise show it under the conditions used. It was also planned to determine the effect of such deformation on the rate of growth in a specimen which would show growth in the unstrained condition. Recently Maddigan and Blank6 have indicated that slightly strained specimens of alpha brass can undergo considerable growth prior to recrystallization if annealed at low temperatures. French7 has reported that at deformations less than 17 pet it is very difficult to detect the beginning of recrystallization in the same material. It was therefore planned to broaden this work to include a complete study of the microscopic behavior of alpha brass under condition~ of temperature, time, grain size and deformation such that recrystallization would not occur or would occur to only a Small extent. Experimental Procedure The brass was prepared by melting cathode copper and commercially pure zinc

Jan 1, 1949

By F. R. Hensel

PuRe silver and silver-lead alloys have been studied as to their suitability for bearing~.' A review of the properties of thallium and the silver-thallium constitutional diagram was made by the author to analyze the possibilities of silver-thallium compositions for antifriction materia1s. t The silver-rich end of the diagram as reported in the literatureg-" was found to be sketchy and it was necessary to carry out corisiderable experimental work to arrive at definite conclusions. Some of the results of this work are reported in this paper. Test Materials In the beginning of the work, only fused alloys were investigated. Later, research Table i.—Composition of Fused Silver-thallium Alloys Tested for Antifriction Properties Percentage Alloy No. of Thallium 1533...................... 0.48 1534.................... 1.06 a31 HT................... 2.04 231....................... 2.10 232 HT................... 3.83 Balance 232....................... 4.07 Silver 233 HT................... 5.86 a33....................... 6.38 a34....................... 9.84 a34 HT................... 10.07 was carried out on electroplating methods and diffusion processes. In preparing the fused alloyst care was taken to exhaust the toxic fumes caused by the thaillium content. The compositions of the series of fused alloys are listed in Table I. The silver-thallium alloys were melted in clay-graphite crucibles and cast into preheated steel molds of 3/4-in, diameter. In the cast condition, they showed a cored structure, as indicated by the micrographs of Figs. I to 3. The etching reagent used was a mixture of 2 grams K2Cr207, 8 C.C. H2S04, and IOO C.C. H20. The cored structure is unsatisfactory for the type of corrosion resistance required for bearing applications, and homogenizing experiments were carried out at various temperatures, the results of which are shown in Figs. 4 through 8. The alloys with a lower thallium concentration, which were heated for 2 hr. at 525°C show an almost completely homogenized solid solution type of structure. With higher thallium concentration, the homogenizing temperature was dropped to 475OC. to eliminate the formation of a liquid phase. It is evident that heating for 2 hr. at this temperature did not iesiilt iii complete elimination of the cored structure. As would be expected, cold-working of the cast structure is an expedient in establishing equilibrium conditions. The fine homogeneous grain structure shown in Fig. 7 corresponds to the cold-worked area under the Rockwell ball penetration when the hardness was taken before heat-treatment. A detailed structural study was made on a cast silver-thallium alloy containing 3.67 per cent thallium. Three micrographs (Figs. 9, 10 and 11) show the transition

Jan 1, 1946

By F. R. Hensel

PuRe silver and silver-lead alloys have been studied as to their suitability for bearing~.' A review of the properties of thallium and the silver-thallium constitutional diagram was made by the author to analyze the possibilities of silver-thallium compositions for antifriction materia1s. t The silver-rich end of the diagram as reported in the literatureg-" was found to be sketchy and it was necessary to carry out corisiderable experimental work to arrive at definite conclusions. Some of the results of this work are reported in this paper. Test Materials In the beginning of the work, only fused alloys were investigated. Later, research Table i.—Composition of Fused Silver-thallium Alloys Tested for Antifriction Properties Percentage Alloy No. of Thallium 1533...................... 0.48 1534.................... 1.06 a31 HT................... 2.04 231....................... 2.10 232 HT................... 3.83 Balance 232....................... 4.07 Silver 233 HT................... 5.86 a33....................... 6.38 a34....................... 9.84 a34 HT................... 10.07 was carried out on electroplating methods and diffusion processes. In preparing the fused alloyst care was taken to exhaust the toxic fumes caused by the thaillium content. The compositions of the series of fused alloys are listed in Table I. The silver-thallium alloys were melted in clay-graphite crucibles and cast into preheated steel molds of 3/4-in, diameter. In the cast condition, they showed a cored structure, as indicated by the micrographs of Figs. I to 3. The etching reagent used was a mixture of 2 grams K2Cr207, 8 C.C. H2S04, and IOO C.C. H20. The cored structure is unsatisfactory for the type of corrosion resistance required for bearing applications, and homogenizing experiments were carried out at various temperatures, the results of which are shown in Figs. 4 through 8. The alloys with a lower thallium concentration, which were heated for 2 hr. at 525°C show an almost completely homogenized solid solution type of structure. With higher thallium concentration, the homogenizing temperature was dropped to 475OC. to eliminate the formation of a liquid phase. It is evident that heating for 2 hr. at this temperature did not iesiilt iii complete elimination of the cored structure. As would be expected, cold-working of the cast structure is an expedient in establishing equilibrium conditions. The fine homogeneous grain structure shown in Fig. 7 corresponds to the cold-worked area under the Rockwell ball penetration when the hardness was taken before heat-treatment. A detailed structural study was made on a cast silver-thallium alloy containing 3.67 per cent thallium. Three micrographs (Figs. 9, 10 and 11) show the transition

Jan 1, 1946

By F. Keller, J. D. Edwards

THE anodic treatment of aluminum presents problems of scientific as well as of commercial interest.1-3 Of particular interest is the fact that, during the anodic oxidation process, the oxide continues to form at the metal-oxide interface under any oxide previously formed. This has led to speculation as to the mechanism involved in the formation of the relatively thick oxide coatings that are used commercially for decorative or protective purposes. Furthermore, the ability of certain types of oxide coatings to adsorb dyes and other substances has stimulated research to determine the actual structure of these adsorptive coatings. It has been found that anodic oxide coatings on aluminum are composed essentially of aluminum oxide. They are formed by the action of oxygen ions penetrating to the metal surface during the electrolytic oxidation treatment. These coatings can be formed in a number of different electrolytes, as for example, those which contain sulphuric acid, chromic acid, oxalic acid, or boric acid. These are the commonest and most useful electrolytes employed commercially. Except for certain specific conditions of formation, the coatings in general have been found to be amorphous alumina, as far as can be determined by X-ray or electron-diffraction methods. Anodic oxidation processes can be arranged in three rather general classes if they are grouped in relation to the solvent action of the electrolyte on the coating.4 In the first class, the electrolyte has little or no solvent action on the coating that is formed. In general, coatings produced under such circumstances are nonporous and non- adsorptive. In the second class, the electrolyte exerts an appreciable solvent action on the coating. These coatings are porous and adsorptive. Finally, for the third class, the electrolyte tends to dissolve the coating about as rapidly as it is formed. This action produces electrolytic brightening or anodic polishing of the aluminum surface and at most leaves only a very thin film of oxide. The nonporous and nonadsorptive type of oxide film is represented by the coatings that are formed when solutions of boric acid are employed as the electrolyte. It is especially significant that these impervious films are formed in electrolytes that exert little or no solvent action on the coating. Where a boric acid electrolyte is used, the coating tends to form rapidly, with the result that the flow of current is soon reduced to substantially zero. This indicates that the growth of the coating has stopped. As a rule, the thickness of the coating is roughly proportional to the voltage employed for formation and the coatings of this type are exceedingly thin. In an electrolyte of this type, the coating has a high resistance when the aluminum is made anode; consequently, any current that may flow (leakage current) is very

Jan 1, 1944