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By Chandler Morse

RENEWABLE VS. NONRENEWABLE NATURAL RESOURCES Nonrenewable resources, such as minerals, are the inevitable center of attention in discussions of depletion and exhaustion. Nevertheless, it may well be proper to regard some nonrenewable resources as not subject to exhaustion, and renewable resources may sometimes be treated as if they were finite stocks. Thus, the availability of nonrenewable resources is not and probably never will be known completely Chap. 2.5A, and therefore is not subject to firm predictions concerning exhaustibility. Moreover, because exploration and discovery are more or less continuous processes it is often appropriate to regard mineral supplies as flows, and to treat the estimated reserves as working capital, an inventory, continually depleted by use and augmented by discoveries.23 The aggregate economically exploitable stocks of a given mineral are seldom estimated (or estimatable) with precision, as Chap. 2.5A shows, and even when they are, forecasts concerning years of remaining life can be and often are falsified by changes in one or more of the multidimensional conditions of supply and demand; or the productive services formerly derived from an exhausted stock may continue to provided without material impairment by one or more substitutes b Conversely, the renewable resources are all subject to depletion when the rate of use exceeds the natural or induced rate of replenishment, and cases of exhaustion or near exhaustion, as through soil erosion, overcuttmg of forest lands, and overfishing, are rather common c Where exhaustion is a clear possibility the resource may either be exploited on a consciously adopted "sustainable yield" basis or be treated as an exhausting asset." In some cases, conscious treatment

Jan 1, 1976

By M. H. Waxman, M. Gondouin, H. J. Hill

Streaming-potential experiments were conducted within the Muddy- and Dakota-sandstone interval of a Denver basin well. Analysis of the data shows that, for this case, streaming potentials opposite sands were higher than those opposite shales when the mud was fresh. Streaming potentials opposite shales, however, were of sufficient magniiIlde to be important in SP interpretation. They were linearly dependent upon pressure differential, and they increased with mud filtrate resistivity. The magnitude of streaming potentials opposite sands was influenced by the characteristics of the original mud cake formed at the time of drilling. Use of mud samples taken at the time of logging may not always be satisfactory for determining streaming-potential corrections. Both the streaming and electrochemical potentials were found to be affected by the previous history of the borehole system. Following a change in mud characteristics, several days were required for SP stabilization. This was, in part, due to the mud cake acting as an imperfect shale membrane. INTRODUCTION Laboratory investigations by Wyllie,1 Salisch,2 Moore," Sen Gupta and Bannerjee,0 and Hill and Anderson' have shown that streaming potentials developed across mud cakes deposited on permeable filter beds are of sufficient magnitude to be critically important in SP interpretation. Streaming potentials across shales have been reported by Schenck,' Gondouin and Scala; and Hill and Anderson." The magnitude of the shale streaming potentials obtained by Schenck and by Gondouin et a1 led these authors to conclude that in many cases the shale streaming potential would approximately equal the mud-cake streaming potential. Hill and Anderson, however, obtained somewhat lower magnitudes of shale streaming potential. The field experiment described in the present paper was a cooperative project carried out by the respective operations and research departments of Schlumberger Well Surveying Corp., Shell Development Co. and Shell Oil Co. The primary objective of the experiment was to determine in the borehole the streaming-potential behavior of both shales and mud cakes under conditions approaching, as nearly as possible, those normally encountered in logging practice. METHODS AND EQUIPMENT WELL A Muddy- and Dakota-sandstone vie11 in the Denver basin was chosen for the experiment. Both sandstones were water-bearing and, since reservoir pressures in these sandstones are abnormally low (gradient of approximately 0.25 psi/ft), it was expected that studies of streaming potential could be conducted from low-pressure differentials (approximately 200 psi) to about 27000 psi by bailing mud from the hole, filling up and then applying wellhead pressure. The selected well encountered the Muddy sand-

By C. O. Rison

HIGH explosives, particularly nitroglycerin, have been used in torpedoes for the purpose of shooting oil and gas wells for more than 60 years. The early history of the oil industry in Pennsylvania is not clear as to who actually torpedoed the first well, although in 1865 the Roberts Torpedo Co. procured a patent covering the process. Gunpowder was first used, although nitroglycerin was substituted shortly afterwards. Wells are shot for the purpose of increasing the flow of oil and gas A shot-hole in the producing horizon, with its contributory fissures and fractures, increases the area of and stimulates drainage into the hole. The shot-hole also acts as a collecting basin from which the oil is pumped. As a rule, hard or close-grained sands or limes are shot, other more or less porous and soft formations usually do not require shooting. and might be injured by blasting. Shooting is also resorted to in mechanical trouble such as straightening crooked holes, sidetracking pipe or tools, and for severing frozen strings of casing or drill pipe. Explosives arc also used sometimes to extinguish oil or gas-well fires although that work, which involves unusual conditions and methods, does not properly come within the classification of oil-well shooting. Some Factors to Be Considered in Shooting Wells Although nitroglycerin has been used extensively for more than half a century in shooting oil and gas wells, there is still a great deal of uncertainty as to the proper method of shooting or the amount of explosive required to produce best results in a particular formation. The possibility of shooting unproductive or cavey formations above or below the productive horizons, shooting into lower water, destroying casing seats, and the splitting or collapsing of casing strings, are factors that require consideration. The engineering departments of a number of the larger oil companies are making a study of methods of shooting, and the amounts of liquid nitroglycerin or other explosives required in shooting various productive

Jan 1, 1929

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 Charles P. Williams

The lead-bearing area of Missouri has been subdivided, geographically, into the Southeastern, the Central, and the Southwestern

By S. Norton

GEORGE C. FOOTS, Port Henry, N. Y. (written discussion).-The paper by Mr. Norton and Mr. LeFevre will bear the most careful consideration by all interested in the iron business, particularly in the East. There is much information contained therein which should be emphasized. The idea of handling iron-bearing rock in quantities comparable to the porphyry coppers does seem at first blush to be beyond the pale of commercial possibility. Yet, today in the Adirondack region 25 per cent.

Jan 4, 1917

By S. K. Asunmaa, W. D. English, N. A. Tiner, W. A. Cannon

This paper discusses the reaction of metal surfaces with fluorine. Fluorination reactions result in the formation of metal fluoride films which are "passive" toward further reaction of the metal with fluorine. These films are very adherent, and do not easily detach from the substrate metal by mechanical flexing or thermal shock. Exposure of passive films to a humid atmosphere produces hydrated metal fluorides which cause secondary fluorination reactions upon reexpo-sure of the metal surface to fluorine. The surface films formed range from 10 to 30A in thickness and they pow at the expense of surface oxide films. The apparent film formation is completed rapidly in 15 to 30 min on stainless steel and nickel surfaces. On copper and on Monel surfaces, the film at first grows rapidly, then increases slowly over an extended period of time. Passive films are formed at all fluorine pressures in the range from 0.1 to 1.4 atm at room temperature. ALL metals react when exposed to fluorine. These reactions generally produce surface films which consist of metal fluorides. The rate of reaction is largely determined by the extent to which these films are protective. Although there is an extensive literature concerning reactions of oxygen with metals, there are very few investigations reported concerning fluorine-metal reactions. Brown, Crabtree, and ~uncan' investigated the kinetics of the reaction of gaseous fluorine with copper metal which had been freshly reduced in hydrogen. The reaction rate was independent of pressure over the range from 6 to 60 torr. A logarithmic rate law was obeyed in the temperature range from 25" to 300" ~. There was some deviation at higher temperatures which could have been the onset of a parabolic law. The calculated film thicknesses ranged from about two molecular layers, 10A, for 5 hr exposure at room temperature to thirty-five molecular layers for 5 hr exposure at 200" . The authors concluded that no single mechanism could explain all the observations. O7Donnell and spatkowski2 studied the reaction of fluorine with copper at 450°C at pressures from lo to 133 torr. The reaction was found to be pressure -dependent and followed a logarithmic rate law. It was not entirely diffusion-controlled, and fluorine was thought to be the migrating species in the reaction. Miscellaneous metal-fluorine reactions were investigated by Haendler et ~1.~ Reaction products were identified but no rate data were determined. Air Prod- ucts and Chemicals, Inc., have conducted an investigation of reactions between fluorine and various metal powders at room temperature and 85° C. Fluoride film thickness as a function of time of exposure was reported on the assumption that the reaction takes place between fluorine and metal to form the normal metal fluoride. Surface areas of the powders were only estimated so the relative film thicknesses may not be exact. The data showed reaction rates which were generally logarithmic in character, the rate of film growth virtually ceasing after a few hours exposure time for some alloy powders. The effect of moisture on fluoride films was also investigated by measuring additional reaction with fluorine after exposure of passivated powders to atmosperic moisture. The fluorination of iron was studied by 0'~onnell~ at temperatures from 225" to 525" ~ and at pressures ranging from 20 to 200 torr. In all ranges, the reaction followed a logarithmic rate law and was dependent on the square root of the gas pressure. The author concluded that fluorine gas passes through pores in the film. As the film grows, the blocking of pores leads to a rapid decrease in reaction rate; hence a logarithmic rate law is observed. Jarry, Fischer, and Gunther' investigated the mechanism of the reaction of fluorine with nickel at about 600" to 700°C. On the basis of the metallographic examination of fluoride scales growing on the nickel and from separate radioautographic data, it was claimed that fluorine is the migrating species in the reaction. This is in sharp contrast to the growth of oxide films on nickel where it has been shown that nickel ions migrate through the scale to the gas-solid interface to react with oxygen. Few investigations have been reported of the reaction of fluorine with metal oxides. Such investigations should be of great significance for a better understanding of passivation in view of the ubiquitous oxide films on technical alloys. Haendler et al.3 studied the reaction of fluorine with oxides of copper, tin, titanium, zirconium, and vanadium. Copper (I) oxide reacted as follows in the temperature range 150" to 300"~: temperature above 300" ~ was required for the CuO to react to form additional copper fluoride. Ritter and smith7 also investigated the reaction of fluorine with copper (11) oxide. An oxide powder comprised of spherical particles with a fairly high surface area was reacted with fluorine, starting at room temperature and increasing to 100° C over a period of 3 or 4 hr. The initial reaction was slow until the fluoride film thickness reached about to or 15R at which time the reaction rate accelerated, then decreased again. Most of the kinetic data was obtained during this final phase of reaction. The authors conclude that the film grows slowly at first until the stresses developed in the distorted lattice are sufficient to rupture the initial

Jan 1, 1969

By S. P. Rothwell

ABOUT thirty miles north of, the city of Belleville (which is situated on a branch of Lake Ontario), and in the township of Marmora, Ontario,: there is found a. belt of gold-bearing quartz veins, which present geological, mineralogical, and economic features of great interest to the profession. The district in which these veins are found is characterized as a rolling country, with low rounded bills of syenitic granite, overlain on the flanks of the hills by Silurian limestones, which lie in nearly horizontal beds, and in some places are so fine in texture as to afford lithographic stone of a fair quality. The gold-bearing veins run north and south through this belt of syenitic granite, and are quartz-filled true fissures, with micaccous or talcoid slates forming the walls of and horses in the veins. This

Jan 1, 1881

By E. A. Gulbransen, J. W. Hickman

IN a previous paper1 the authors have investigated the structure of the oxide films formed on most of the metals that make up the alloys of this study. The metals were studied in order to provide basic information on the structures, both physical and chemical, of the oxide films and to determine how these structures are effected by the temperature, time of oxidation, and surface preparation. It was felt that an understanding of the physical and chemical structure as well as the stability of the oxide film might furnish clues as to the nature of the reaction process and the protective quality of the film. The oxidation of the metals was studied over the temperature range 300° to 700°C. except for copper, where the range selected was 100° to 500°C. The results of these studies were presented in graphical form as existence diagram, of the oxides on a time-temperature scale. For some of the metals the existence diagrams were simple and showed few chemical transitions, but there were numerous cases where the physical state of the oxide surface was a function of time and temperature. In general the physical state of the oxide surface changed with increasing temperature so as to increase the sharpness of the diffraction patterns and to cause orientation effects to be more pronounced. Deviations in lattice parameters from X-ray values were noted. In general these deviations were of positive nature and may be due to solid solution of the metal in the oxide lattice. This effect might be expected in thin oxide films. In a study of the oxidation of alloys containing two or more metals, there may arise the complicating factor of identification of the oxides formed. A thorough understanding of the oxides formed on the pure metals, therefore, was, essential before investigation of the oxidation of alloys. In this paper it is our purpose to present a study of the following problems: I The existence diagrams of various alloys. [2.] The effect of the structure of the [ying] metal on the existence diagram of Iron. 3. The effect of the percentage of chromium on the oxides formed on Fe-Cr alloys. 4. The relationships, if any, between the oxides formed and the protective quality of the oxides. The following alloys are included in this study: alloys of iron with body- centered cubic, face-centered cubic and other metals, 13 Cr-Fe, 18-8 stainless steel, K42B1 Nichrome V, Hipernik, Inconel, Stellite " 21," Refractaloy, Kovar, mild steel, a series of Cr-Fe alloys and a series of Co-Fe alloys. Since many of the commercial alloys in this list contain more than two metals, various complicating factors in the identification of the oxides formed may arise.

Jan 1, 1946

By R. P. Smith

The diffusivity of carbon in iron, cobalt, and alloys of 89.7 and 79.3 wt pct Co has been determined by a decarburization method for the temperature range 850° to 1100°C. The Plots of log D us 1/T for the two Fe-Co alloys are linear through the region of the Curie temperature, showing that, unlike some cases of substitutional diffusion, carbon diffusion in these alloys is not affected by electron spin order. RECENT investigations1-' have shown that for substitutional diffusion in iron the change in diffusivity with temperature does not follow an Arrhenius equation, at temperatures near the Curie temperature. Data on the diffusivity of carbon in a iron5"9 indicate that this anomaly does not exist for interstitial diffusion; however, this has not been definitely established. Since cobalt and Fe-Co alloys, 80 to 100 pct Co, have Curie temperatures in a temperature range convenient for carbon-diffusion measurements they are suitable systems for studying the relation of interstitial diffusion and the Curie temperature. EXPERIMENTAL The carbon diffusivity, D, was determined by a decarburization method. The diffusion cylinders, made from small vacuum melts of electrolytic cobalt and plastiron, were about 0.76 cm diam and 6.3 cm long. A small amount of carbon was added to each melt to keep the oxygen content as low as possible. The cylinders were first treated with a hydrogen-3 pct water vapor mixture at 1100°C to constant weight, then carburized to the desired initial carbon content with a suitable CO-C02 gas mix-

Jan 1, 1964

By F. S. Young, K. E. Gray

Drilling tests with a 11/4-in. diameter roller bit were performed on Berea and Bandera sandstones and Leuders limestone using water and two conventional drilling muds as circulating fluids to evaluate the influence of dynamic filtration on penetration rate. The muds possessed widely differing API fluid-loss properties. Mud filtrate was constrained to flow beneath the bit; no filtrate flowed radially through the borehole wall. Rock pore pressure at three different locations ahead of the bit, cumulative filtrate volume, borehole pressure and bit location were monitored during drilling. The rock samples, cored in three orientations with respect to bedding planes, possessed a wide range of liquid permeabilities. and were drilled at borehole-to-formation pressure differentials of 0, 250, 500 and 1,000 psig. The effect on penetration rate of API fluid loss, borehole pressure and rock permeability was studied. Rock permeability damage and pore pressure gradients beneath the bit were evaluated. The importance of borehole-to-formation pressure differential was illustrated for each drilling fluid and rock permeability combination. Penetration rates decreased with increased borehole pressure and reduced fluid loss. The observed penetration rate reduction due to changing fluid Ioss was attributed to decreased filtrate flow and improved mud cake plastering hy the low fluid-loss mud. The reduction in filtrate flow could not be related to spurt-loss phenomena. Rock permeability influences penetration rate through particle invasion ahead of the hit, which damage leads to high pressure gradients. Penetration rate variance with sample orientation was evident for water-drZled samples but less obvious for mud-drilled rocks. Permeability damage beneath the bit ranged from 1 to 3 cm. Maximum damage occurred in the first 0.1 cm. Pressure gradients varied with API fluid 10.s.s and could be correlated with penetration rate. The pressure gradient was found to influence penetration rare in rocks of all permeabilities tested. INTRODUCTION Early microbit and small-scale drilling experiments proved to be invaluable contributions to understanding the mechanics of drilling at depth. For example, the effect of borehole-to-pore pressure differential on drilling rate was demonstrated conclusively by Murray and Cunningham', Eckel' and others .' However, the effects of various drilling fluid properties on drilling rate, particularly filtration, have not been studied extensively on a laboratory basis. Microbit correlations of penetration rate with different viscosity and API fluid-loss muds led EckelV o conclude that viscosity and density. more than API fluid loss, were the most important fluid properties in controlling drill bit penetration rates. Ferguson and Klotz6 studied filtration beneath the bit and stated that the maximum amount of filtrate which could conceivably flow beneath a drilling bit could be described by a potential function associated with flow from a moving disc source. and be characterized by a depth-of-filtrate invasion. Invasion depth is a function of penetration rate, formation porosity and permeability, flooding efficiency, pressure difference between borehole and formation and borehole radius, assuming that no filtrate flows through the borehole walls. Electric analog and experimental measurements were obtained, assuming no plugging of the formation pores. Theoretically, filtrate invasion was predicted to extend from 1- to 15-hole radii beneath the cutting surface; experimental results indicated that the extent of invasion was only Y2 in. Comparing these data with results of core-plugging experiments by Norwak and Krueger' led Ferguson and Klotz to state that the drilling operation apparently contributes to higher filtration rates than are observed in nondrilling core filtration tests in which the core face is jetted and scraped. Glenn and Slusser: in describing a linear filtering system in which a rotating bit continuously scraped mud cake from the surface but did not penetrate Alundum cores, stated that mud-solids invasion and permeability damage of the cores were most severe in the first 2 to 3 cm. The filtrate flow rate through the core was found to stabilize after sufficient time had elapsed for the formation of an internal mud cake whose effective permeability was estimated to be 50 to 300 times as high as that of bulk filter cake. Krueger and Vogel reported core permeability damage depths up to 12 in. during a 5-day exposure period in which filter cake buildup was prevented. Havenaar pointed out that the discrepancy between reported and calculated values of filtrate volume obtained in the experiments of Ferguson and Klotz was due, among other things, to failure of the reported API fluid loss to truly represent filtration beneath the bit. Williams," Pro-koplz and others"" have shown that dynamic filtration tests (where a flow of fluid parallel to the filter surface continually erodes the deposited filter cake until a dynamic equilibrium between wall-shearing forces and normally directed compaction forces is attained) yield higher filtration rates than do static tests. Cunningham and Goinss reported results of drilling tests in impermeable shales. They found that by reducing

By Frank Tolonen

IRON-ORE beneficiation is becoming of vital importance to the Lake Superior region, since only a few decades will be needed to exhaust the direct shipping ores even if generous allowances are made for discoveries of new orebodies. If the region is to continue as the chief source of ore to the steel industry of the United States, it must concentrate or otherwise beneficiate the enormous tonnages of available iron formations. A beginning along this line has already been made. About one-fifth of the total shipment, even now, is the product of some sort of concentrating process, while another fifth is improved in physical structure by crushing, screening, drying, sintering, or some other similar method. The amount of material amenable to these processes is limited, however; and, in order to be able to utilize the billions of tons of iron formations that cannot be so beneficiated, an intensive study of their nature and concentration possi-bilities is necessary. As long as high-grade ores are available in ample quantities, ore dressing is economically impossible, but as soon as the supply nears exhaustion it becomes necessary. At first the products of ore dressing must meet as nearly as possible the same specifications as the rich ores in order to be adapted to the reduction processes already established. The future requirements as to quality will depend on the one hand upon the ability of the ore dresser to eliminate undesired constituents and charac-teristics in the material, and on the other upon the adaptation of the reduction processes to the product that can be economically supplied. A better understanding of the blast furnace and other reduction reactions, and improvements in the preparation of raw materials, should enable the Michigan districts to continue to supply ore for a long time to come. The study and testing of the iron formations necessary to bring a utilization of the low-grade ores, though requiring time and effort on the part of all concerned, should not be postponed, especially since the economic situation forces the use of the highest grade ore in preference to the leaner material.

Jan 1, 1933

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 Howard Reiss, C. S. Fuller

A theoretical and experimental study has been made of those interactions between holes and electrons which influence the solubilities of donors and acceptors in semiconductors. The major portion of the work concerns the solubility of lithium in silicon doped to varying degrees with boron. This solubility increases with increasing boron content in a manner predicted by theory and exhibits the expected temperature dependence. A qualitative experiment in germanium is described which demonstrates, in accordance with theory, that doping with a donor decreases the solubility of another donor. SEVERAL authors have discussed the possibility that holes and electrons behave like chemical entities and influence the solubilities of ionized impurities, Wagner was the first to invoke this concept in connection with his studies on nonstoichio-metric oxides. He used it again in explaining the solubility of hydrogen in molten binary alloys. In a theoretical paper,' Reiss drew attention to the fact that solutions of impurities in semiconductors

Jan 1, 1957

By Henry Rawdon

THE METHOD of demonstrating the structure existing in a metal or alloy at high temperatures, by etching a polished sample after it has been heated to the desired temperature, is quite familiar to metallographists. The usual procedure1,2 is to heat the specimen, previously polished for microscopic examination, to the desired temperature, in a neutral atmosphere (hydrogen or nitrogen), then admit the etching gas. (chlorine, hydrochloric acid or similar gas) for. a few seconds, and finally, after flushing out the etching gas with the neutral one, cool the specimen in the neutral atmosphere. The pattern produced by etching at a definite temperature is usually taken as a record of the microstructure prevailing at that temperature. It has frequently been pointed out that changes in composition of the surface metal occur during the preliminary heating in the neutral atmosphere, so that the appearance produced' by the etching at high temperature may not exactly represent the condition of the interior of the specimen. To overcome this uncertainty, the heating has sometimes been done in vacuo,3 the etching gas being ad-mitted when the desired temperature was reached, then pumped out and the specimen cooled in vacuo.

Jan 2, 1920

By J. B. Austin

IN considering so complex a process as the smelting of iron in the blast furnace, there is obviously no single method of calculating efficiency that gives a complete appraisal of the performance of the furnace in all its several functions; such a comprehensive view as is required to evaluate producing ability and manufacturing costs for a given furnace is obtained only by considering a group of efficiencies, each of which measures the performance of the furnace from a specific point of view. For instance, there is the rate of consumption of coke per ton of iron produced, which is probably the most frequently considered, and is certainly one of the most important of the group; there is the efficiency of recovery of iron charged; and there is the efficiency of utilization of energy, both chemical and thermal, in some respects related to the former two yet in other ways independent of either. In each of these cases, the calculation can be made on the basis of the actual input of material or energy, or it may be based . upon a comparison with the minimum amount of material or energy that would be required by a "perfect" furnace; that is, an imaginary ideal furnace analogous to the perfect steam engine used in thermodynamic calculations, when this furnace is operating under optimum conditions. Moreover, the furnace itself can be considered either as an apparatus for smelting iron or, taking a somewhat less common point of view, as a gas producer yielding iron and slag as by-products. Some of these effi-ciencies are more useful than others, yet all are instructive; for a knowl-edge of them not only leads to good engineering practice from the standpoint of control but also discloses limits to possible improvement in performance and indicates the lines along which improvement is most likely to be profitable. Estimates of some of these efficiencies have appeared from time to time in the literature, but many of them are open to objection because they are based on data of uncertain accuracy or because they have been calculated without due regard to the thermo-dynamic principles involved. Moreover, so far as the author is aware, no general survey of the blast furnace comparing its performance in all the aspects mentioned has been made.

Jan 1, 1938

By C. E. Shoenfelt

Jan 1, 1942

By C. E. Shoenfelt

Jan 1, 1942

By T. C. Campbell

Copper is extracted from the Chuquicamata oxide ore by a hydro-metallurgical process. The ore is crushed to 3/8-in. sizing, and leached with a sulfuric acid electrolyte. Chlorine is precipitated. and the ferric iron reduced in the enriched electrolyte, after which the copper is recovered by electrolysis with insoluble Chilex and lead-antimony anodes, the spent electrolyte being returned to leaching. Cathodes are melted and refined in market furnaces and cast into commercial wire-bar and cake shapes. Sulfuric acid for the process is supplied by the brochantite in the ore. Water for washing the ore is advanced through the solution system and finally after cutting by electrolysis to from 6 to 16.0 grams per liter is completely stripped by the cuprous chloride method and run to waste. The cuprous chloride so obtained plus that resulting from precipitation of chlorine from strong solution is dissolved in ferrous chloride brine and the copper cemented on scrap iron. The cement so obtained is in part used to reduce ferric iron in electrolyte, and as it is of exceptional purity is also furnace refined and cast into an exceptional quality of fire-refined copper. Fig. 1 is flow sheet of the operation. The reduction plant is composed of seven divisions as follows: (1) crushing, (2) leaching, (3) tailings disposal, (4) dechloridizing, (5) sulfur dioxide treatment, (6) electrolytic tank house, (7) smelting and melting. A brief description of each of these divisions will be given. Crushing Ore that is frequently blocky and up to 5 ft. in section is crushed in four stages to 3/8-in. mesh. The first stage of crushing is called primary and the next three stages are known as secondary crushing. The first stage is accomplished with two 60-in. Superior McCully gyratory breakers by which the ore is broken to 9 in. The second coarse gyratory breakers crush the ore to 3-in. sizing. There are seven No. 10 McCully gyratories in this service, for one of which recently has been substituted a No. 7 cone crusher. The third and fourth stages of crushing are accomplished by fifty 48-in. disk crushers. In the third stage 14 disk crushers break the ore to 1 in., and in the last stage 36 disk crushers turn out the final product of 0.371-in. sizing. Reference to the flow sheets of Figs. 2 and 3

Jan 1, 1934