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By G. H. Anderson

Cadmium-coppeR precipitate, a byproduct of the purification stage of the zinc plant, is composed mainly of zinc, cadmium and copper in varying amounts depending on the efficiency of precipitation and the cadmium and copper contents of the impure solution treated. The composition range is approximately: cadmium 10-12 pct, copper 6-8 pct, and zinc 3&35 pct. As received at the cadmium plant, the precipitate is a dark gray to black press cake produced by filter pressing the flocculent cadmium-copper precipitate formed when impure zinc solution is agitated with zinc dust. The details of the cadmium-copper precipitation are to be found in the paper "Electrolytic Zinc at Risdon, Tasmania," by W. C. Snow. Transactions AIME, 121, 501. The treatment, in addition to recovering cadmium as metal, yields a copper product as a residue for realization and recovers in solution for return to the zinc plant, the excess of zinc dust used during purification. The recovery of cadmium metal is approximately 200 tons† per year, but, with the amount of copper residue recovered, varies with the zinc production tonnage, composition of the original concentrates, degree of roasting and other operational factors. The operations involved in the recovery of the foregoing materials are carried out in a building adjacent to the purification section of the zinc plant and can best be described by dividing the process into the following stages: 1. Oxidation and Grinding of the cadmium-copper precipitate. 2. Leaching and Filtering. 3. Precipitation of cadmium. 4. Oxidation and Grinding of the precipitated cadmium. 5. Leaching oxidized cadmium precipitate and Purification of leach solution. 6. Electrolysis. 7. Melting, Casting and Packing. A feature of the process is the use of two distinct solution circuits. Spent electrolyte from the zinc plant circuit containing about 10 pct sulphuric acid is used as the primary solvent of the cadmium and zinc present in the oxidized precipitate. When the cadmium is later separated by precipitation and filtering, the filtrate, originally zinc plant spent electrolyte and now fortified in zinc, is returned to the zinc plant. The precipitated cadmium, after oxidation, is redissolved in spent electrolyte from cadmium electrolysis which solution is in closed circuit within the cadmium plant except for discards to the zinc plant circuit as mentioned in Section 5 hereinafter. (Fig 1.) Details of the various operations follow. I. Oxidation and Grinding of the Cadminm-copper Precipitate The precipitate having had a preliminary drying by compressed air in Dehne filter presses in the zinc plant is trucked to a storage platform of sufiicient length to store 3 to 4 days' production separately. After 48 hr exposure to atmosphere, oxidation is sufficient to enable all cadmium and zinc but only a portion of the copper to be dissolved in dilute sulphuric acid. The oxidized precipitate is shovelled into trucks and, after weighing and sampling, is broken in size by means of

Jan 1, 1950

By C. R. Dale

The need for instruments to measure the movement of fluids and gas in wells has been recognized by engineers for many years. Information regarding flow in the producing interval has a direct bearing on completion practices in new wells and also provides information on the production characteristics of the well. Many hours of engineering time are spent in planning and completing wells but knowledge as to whether or not the original planning has produced the desired results has not always been complete. Many questions such as the following often arise: Why is it that two wells are completed under supposedly identical conditions, yet one well is a good one and the other is a poor one? Are the sands that look the best on the electric log contributing to the production? These and many other conditions in the producing well need to be under- stood in order to develop more efficient production practices and to improve on methods of completing new wells. It is the purpose of this paper to briefly describe one type of instrument, outline the methods of running the equipment and show the results of surveys made under various conditions. With an understanding of the use of this type of survey its importance can be evaluated in relation to the problems encountered by the operator. DESCRIPTION OF INSTRUMENT The instrument is a velocity recorder employing a clock-controlled 16mm film for recording the rpm of an extremely sensitive rotor which is rotated by the flow of fluids or gas in a well. The helical-vaned rotor and shaft, weighing one-half of one ounce are an integral unit exposed to the well fluids and are the only moving parts not enclosed in the fluid-tight housing. No packing or fluid seal of these parts is necessary and the shaft is mounted top and bottom on special jeweled bearings. Fig. A is the lower part of the instrument showing rotor and shaft with the protecting housing sleeve removed. The rpm of the rotor is recorded on the moving film by a combination electrical and optical system. The record is a series of dashes on the film, each dash and space representing twenty (20) revolutions of the rotor. (Film record of survey made in California well showing station recordings at various depths.) As the movement of the film is controlled by the clock the number of dashes and spaces in one minute of film travel represents the rpm of the rotor. The range of the instrument is from 0 to 2,500 rprn. The barrel or housing is 1-11/16 in. OD and seven feet long. Various types of expanding fluid traps are attached to the lower end of the instrument to direct the flow through the 1 in. orifice containing the rotor. The fluid trap for upward flow is shown in Figs. B and C. This assembly consists of eight arms with light spring

Jan 1, 1949

By C. R. Dale

The need for instruments to measure the movement of fluids and gas in wells has been recognized by engineers for many years. Information regarding flow in the producing interval has a direct bearing on completion practices in new wells and also provides information on the production characteristics of the well. Many hours of engineering time are spent in planning and completing wells but knowledge as to whether or not the original planning has produced the desired results has not always been complete. Many questions such as the following often arise: Why is it that two wells are completed under supposedly identical conditions, yet one well is a good one and the other is a poor one? Are the sands that look the best on the electric log contributing to the production? These and many other conditions in the producing well need to be under- stood in order to develop more efficient production practices and to improve on methods of completing new wells. It is the purpose of this paper to briefly describe one type of instrument, outline the methods of running the equipment and show the results of surveys made under various conditions. With an understanding of the use of this type of survey its importance can be evaluated in relation to the problems encountered by the operator. DESCRIPTION OF INSTRUMENT The instrument is a velocity recorder employing a clock-controlled 16mm film for recording the rpm of an extremely sensitive rotor which is rotated by the flow of fluids or gas in a well. The helical-vaned rotor and shaft, weighing one-half of one ounce are an integral unit exposed to the well fluids and are the only moving parts not enclosed in the fluid-tight housing. No packing or fluid seal of these parts is necessary and the shaft is mounted top and bottom on special jeweled bearings. Fig. A is the lower part of the instrument showing rotor and shaft with the protecting housing sleeve removed. The rpm of the rotor is recorded on the moving film by a combination electrical and optical system. The record is a series of dashes on the film, each dash and space representing twenty (20) revolutions of the rotor. (Film record of survey made in California well showing station recordings at various depths.) As the movement of the film is controlled by the clock the number of dashes and spaces in one minute of film travel represents the rpm of the rotor. The range of the instrument is from 0 to 2,500 rprn. The barrel or housing is 1-11/16 in. OD and seven feet long. Various types of expanding fluid traps are attached to the lower end of the instrument to direct the flow through the 1 in. orifice containing the rotor. The fluid trap for upward flow is shown in Figs. B and C. This assembly consists of eight arms with light spring

Jan 1, 1949

By G. W. Hodges

The Basic Oxygen Process shop at Gary Works is a three vessel shop tapping 220 ton heats. The larger portion of the heats are teemed into ingot molds with the remaining heats being continuously cast in a single strand continuous slab caster. Ingot production includes a wide range of carbon, alloy, and high-strength steels in many ingot sizes for bar, structural, plate and sheet and tin products. Individual ingot weights vary with the number of ingots per heat ranging from a high of 48 to a low of five. Caster production is primarily Riband, a proprietary low carbon grade for sheet and tin applications developed by United States Steel for continuous casting; some Riband steel is vacuum degassed prior to casting. Maintaining a satisfactory level of ladle performance on both ingot and caster heats with a high production rate and widely varied product mix is a demanding and exacting job requiring the best of equipment, materials, and, most importantly, personnel. The improving trend in ladle performance in the No. 1 BOP shop at Gary is due to a combination of factors, which will be described in the following presentation.

Jan 1, 1972

By Chester R. McKee, Robert W. Terhune, Merle E. Hanson

The relationships describing the enhancement of permeability by firing explosives in boreholes have been derived and combined to yield permeability enhancement as, [ ] or the case in which the stress decays asymptotically as a power law kc and nc represent permeability and fracture density at the edge of the pulverized region near the cavity wall, f is a geometric attenuation factor, m is the dissipation due to real material effects, ko is the original permeability and rd is the scaled radius. This relationship has been compared with available measurements from the American nuclear shot "Hardhat", the French nuclear events in Hoggar granite and the chemical explosive shot in coal near Kemmerer, Wyoming. Significant correlation between this theory and the experimental measurement is observed. A comparison between single and multiple detonations shows that permeability enhancement falls off steeply near the shot; however enhancement can be considerable midway between two shots spaced 10 cavity radii apart. The degree to which enhancement, can be significant depends on material properties and fracture density. Porosity distribution from the explosive 1s the dominate parameter in permeability enhancement. Existing theories of permeability enhancement have also been reviewed.

Jan 1, 1976

By C. S. Barrett

Measurements of impact hardness of ß-brass are reported for a wide range of temperatures. Abrupt softening is observed when temperatures are raised above 425ºC, accompanied by abrupt widening of deformation bands in the deformed samples. Current theories of these effects, and of the lack of twinning, are discussed. HARDNESS1 and flow stress2 of a sample of ß-brass at room temperature depend upon the temperature from which the sample is quenched. It is believed that the state of order in the superlattice is responsible for this dependence—not the order within individual domains, which reaches near-perfection during the quench from any temperature, but the size of the domains which is presumed to be a minimum in the hardest samples, those quenched from temperatures near the critical disordering temperature of 468°C. Measurements of impact hardness made over a range of temperatures and microstructural studies of samples deformed both rapidly and slowly over a range of temperatures, reported herein, should be of aid in reaching a more complete understanding of the underlying factors controlling the properties of the disordered body-centered-cubic material and the ordered material. It appears that such data have not

Jan 1, 1955

By Paul E. Richardson, Edwin E. Maust

Cyclic voltammetry and surface potential (photovoltage) measurements have been carried out on galena electrodes in sodium tetraborate solutions with added HC1 and NaOH to adjust the pH over the range 2 to 13. The first technique shows that the surface species formed on moderate anodic polarization and reduced on subsequent cathodic polarization are the same over the entire pH range. At anodic potentials, a soluble metal species and excess sulfur are formed; at cathodic potentials, sulfur is reduced to a soluble species. More importantly, excess surface sulfur is formed spontaneously under zero current conditions in alkaline solutions. This has been shown to occur on both polished surfaces and on virgin surfaces produced by in situ cleavage under the electrolyte. The photovoltage gives some insight into the charge and potential distribution at the galena surface. This is found to depend on past electrochemical history and the n- or p-type semiconducting character of the electrode and is interpreted in terms of changes in the surface stoichiometry that occur during reduction or oxidation. The effect of surface stoichiometry on subsequent xanthate interactions is discussed.

Jan 1, 1976

By Charles White Merrill

A forecast of mineral demand during the remaining years of the 20th century can serve as an excellent starting point for student mining and mineral engineers in planning their professional careers. This approach of appraising demand before seeking supply is not new. of course, but, it is quite the opposite of the traditional attack on mineral resources in which adventurous prospectors, followed by practical miners and engineers, have in the past sought out and developed mineral supply with a faith that markets existed for the products they were preparing to offer. Such faith, even to this day remains fully justified if the product is gold, which still enjoys an unlimited market at $35 a fine ounce, but other mineral products must compete in markets of varying stability and capacity for adsorbing new supply. The world is in a period of rapid expansion. Most basic is the worldwide increase in the number of people which has reached proportions popularly termed "the population explosion." Conservative demographers, noting an increase from 1 ?h billion people at the beginning of the 20th century to 3 billion today, are predicting 5 billion by the year 2000; some predictions are much higher.

Jan 2, 1964

By A. S. Grove, C. T. Sah, E. H. Snow, B. E. Deal

A summary of- several recent investigations in to the properties of the metal-oxide-silicon system is presented. A major portion of these studies makes use of the MOS capacitance-z)oltage method of' analysis. The particular areas of investigation which are reported include: 1) a general survey of the electvical properties of thermally oxidized silicon surjbccs; 2) a study of ion migration through silicon dioxide films ; 3) measurements of electron and hole mobilities in surface inversion layers; 4) a study of impurity redistribution due to thermal o.ridatiotz; and 5) measurements of the rates of oxidation oj-heavily doper7. silicon. THE importance of the metal-oxide-semiconductor (MOS) system in the semiconductor industry is well-known. In addition to its importance in the "planar" device technology,' the MOS structure is now also used in the fabrication of active solid-state devices. Consequently, extensive efforts have been made recently to obtain a better understanding of the characteristics of this system. A summary of some studies of the MOS system conducted in our laboratories during the past year is presented. For the most part these studies used silicon as the semiconductor, along with silicon dioxide and aluminum as the other two components of the system. Since the MOS capacitance-voltage method of analysis was used extensively in these studies, we will first briefly describe its nature and consider some of the possible causes of deviation of experimental observations from the simple theory. We will then outline the various related areas of investigation carried out in our laboratories and will briefly indicate some of the results. It should be noted that the purpose of this paper is merely to provide a brief summary of MOS studies. More detailed discussions of the various areas of investigation are given in the references cited. PRINCIPLES OF THE MOS C-V METHOD OF ANALYSIS' A sketch of the MOS structure is shown in the upper portion of Fig. 1. In this case the insulating film is Si02 and the semiconductor p-type silicon. If a large negative bias is applied to the metal field plate, holes are attracted to the silicon surface. The silicon then behaves much like a metal and the capacitance measured is that of the oxide layer alone, Co. If a small positive bias is applied to the aluminum, holes are repelled and a region depleted of majority carriers is formed at the silicon surface. This depletion I-egion adds to the width of the dielectric and the measured capacitance begins to drop. With increasing positive bias, the width of the electrical depletion region increases. At some large positive bias an inzevsion regiotr is formed at the surface and additional charges induced in the silicon appear in the form of electrons in this narrow inversion region. Thus the depletion-region width approaches a maximum value and, consequently, the capacitance reaches a minimum value and then either levels off or rises again depending on the measurement frequency and the rate of equilibration of the minority carriers in the inversion layer.3 Band diagrams, along with the corresponding charge distributions, are shown in Fig. 1 for the above bias conditions. If minority carriers cannot accumulate at the surface to form an inversion region, the depletion-region width continues to increase with increased positive bias and the capacitance drops toward zero as in a reverse biased p-n junction. The effect of a work-function difference $hs between the metal and the silicon, and of surface charges per unit area Qss located at the oxide-silicon interface, is simply to attract charges in the silicon much like the applied bias. It can be shown that this results in a parallel shift of the capacitance-voltage characteristic along the voltage axis by an amount corresponding to AV = -$bIs + Qss/Co. Theoretical curves have been calculated4 giving the capacitance of the MOS structure C normalized to the oxide capacitance Co vs the quantity VG here VG is the voltage applied to the metal field plate. In Fig. 2 such calculations are shown as points for a particular oxide thickness and bulk impurity concentration for a p-type semiconductor. (For an n-type semiconductor the curves would be mirror images of these.) All three cases, i.e., low frequency. high frequency, and depletion, are indicated. Also shown in the figure are recorder tracings of the characteristics of actual devices. These characteristics have been shifted along the voltage axis to compensate the effect of surface charges and work-function difference. It is evident that agreement between experiment and theory is good. The nature of this shift along the voltage axis is

Jan 1, 1965

By Reaves. M. J.

The title of my talk, "What Happened to the Uranium Boom?" is old news. Certainly it is for this group. All of us that make our living in uranium know that the boom of the last half of the 1970's is over. U.S. production has been exceeding consumption by more than two to one. Mines and mills are closing and yellowcake prices have been dropping for over 20 months. The gloomy outlook for the industry in the near term has been well documented by soothsayers of various descriptions, your daily newspapers, and in the Nuexco Monthly Reports. I'd like to attempt to describe the next upturn in the market (speculate, really) based upon the clues we're seeing now. In order to do that, I'd first like to go over briefly, some of the market factors that contributed to the recent price drop and resultant production cutbacks, and then hypothesize on the way these factors are changing and will change. Market prices are greatly affected (maybe even entirely determined) by buyer perceptions. This is particularly true with uranium, because of the long lead times associated with nuclear plant construction and also with conventional mine/mill development. Before the price rise (say, 1975) utility uranium buyers believed that: 1) U.S. producers would have difficulty expanding to meet U.S. demand. 2) Australian and Canadian production was essential to avoid shortages in the early 1980's. 3) Uranlum prices would continue to rise as demand exceeded supply. 4) Enrichment capacity would become inadequate. It was thought necessary, therefore, to build enriched inventory in the early 1980's for use in the late 1980's. Artificially accelerated expansion of the uranium producer industry was necessary to accommodate anticipated enrichment demand. Current perceptions are largely the opposite. These are the beliefs that were held most of this year and late last year as prices dropped. 1) U.S. production is far in excess of domestic need. Contraction of the U.S. production lndustry is necessary. 2) Canadian and Australian supply is optional and not essential. Producers in those countries are expanding mainly by displacing higher cost production and not because they fill a void, 3) Prices may be essentially stable for some time. 4) Enriched uranium is in excess supply. That is 1981. 1982 is shaping up to look like this: 1) Prices will have bottomed out. (That is not Nuexco's opinion necessarily, by the way, but it is my opinion.) 2) There will still be substantial utility inventories, but fewer spot sales. 3) Canadian and perhaps Australian sellers will have made substantial sales in the U.S. and will be aggressively seeking more. 4) U.S. production will have been dramatically curtailed. U.S. utilities that wish to con- tract long term will have difficulty in finding domestic sellers. Concern will develop about the availability of U.S. production capability. Virtually all long term con- tracts signed will be with non-U.S. sellers. 5) An awareness will begin to develop among U.S. buyers that we are approaching a period of dependence upon foreign uranium (which will be true). The history of the uranium market has been one of dramatic changes and overreaction to those changes. The rapid price rise of a few years ago generated excess U.S. production capacity and the rapid price drop of the last two years will almost certainly result in too little capacity. It will soon be difficult for U.S. buyers to buy domestic material except on the spot market. The question is, "will they care?" The lack of demand, of course, is the underlying reason for the current poor health of the uranium industry. In 1972, 1973 and 1974 collectively, there were 105 nuclear reactors ordered in the U.S. That ordering rate was expected to continue and accelerate throughout this century. In 1975, 1976, 1977, 1978, 1979, and 1980 altogether, there were 56 more reactors cancelled than ordered. The net growth of our only customer since 1974 has been a negative 56. TO put this in perspective, if these 56 reactors were operating now it would more than double present U.S. uranium consumption. Underlying lack of demand is something that is simply not going to change in this decade. Time is going to be required. The NRC indicates that the maximum feasible number of new reactors that can be licensed each year is six. That would increase uranium consumption by only 10% per year. New reactors, if ordered tomorrow, would not generate new uranium demand until after 1990. Even so, United States' consumption of uranium will rise from the 1980 level of 18 million pounds per year, to

Jan 1, 1982

By Tell Ertl

THE Piceance Creek Basin in northwestern Colorado is believed to contain the richest large deposit of oil shale in North America. The major portion, about 1650 sq miles, is bounded by the White River on the north, the Grand Hogback, which runs from Meeker to Rifle, on the east, the Colorado River to the south, and the drainage basin of Salt and Douglas Creeks on the west. The Basin is a plateau 7000 to 9000 ft high, composed of 3000 ft of the Green River series of Eocene age and surrounded by a steep escarpment of 1000 to 3000 ft. From the escarpment the beds dip gently toward the center. Although oil shale is found in all members of the Green River series, the rich thick beds are found chiefly in the Parachute Creek member. This is normally capped by 100 to 200 ft of the Evacuation Creek, the youngest member of the Green River series. Actually the Piceance Creek Basin oil shale is not a shale, nor does it contain oil. It is magnesium marlstone holding solid organic matter capable of being broken down by heat into gases, some of which can be condensed into oil. The marlstone is resilient nonporous rock, difficult to sample by pick or hammer and moil. Many companies and individuals prospected the Colorado oil shale shortly after the first World War,1 see Fig. 1, but because of the discovery of large quantities of petroleum in the late 1920's in California, Oklahoma, and East Texas, interest in oil shale development waned and did not revive until World War II. In 1944 the writer, employed by the Bureau of Mines, prospected the high grade oil shale in numerous places along the southern outcrop of the Piceance Creek Basin. Several channel samples about 100 ft in length were cut, see Fig. 2. An eightman crew needed a week to cut a satisfactory channel 80 ft long in the cliff face. The Phillips Petroleum Co., the Union Oil Co. of California and others also prospected the oil shale outcrop. In 1945 the Bureau of Mines initiated a core drilling program for the purpose of obtaining accurate samples from the Piceance Creek Basin. The U. S. Geological Survey set up a program for the geological study of the Basin that is still going on.2 Until the end of 1951 a total of 31 holes was drilled for core with diamond drills, and, in addition, cuttings through the oil shale have been obtained from 4 gas wells drilled by standard rotary oil well rigs. The Bureau of Mines drilled 12 of the holes, the Union Oil Company of California 8, the Standard Oil Company of California 6, the Sun Oil Company 3,

Jan 1, 1952

By Marston G. Fleming

CRITICAL pH has been defined by Wark1 as that pH value below which a mineral will float and above which it will not float in solutions containing a given concentration of collector but free from other depressants or activators. - The relationship between mineral, collector concentration, and pH is expressed in the form of a critical pH curve determined by the captive bubble method and is generally regarded as being fundamental to the system involved. The mechanism of alkali depression is currently in dispute, two general theories having received authoritative support. The view expressed in Taggart's chemical theory of flotation2 is that in the presence of a critical concentration of hydroxyl ions, all the metal ions available at the surface of the mineral are present as anions of the form [M (OH)x]-y. The formation of the necessary metal xanthate is thus precluded and, furthermore, any metal xanthate coating previously formed, at a lower pH, will be dissolved. Gaudin3,4 and the Melbourne school under Ware hold that alkali depression is caused by the preferential adsorption of hydroxyl ions by the mineral surfaces. This paper describes an investigation of the mechanism of alkali depression in each of the three systems: cerussite-aqueous carbonate-xanthate, cerussite-xanthate, and galena-xanthate. Alkali Depression of Cerussite by Control of Carbonate Ion Concentration Wark and Cox6 have shown that in the presence of Na2CO3 a higher concentration of xanthate is required to effect bubble contact with a cerussite surface than in carbonate-free solutions. To examine this depression of cerussite by sodium carbonate, a series of captive bubble tests was carried out on cerussite specimens in solutions containing 100 mg per liter of potassium ethyl xanthate and varying concentrations of sodium carbonate. The pH was adjusted by the addition of dilute hydrochloric acid. For purposes of comparison a standard critical pH curve was determined for cerussite with potassium ethyl xanthate in solutions containing no added carbonate. In the latter case pH adjustment was made with sodium hydroxide. The experimental method employed in both series was broadly similar to that described by Wark and Cox;7-9 a number of refinements suggested by Sutherland10 were adopted, and the procedure was further developed and modified to suit the particular requirements of the investigation. The relationship between pH and the concentration of potassium ethyl xanthate necessary to induce bubble contact at cerussite surfaces is shown in Fig. 1. The relationship between pH and the concentra- [ ] tion of sodium carbonate necessary to prevent bubble contact at cerussite surfaces in the presence of 100 mg per liter of potassium ethyl xanthate is shown in Fig. 2. Comparison of the. two curves shows that at a collector concentration of 100 mg

Jan 1, 1952

By H. K. Livingston

A technique has been developed which makes it possible to determine the spreading pressure of liquids and solids, for simple systems. Data for surface tensions, interfacial tensions, spreading pressures, and contact angles for water, heptane, and silica are tabulated.' These results can be applied to the evaluation of capillary rise and displacement pressure in a petroleum reservoir. Appropriate equations are presented and the application of these equations is discussed. The presence of surface-active components affects both capillary rise and displacement pressure and also seems to influence the rate of fluid flow. The purpose of this paper is to supplement and bring up to date the last article on the subject of the surface chemistry of petroleum reservoirs, that of Garrison in the 1935 Oil and Gas Journa1.1 A discussion of the "adhesion tension" concept used by Garrison has been presented in another publication,2 together with the reasons for the recommendation that the term "adhesion tension" be abandoned. In view of the fact that some of the data used by Garrison have been superseded by more recent work, it seemed advisable to call attention to this fact and present the more important data currently believed to be correct. In the earlier paper, Garrison set up the equations that 'relate solid-oil and solid-water interfacial tensions to each other, and applied data from Bartell and Miller3 to these equations. However the adhesion tension measurements made by Bartell and Miller involved a confusion of symbols, so that they did not actually measure the spreading pressure, ?s — ?sf.2 The spreading pressure is a convenient method of indicating the amount by which the surface energy of a solid surface is lowered on immersion in a liquid or vapor. Since the initial value of the free surface energy is represented by the symbol ?s and the final value is ?sF, the spreading pressure is ?s — ?SF. A technique has now been developed4 that makes possible the determination of ?s — ?sF for simple systems. This method would be very difficult to carry out with a multicomponent system such as exists in the petroleum reservoir. However, already results have been obtained for ?s — ?sF for water and heptane in contact with silica and graphite. These values will be of the same order of magnitude as those in the petroleum reservoir. Accordingly, it is possible for the first time to discuss the surface-energy relations of the petroleum reservoir on a semi-quantitative basis. Preliminary Generalizations A petroleum reservoir may contain the following four phases: gas, hydrocarbon liquid, aqueous liquid, and solid. The three fluid phases are dispersed through the solid reservoir rock. If gravity were the only force acting, it is obvious that the

Jan 1, 1943

By H. K. Livingston

A technique has been developed which makes it possible to determine the spreading pressure of liquids and solids, for simple systems. Data for surface tensions, interfacial tensions, spreading pressures, and contact angles for water, heptane, and silica are tabulated.' These results can be applied to the evaluation of capillary rise and displacement pressure in a petroleum reservoir. Appropriate equations are presented and the application of these equations is discussed. The presence of surface-active components affects both capillary rise and displacement pressure and also seems to influence the rate of fluid flow. The purpose of this paper is to supplement and bring up to date the last article on the subject of the surface chemistry of petroleum reservoirs, that of Garrison in the 1935 Oil and Gas Journa1.1 A discussion of the "adhesion tension" concept used by Garrison has been presented in another publication,2 together with the reasons for the recommendation that the term "adhesion tension" be abandoned. In view of the fact that some of the data used by Garrison have been superseded by more recent work, it seemed advisable to call attention to this fact and present the more important data currently believed to be correct. In the earlier paper, Garrison set up the equations that 'relate solid-oil and solid-water interfacial tensions to each other, and applied data from Bartell and Miller3 to these equations. However the adhesion tension measurements made by Bartell and Miller involved a confusion of symbols, so that they did not actually measure the spreading pressure, ?s — ?sf.2 The spreading pressure is a convenient method of indicating the amount by which the surface energy of a solid surface is lowered on immersion in a liquid or vapor. Since the initial value of the free surface energy is represented by the symbol ?s and the final value is ?sF, the spreading pressure is ?s — ?SF. A technique has now been developed4 that makes possible the determination of ?s — ?sF for simple systems. This method would be very difficult to carry out with a multicomponent system such as exists in the petroleum reservoir. However, already results have been obtained for ?s — ?sF for water and heptane in contact with silica and graphite. These values will be of the same order of magnitude as those in the petroleum reservoir. Accordingly, it is possible for the first time to discuss the surface-energy relations of the petroleum reservoir on a semi-quantitative basis. Preliminary Generalizations A petroleum reservoir may contain the following four phases: gas, hydrocarbon liquid, aqueous liquid, and solid. The three fluid phases are dispersed through the solid reservoir rock. If gravity were the only force acting, it is obvious that the

Jan 1, 1943

By H. H. Keller, E. J. Couch

Damage to production wells subjected to the high temperatures associated with in-situ combustion projects has been a problem since the advent of this thermal recovery technique. Injection of water down the annulus of hot wells has been successfully utilized for cooling and prolonging the life of such wells. A mathematical model that is suitable for predicting the effectiveness of cooling water in a particular application is developed. Typical results for practical ranges of the various parameters involved are presented. INTRODUCTION In the normal course of in-situ combustion operations, highly damaging conditions develop in the production wells as the combustion zone approaches, and these wells are subjected to high temperatures (up to 1500F). The resulting well damage is recognized as one of the more serious operating problems unique to the in-situ combustion process. Even in operations where well completions have been specifically designed to cope with this problem, the question arises as to how this destructively high temperature can be kept within tolerable limits. A simple and economical approach to this problem is to circulate cooling water down-hole. This method has been used with some success in shallow reservoirs. At greater depths, however, the heat exchange with the overburden surrounding the well and between the fluids in the tubing and the annulus tends to equalize the temperatures of the two fluid streams so that the cooling capacity delivered to the bottom of the hole decreases with well depth. This method would provide no appreciable control over the bottom-hole temperature at great depths. In order to delimit the condition under which cooling by water circulation is effective, the wellbore temperature must be related to the water inlet rate and temperature; to the reservoir depth, production rate, and initial temperature; and to the combustion at at bot tom-hole depth. A model that meets these requirements and that will offer an approach for developing engineering solutions to practical design and operating problems is described in this paper. MATHEMATICAL MODEL Previous studies of temperature distributions include those for flowing wells1p2 and those for hot fluid injection. Adams and Haddenhorst 6 presented solutions for the down-hole circulation of hot oil in the treatment of paraffin-deposition problems. In this paper the thermal model presented by Ramey 4 is adapted to the flow system shown schematically in Fig. 1. Water at temperature Ti is injected at a rate wi and flows down the annulus outside the tubing. It mixes at bottom-hole depth D with the fluids produced at race w from the hot reservoir at temperature T. This mlxtureJ. of injected water and reservoir fluids flows up the tubing and is produced at the surface at TI,. In order to describe the temperature response in this system, we make use of the usual conservation of

Jan 1, 1969

By Yap Chu-Phay

ALTHOUGH chronologically, the Sb-Bi system was the first one studied by the writer, the theoretical basis of the equations used in this paper is fully discussed in the writer's paper on the iron-carbon system,1 because he believed that many would be more interested in the iron-carbon alloys. He suggests, therefore, that the reader consult that paper to familiarize himself with the theoretical aspect of the thermodynamic treatment outlined herein. This paper is divided into two parts: Part I deals with the Sb-Bi system and Part II deals with the lead-rich side of the Sb-Pb system. Although the former system has not much practical interest now, it has great theoretical interest in that it, is the one system that for a long time was thought to have (and under specific conditions still has) an anomalous solidus, which no amount of physical investigation could adequately account -for. The latter system of course, is particularly interesting in the lead-rich end. It will be shown that the thermodynamic method is capable of predicting reliably the equilibrium position of the solidus, and thus acts as a check on the experimentally derived solidus.

Jan 1, 1931

By Fred P. Peters

At first glance this paper may seem unique among those comprising this symposium on designing for powder metallurgy, since it is evidently concerned with everything but Powder metallurgy. This paradox mill be at once resolved, however, when the real Purpose of the symposium meeting is understood—to present factually and objectively the things that can and cannot he done with powder-metallurgy methods, and especially to set forth with brutal frankness the limitations of Powder metallurgy, so that costly over-enthusiasm and misapplication may be prevented. Since much of powder metallurgy's future development (and many of its present disappointments) has been in competition with other and long-established methods of fabricating parts, it is easy to see that its true competitive possibilities in any given case cannot be accurately appraised without rudimentary knowledge of what the competition can do. This paper, therefore, presents a few reminders of things you all know—a background to be kept in mind as you examine the data on each of their specialties given by the authors of the papers that follow. From the standpoint of the design engineer powder metallurgy is often in Competition with one or more of the following: sand casting, die casting, permanent-mold casting, precision investment casting, ma- chined bar stock, screw-machine parts, cold-heading, drop-forging, and stamping and drawing. We will here briefly discuss each of these individually, and set forth so, rough (and therefore dangerous) generalizations about its competitive position, especially with respect to powder metallurgy. Sand Casting Sand-casting of small parts is sometimes an inexpensive method of manufacture, for its raw-material costs (i,e., for gray iron) are the lowest of the various methods and it involves the use of no tools and dies of jewelry quality. its design flexibility— that is, the ability to make complicated, cored and undercut parts in one piece—is about the highest of the competing processes and in this respect it can do many things that are impossible by powder metallurgy. For small castings its production rates may be higher, by using multi-impression molds, than can be achieved with parts of the same size by powder metallurgy. But its labor charges for melting, pouring, patternmaking and molding are comparatively high and the waste it entails in gates and risers is always considerable. Tolerances of sand castings are wide (+1/6 to 1/32 in- per in.) and where precision approaching that of powder metallurgy is required sand castings must be machined to final size, thus increasing their cost. Steel sand castings are more expensive and less precise than iron, and nonferrous the most costly of all.

Jan 1, 1945

By A. W. Schlechten, A. H. Larson

Equilibrium H2S/H2 ratios were determined as functions of temperature (500o to 900°C) and composition in a hydrogen-circulation apparatus. Within the composition range studied there exists a two-phase region of "Zr3S4" and "ZrS2". The upper composition limit of this two-phase region is hounded by a disulfide phase and is practically constant over the temperature range investigated. The lower composition limit of this two-phase region is bounded a "Zr3S4 " phase and varies appreciably with tem- perature. The upper composition limit of the homogeneous region of the disulfide phase is not definitely determined, but it appears to he bounded by the stoichiometric composition of ZrS2. The lower composition limit of the homogeneous region of the Zr3S4 phase could not he determined due to the extremely low values of the equilibrium H2S/H2 ratios. Various thermodynamic quantities are evaluated from the data. PUBLISHED free-energy data for the Zr-S system are practically nonexistent. Strotzer, Biltz, and Meisel1 measured the sulfur pressures for the reaction 2ZrS2(s) + S2(g) = ZrS3(s) in the temperature range 783" to 874°C. The average heat of reaction calculated from the temperature dependence of the sulfur pressure is -47 keal. It should be noted, however, that according to these investigators, the two-phase region as determined by sulfur pressure constancy under isothermal conditions extended from approximately ZrS2, 3 to ZrS2.7. From consideration of X-ray data they concluded that the homogeneous regions of the disulfide and trisulfide phases are ZrS1.8-2.0 and ZrS2.8-3.2, respectively. Hahn and coworkers2 have made a structure study of the zirconium sulfide phases. They summarized the zirconium sulfide phases as follows: the compounds ZrS3 and ZrS2 with narrow homogeneous regions, a "Zr3S4" phase with a homogeneous region roughly within the limits of ZrSl.5 and ZrSo.9, the compounds ZrS and Zr4S3, and a "Zr3S2" phase with a homogeneous region within the limits ZrSo.8 and ZrSo.5. It is noted that the compounds ZrS and Zr4S3 are only formed in the gaseous state through sublimation of a phase which has the approximate composition of the compound. This paper describes the determination of the stability of the zirconium sulfide phases by a hydrogen-reduction method in which hydrogen is circulated over the heated sulfide until equilibrium is attained. The resulting H2S-H2 mixture is then analyzed. Partial molar free energies, enthalpies,

Jan 1, 1964

By R. A. Bell, R. Schultz, P. G. Hallof

The Ballyvergin area is located in County Clare on the southwest coast of Ireland. It is one of six areas in County Clare in which mining operations were carried out during the last century. The ores mined were high grade Cu-Pb-Ag deposits in the form of small fracture fillings and gash veins in the lower Carboniferous limestones. The zone of primary economic interest is situated on the north limb of a geosyncline which plunges moderately to the southwest. The zones of mineralization previously mined were associated with local structures and folds, and the initial geophysical investigations took the form of reconnaissance induced polarization measurements around, and between, the old mines. This work located an anomaly which, on drilling, resulted in a small extension of the Pb-Cu ore at the Ballyvergin mine. However, a potentially more important zone of mineralization resulted from the drilling of another IP anomaly near Ballyvergin. This wide anomaly was found to be a domal shaped deposit of disseminated chalcopyrite located at a depth of more than 100 ft. The deposit is controlled by local folding in the sediments and is of a type previously unknown in the area. More IP investigations are under way to locate other deposits of the same type. The Ballyvergin area is located in County Clare, about 35 miles northeast of Shannon Airport, near the Atlantic west coast of Southern Ireland (Fig. 1). Interest in the area stems from a number of occurrences of small, but high grade, Pb-Ag deposits. From the summer of 1960 to the spring of 1961, Irish Base Metals carried out a comprehensive exploration program on a 38-sq mile concession in east-central County Clare in an attempt to locate additional deposits of this type. Field operations consisted of geologic mapping, geochemical soil and stream sampling, geophysical surveying and diamond drilling. The geophysical program consisted primarily of detailed induced polarization (IP) surveys in the general vicinity of old mine workings, supplemented by electromagnetic and self-potential investigations. Subsequent diamond drilling of a well defined IP anomaly close to the old Ballyvergin mine disclosed a sizeable deposit of low grade disseminated copper, a type of deposit previously unknown in this area. REGIONAL GEOLOGY Topography: The topography is of the Karst type with low regional relief. The northern parts of the area are covered almost completely with glacial deposits including a large number of drumlins. Elsewhere the overburden is patchy and only moderately deep. A close network of roads makes every part of the area readily accessible, and rail and harbor facilities are available nearby — Fig. 2. Stratigraphy: The area was mapped on a reconnaissance basis by the Geological Survey of Ireland during the latter part of the 19th century at scales of 1 and 6 in. to the mile. Mapping is complicated in

Jan 1, 1962

By B. F. Bush

THE coal-fields of Missouri, situated hi the northern and western portion of the State, are distributed, in whole or in part, over 57 counties, embracing an area estimated by Mr. Broad-head to be practically 23,000 sq. miles, including small detached beds and outliers in St. Louis, St. Charles, Lincoln and Warren counties in the eastern part of the State. This area includes about 8,000 sq. miles of Upper or Barren Measures, 2,000 sq. miles of exposed Middle, and 12,420 sq. miles of exposed Lower Measures. In a general way, the Missouri coal-field is bounded on the east by an imaginary line entering the northern part of the State just east of the 92c1 Meridian and passing across the State in a southwesterly direction to a point on the Kansas-Missouri line a little below the southern boundary of Barton county. An important part of the field overlaps this line and extends down the northern side of the Missouri river, under¬lying the greater part of Randolph, Howard, Boone and Audrain counties. In all, 34 counties produced coal during the year 1903. Fig. 1 shows the position of the coal-fields in Missouri. GEOLOGICAL FEATURES. The Coal Measure formations, all of the Carboniferous age, rest unconformably upon the rocks of the sub-Carboniferous or Mississippian series, and, in some cases, upon the rocks of the Devonian and Silurian ages. From their outcrop on the eastern and southeastern borders of the field, the Measures dip west to northwest at the rate of 10 ft. per mile, reaching a maximum thickness estimated by

Jan 1, 1905