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By J. M. Bugbee

The engineer and the conservationist agree that effective water drive is the desirable reservoir production mechanism. Water drive may result either from the expansion of edge water, the reservoir water bordering an oil pool, or from the artesian flow of edge water from the outcrop. Thus, the extent of the reservoir has an important bearing upon both the rate and the ultimate quantity of water influx to an oil pool. Lens-type reservoirs are generally recognizable, but the complete structure of the more important domal types, having possible limitations from crestal and synclinal faulting, is not well understood. The delineation from cores, electrical logs and exploitation phenomena of the crestal portions of reservoirs is increasingly exact. This paper suggests that inference from these factual pictures, combined with the scattered well and geophysical data of the synclines and with consideration of the dynamics of structural formation, may be applied to solving the complete geologic structure. Since faulting on the domes and in the synclines may effectively seal and thus limit the size of a reservoir and bar additional water influx, consideration of geologic structure and its possible effects is essential to complete analysis and prediction of reservoir performance. Introduction Implicit in reservoir studies is the fact that the oil must be displaced from the reservoir rock by some other fluid, either gas or water, and this understanding yields the terms descriptive of the major reservoir production mechanisms, gas expansion and water drive' Three recent papers1-2-3 make clear the economic and conservation preeminence of Water drive as a production mechanism; in fact, the title of the latest of these is " Production under Effective Water Drive as a Standard for Conservation Practice." There appears to be an assumption at times among analysts that the effectiveness of a water drive is solely dependent on the rate of oil production; that is, if water drive appears to be insufficient or lacking, a lower oil-recovery rate would increase or reveal it. This assumption might result from the fact that the analysis has been wholly developed during the period of production curtailment; that is, since 1929. The writer takes it that the recurrent phrase in De Golyer's paper,3 "some degree of water drive," is related to this assumption. In California, an extraordinary phrase, "inactive water drive," is rather common and the connotation of uncertainty regarding our knowledge of reservoir performance is evident. Wyckoff2 speaks of the type of reservoir and performance as follows: "In general, reservoirs may be any one or a combination of domal, faulted, lenticular, or stratigraphic traps. Insofar as the dynamic performance of such reservoirs is concerned, the particular type merely determines whether regional flow is symmetrical as in a uniformly developed domal or lenticular type, or one-sided as in many stratigraphic or faulted traps." But whether the flow is

Jan 1, 1943

By J. P. Myers, A. H. Flagg, E. S. Mardock, J. L. P. Campbell, J. M. Terry

The development process for the use of radioactive tracers as a means of locating zones of permeability is discussed. The general techniques for the safe handling of radioactive materials is given as developed by the Lane-Wells Co. and Well Surveys, Inc. The prob1em and. successes with tracers in waterflood systetns, oil and gas injection profiles, fracture sand tracing, squeeze (ement tracing. lost circulution, and cement top localion are discussed and illustrated. INTRODUCTION The exact location of the permeable zones lying within the productive horizon has been a major problem faced by the petroleum engineer for decades, and it has been a problem which has seldom been solved with certainty. Reservoir engineers usually have to incorporate a question mark in their estimates of future reservoir performance because of blanks in the core data. Although the use of radioactivity or electrical logs for the estimation of porosity has been of great assistance in furnishing a record for the reservoir engineer, this application of logging data has not completely solved the problem. In short, the industry needs an in-situ well surveying method which can locate and estimate the permeability of the zones existing within a given pay section. The initial development work with radioactive tracers has been towards filling the need for permeability information. Progress to date permits the location of permeable zones with a qualitative estimate of their relative importance with respect to permeability. The calibration of the method is still incomplete. but present development work on tracer preparations, borehole effect correction factors, and instrument limitations give a promise of quantitative "permeability profiles" in the near future. The development work on the radioactive tracer method discussed here began several years ago in the laboratories of Well Surveys, Inc., in Tulsa. At the outset of this work, three approaches to the problem were visualized as follows: 1. A fluid carrying a soluble, chemically inert, gamma ray emitting isotope is pumped down the borehole and out into the permeable zones of the formation. The greater gamma activity of the permeable zones thus permits them to be differentiated from the impermeable zones which contain no active tracer. It was found difficult to obtain a tracer material which was chemically inert. Absorption to some degree was noted in all experiments. Also, it proved impossible to hold the tracer near the horehole where it could be logged. 2. A fluid carrying a soluble, gamma ray emitting isotope is pumped down the borehole into the permeable formations. In contrast with proposal 1, above. the tracer is chemically active with the fluids and materials in the pore spaces of the permeable zones. The permeable zones are thus indicated by their higher radioactivity level. The main difficulty in this proposal was finding a tracer material which would not be absorbed by shale as well as in the permeable porosity. Very little field work was done with this system. 3. Radioactive particles suspended within the injection fluid are pumped down the well. As the fluid enters the permeable formations, the radioactive particles are filtered out on borehole wall. The permeable zones are differentiated from the impermeable by the gamma ray activity deposited on the formation wall.

Jan 1, 1956

By J. M. Bugbee

The engineer and the conservationist agree that effective water drive is the desirable reservoir production mechanism. Water drive may result either from the expansion of edge water, the reservoir water bordering an oil pool, or from the artesian flow of edge water from the outcrop. Thus, the extent of the reservoir has an important bearing upon both the rate and the ultimate quantity of water influx to an oil pool. Lens-type reservoirs are generally recognizable, but the complete structure of the more important domal types, having possible limitations from crestal and synclinal faulting, is not well understood. The delineation from cores, electrical logs and exploitation phenomena of the crestal portions of reservoirs is increasingly exact. This paper suggests that inference from these factual pictures, combined with the scattered well and geophysical data of the synclines and with consideration of the dynamics of structural formation, may be applied to solving the complete geologic structure. Since faulting on the domes and in the synclines may effectively seal and thus limit the size of a reservoir and bar additional water influx, consideration of geologic structure and its possible effects is essential to complete analysis and prediction of reservoir performance. Introduction Implicit in reservoir studies is the fact that the oil must be displaced from the reservoir rock by some other fluid, either gas or water, and this understanding yields the terms descriptive of the major reservoir production mechanisms, gas expansion and water drive' Three recent papers1-2-3 make clear the economic and conservation preeminence of Water drive as a production mechanism; in fact, the title of the latest of these is " Production under Effective Water Drive as a Standard for Conservation Practice." There appears to be an assumption at times among analysts that the effectiveness of a water drive is solely dependent on the rate of oil production; that is, if water drive appears to be insufficient or lacking, a lower oil-recovery rate would increase or reveal it. This assumption might result from the fact that the analysis has been wholly developed during the period of production curtailment; that is, since 1929. The writer takes it that the recurrent phrase in De Golyer's paper,3 "some degree of water drive," is related to this assumption. In California, an extraordinary phrase, "inactive water drive," is rather common and the connotation of uncertainty regarding our knowledge of reservoir performance is evident. Wyckoff2 speaks of the type of reservoir and performance as follows: "In general, reservoirs may be any one or a combination of domal, faulted, lenticular, or stratigraphic traps. Insofar as the dynamic performance of such reservoirs is concerned, the particular type merely determines whether regional flow is symmetrical as in a uniformly developed domal or lenticular type, or one-sided as in many stratigraphic or faulted traps." But whether the flow is

Jan 1, 1943

Report of the Secretary TO THE BOARD OF DIRECTORS AND THE MEMBERS OF THE AMERICAN INSTI¬TUTE OF MINING AND METALLURGICAL ENGINEERS GENTLEMEN As will be shown by the special reports of the Finance, Membership, Library, Papers and Publications, Increase of Membership, and other standing Committees, together with that of the Treasurer, the year 1927 was one in which the Institute made very satisfactory progress in a number of directions. In total numbers the membership is no larger but in revenue from dues there has been a marked increase. This has been due to the promotion to full membership of Junior Associates of earlier years, to the larger proportion that come in originally as members rather than juniors, and to the keener interest in the work of the Institute reflected in prompter payment of dues. The latter is important, since experience shows that of those who fall behind a large number must ultimately be dropped for non-payment. Conditions in the mining in¬dustries have been healthy though not booming. It has been much easier for members to find employment and meet their financial obligations but there has not been that flow of young men into mining, and hence in part into the Institute, that characterized certain earlier years. Rather the tendency toward centralization and larger industrial units has re¬stricted the number, though not the scope, of opportunities for technical men in the mineral industries. The Institute is constantly receiving resignations from members crowded out of mining into other lines of activity. On the other hand, those who remain in mining and metal¬lurgy have a greatly increased necessity for information and contacts with technology. A few years ago many superintendents and most foremen were non-technical men. Today the reverse rule obtains and shift bosses and men who occupy even lower positions in industrial units are called upon to know and to apply such an amount of technical knowl¬edge that graduate engineers are the rule rather than the exception. The curious situation has obtained that with a much smaller enrollment of students in the schools of mining and metallurgy there has been at times an actual shortage of young engineers for beginners' jobs. The young men retort that the conditions of employment and pay offered in mining are not equal to those in other lines and, while it is undoubtedly true that the young engineer beginning in mining is able to start under conditions markedly better as to pay, living, and responsibility than did the men who are now leaders, they are required to know much more and have usually spent more in time and money to qualify for their jobs. The whole matter is one which warrants much more attention than has been given to it. For the Institute it is important since the young men

Jan 1, 1923

By J. Mark Gronseth

The instantaneous shut in pressure often times is not a well defined feature of pressure-time records from in situ stress determinations by hydraulic fracturing. As the applications of in situ stress data become more sophisticated, the grea5er the need for an unambiguous method with which to identify the instantaneous shut in pressure becomes. Controlled experiments suggest that the instantaneous shut in pressure should be equated with the pressure at the inflection point of the pressure-time record following shut in. A method for determining this value is presented. Often times the minimum instantaneous shut in pressure determined after several pressurization cycles is the best estimate of the stress acting perpendicular to the fracture plane.

Jan 1, 1982

US 4,195,426-Manganese nodules are recovered from relatively great depths on the ocean floor using a self- propelled remote-controlled vehicle having a V-shaped tubular structure with a system of crawlers at its apexes. Underneath each side of the V-shaped structure is a scraping system for gathering nodules and directing them into a tubular conveying system for elevation to the surface ship. A given area of sea bed is fully mined in a single pass of the vehicle. V. Banzoli, V. Di Tella, and P Vielmo, assigned to Tecnomare, SPA. Apr. 1, 1980. 5 pp. 137-60) Filed. 3-31-78 (892,197). Priority: Italy, 4-1-77 (84119A/77).

Jan 1, 1982

By Oliver Bololes

UNDER the able leadership of Samuel H. Dolbear, the Committee on Nonmetallic Minerals furnished a program of sixteen papers comprising three sessions. An outstanding accomplishment in technology presented at the first session by Benjamin L. Miller and C. H. Breerwood is the application of flotation to the purification of limestone used in cement manufacture. In place of selective quarrying to provide high-grade raw material, the quarry-run stone is pulverized and treated in froth flotation cells for removal of free silica and mica. Some advantages are cheaper quarrying, more complete utilization of quarry rock, avoidance of purchasing high calcium stone, lower fuel cost and improvement in the finished cement. Paul M. Tyler presented the general subject of milling methods as applied to nonmetal lies. He pointed out the importance of some of the more recent refinements in ore dressing, and urged the need of a wider appreciation of their possibilities. The gypsum industry of Canada was described by L. H. Cole. Crystal growth during the setting process was illustrated by moving pictures. The Coastal Plain and interior salt

Jan 1, 1935

By T. A. Rickard

"The chief aim in style ought to be absolute precision", said Flaubert. "There is only one noun that can express your idea, only one verb that can set that idea in motion, and only one adjective that is the proper epithet for that noun." Let this be your motto. The engineer tries to be exact in all his measurements; he should measure his language with similar exactness. The technical term is a word of precision. It is not only precise, it is a word-saver. To the unscientific the earth is "a ball slightly flattened at the poles, something like an orange". To the scientific it is "an oblate spheroid". A similar contrast between the precision of the technical term and the vagueness of common words is afforded by a conversation between Ivanhoe and Rebecca: "' What device does he bear on his shield?' asked Ivanhoe. 'Something resembling a bar of iron, and a padlock painted blue on a black shield.' 'A fetterlock and shacklebolt azure', said Ivanhoe "-using the technical terms of heraldry. It is good style in writing, however, to adapt your manner of expression to the intelligence and experience of the person or persons to whom the writing is addressed. The description of a mine should be worded differently according as it is intended to inform a mining engineer, a director, or a bishop. REMEMBER THE READER. It is as incorrect to write in a technical way for a non-technical reader as to write in a popular way for a technical or scientific reader. That style is best which enables the writer to place himself in the closest mental touch with his reader, to establish the maximum of sympathetic understanding. Let your precision be\ proportioned to your accuracy. You should not try to be precise in matters that do not admit of

Jan 1, 1931

By Lawrence P. Bonicatto

The steel industry's increased demand for higher grade pellets has caused the pellet producers to investigate methods of upgrading their product and the Hanna Mining Co.'s Groveland plant on the Upper Peninsula of Michigan is no exception. The low grade iron deposit is a complex mixture of magnetite and hematite with chert, quartz, jasper and various iron silicates.1 Beneficiation is by Humphrey spirals and anionic flotation of the iron minerals.2 Flotation of the spiral tailings makes up about 75% of the concentrate, while a minor amount of concentrate (less than 3%) is produced in magnetic circuits. The concentrate is pelletized at the rate of 1.6 million tpy. The initial concentrating facilities were constructed in 1958 and the concentrate was marketed as sinter feed until a pelletizing plant was added early in 1963. Grade improvement soon became a high priority research project, and several methods of concentration were investigated.

Jan 3, 1968

By E. G. Leonardon, C. Schlumberger, M. Schlumberger

Last year the authors presented a paper that discussed the various electrical measurements they perform in drill holes, which they name "electrical coring."' The object of the present paper is to give a brief account of the points of scientific interest that have been elucidated by further field work and laboratory research, as well as the economic results that have been attained recently. The practical examples given in this paper are drawn, for the most part, from the field work performed in Russian oil fields during the years 1931 and 1932. This is due to the fact that, thanks to the comprehensive cooperation of the Russian geologists and scientists, the authors are allowed to make public a large amount of recant information. In other countries in which the authors are engaged in similar work, the competition between private companies makes it imperative, for a considerable lapse of time, to avoid publication of the results obtained. The following points will be discussed successively, under separate headings: 1. Electrochemical phenomena in drill holes. 2. Stratigraphic correlations and tectonic studies. 3. Relations' between the productivity of oil horizons and their electrical resistivity. 4. Location of coal seams. 5. Summary and conclusions. Electrochemical Phenomena in Drill Holes Technical Publication 462l described the author's discovery concerning the existence of important differences of potential spontaneously gener-

Jan 1, 1934

By M. C. Lavine, H. C. Gatos, R. S. Mroczkowski

The structure of GaAs-Ge heterojunctions prepared by a back-melting process was studied by X-rav diffraction, melallographic, and electron-micro-analyzer techniques. The boundary region between the GaAs and the germanium was found to consist of a four-layered band. A discontinuity between the two inner bands was brought about by solidification occurring simultaneously from the GaAs and the germanium side. The junction material OH either side of the central discotinuity was found to have grown as a single Crystal with the orientation of the parent substrate. It was found essential to determine the GaAs-Ge phase diagram. This was accomplished by a series of alloys containing 0 to 40 wt pet GaAs. Over this range the diagram is a simple eutectic with the eutectic point at 74 wt pet Ge and 845 C. The limiting- solubility of Coils in germanium was found to bc less than 5 wt pet. The Kossel divergent-beam X-ray technique was used to study orientation relationships across the boundary lager. A great deal of effort has been recently expended on the electrical properties of heterojunctions. Little attention, however, has been given to the metallurgical variables which may be of importance in the formation of the junctions. The present work was undertaken to investigate some of the more pertinent metallurgical aspects of interface-alloyed GaAs-Ge heterojunctions. Such parameters as solidification processes, composition gradients, orientation effects, and the accommodation of crystal structures have been the objects of study in this program. EXPERIMENTAL PROCEDURES Phase Diagram. The phase diagram of the GaAs-Ge pseudobinary system was determined by means of cooling curves. A Bridgeman furnace was employed with the center section maintained at 1200°C and the upper section at 800°C. Melts varying from 0 to 40 at. pct in GaAs content were used. Each charge was incapsulated under a two-thirds atmosphere of argon in a carbon-coated quartz tube. Five min in the furnace hot zone provided rapid melting and homogenization. The capsule was then removed to the cooler portion of the furnace. Cooling times were of the order of 3 min. The resulting homogeneous microstructure indicated that equilibrium conditions were obtained by this procedure. Formation of Heterojunctions. Rectangular parallelepiped single-crystal samples were cut with the large faces of either the (l00), (110), or (111) orientation. The remaining four surfaces were also cut to specific orientations to permit accurate relative orientation of the GaAs-Ge pairs. The

Jan 1, 1965

By D. K. Bose, C. K. Gupta, K. U. Nair

A new approach to processing an indigenously available low grade molysulfide concentrate by chlorination with elemental chlorine in presence of oxygen is reported. Recovery of nickel and copper values associated with the sulfide concentrate by suitably treating the residue obtained after chlorination is also reported. In the chlorination process, a gaseous mixture of chlorine and oxygen in the volume ratio bf 2:5 has been passed at 1.66 x 10- 5 m3/s for 1800 s over a 0.01 kg batch of molysulfide concentrate at a temperature of 573°K. Most of the molybdenum has been volatilized as molybdenum oxychloride which has subsequently been extracted in water. The molybdenum value from the aqueous solution has been recovered in the form of calcium molybdate (CaO.MoO3) by treatment with calcium chloride (CaCI2). In an alternative processing scheme, the molybdenum rich solution has been treated with an oxidizing agent (K2S20f.J) and allowed to boil to recover a major portion of the molybdenum value in the form of molybdic oxide (MOOS). The spent charge obtained after molysulfide chlorination has been mixed with about 1 wt % sodium chloride and heated at 773K under an oxygen atmosphere. The reacted mass has been water-leached to yield a nickel-copper bearing solution with limited iron. The process liquor appears to be well suited for further processing by known hydrometallurgical recovery processes for nickel and copper. In the conventional process of molybdenum extraction, the molysulfide concentrate (-59% Mo) is first subjected to roasting to produce molybdic oxide. The oxide is then further processed in sequential steps involving vacuum distillation, ammonia leaching, and calcination to higher purity prior to hydrogen reduction to metal. In India there is at present some small tonnage production of molysulfide concentrate from a byproduct recovery plant of the M/s. Uranium Corp. of India Ltd. (M/s UCIL), Bihar. Efforts are being made at this laboratory to process the low grade fraction of the concentrate which contains sulfides of copper, nickel, and iron; quartz; and chlorites. Here, the conventional routes involving roasting and vacuum distillation appear unsuitable to produce an acceptable quality of molybdic oxide at high recoveries. Formation during roasting molybdates of some of the impurities present in the sulfide concentrate make subsequent vacuum distillation less efficient. In view of these problems, in earlier work reported from this laboratory the low grade concentrate has been processed hydrometallurgically to P. produce calcium molybdate. Starting from this molybdenum intermediate, processes have also been developed for the production of molybdenum and ferromolybdenum. Chlorination as an alternative to roasting for metal sulfides has been drawing considerable interest. The high reactivity of chlorine, the relatively low temperature of operation, the suitability of application to low grade resources, the convenience of recovering sulfur in non-polluting form, and the purity of chlorides which are separated by distillation all favor chlorination. In recent years, considerable work has been reported on the chlorination of common metal sulfides. In the field of molybdenum extraction from its sulfide resource, use of chlorination technology has been rather limited. Senderoff and Labrie3 were the first to chlorinate molysulfide concentrate with elemental chlorine at about 823°K to molybdenum pentachloride for use in the electrolytic preparation of molybdenum. The only other reported work, by Haver, Uchida and Wong, involved reaction between molysulfide and chlorine at 673°K to recover sulfur. The reaction products were, however, identified as molybdenum pentachloride and sulfur monochloride.

Jan 1, 1979

By L. VOGELSTEIN

OUTSTANDING among the year's events in copper has been the reimposition of an import duty of 4r. per pound in this country which became effective June 21. In consequence of this action by Congress, the Ottawa Empire conference recommended a duty of 2d. per pound equivalent at normal rate of exchange to our 4c. duty, on all copper originating outside of the Empire. Lip to the middle of this year only Russia and Japan had a closed market; the import duty on copper in Russia is 30 per cent ad valoremm and in Japan about 2c. Russia's consumption has always been in excess of production and she has imported from 2(1,000 to 40,000 ton, of copper per annum. Japan, with a production of 6,000 to 7,000 tons per month, has absorbed, in normal times, its production, but during recent: sears has exported varyiug quantities in 1929. 2,200 ton-: in 1930, 2,700 tons, and in 1931. 3,600 ton-. Aside from the-e two countries, the international market has heretofore been free. It and when the British Empire duty become, effective the world's markets will be divided into four unit: 1. Russia and Japan, 2. United States. 3. British Empire. 4. Rest of the world. The world's production at present is rennin it the rate of 930.000 tons per annum. This year's production will be over 1,000,000 tons because the several curtailment did not become effective until the second quarter. consumption will be slightly in excess. Deducting from 30,000 tons Russia's and Japan's production of 121.000 tons, 806,000 tons is left divided a, follows:

Jan 1, 1932

By Effingham Humphrey

THE Lehigh Valley. Coal Co. finished the rebuilding of its Drifton No. 2 breaker at Drifton, Pa., in the summer of 1917. The new construction comprises an addition and the complete remodeling of the old breaker. It is of interest to note that the old structure was the first iron breaker erected in the anthracite region. THE OLD BREAKER This old breaker was built by the Cross Creek Coal Co., under the direction of the late Eckley B. Cole, in 1888-89, and was fully described by him in the Transactions.1 The columns were cast iron, 8,'10 and 12 in. square. The floors and partitions in pockets were cast-iron ribbed plates. The struts were cast iron of "H" section; the other members were of structural iron either rolled I-beams or built-up sections. The sizes of the rolled beams varied from 6 to 20 in. deep, while the built-up sections, made of plates and angles, varied from 6 to 63 in. in depth, so that there apparently was no rule to determine the type of section used. In the remodeling of the old structure, practically everything was taken clown excepting the columns and roof, and such beams as were necessary for temporary construction purposes, and, therefore, a close inspection of the old structural members could be made and the effect of the acid water oil them could be noted. The cast-iron members were but slightly attacked by the water, while the wrought-iron beams, in the wet places, were corroded almost to failure.

Jan 2, 1918

By J. Armanet

THREE MINING colleges are maintained in France; the École Nationale Supérieure des Mines, of Paris; École Nationale Supérieure des Mines, of Saint Etienne; and the École Supérieure de la Metallurgie et des Mines at Nancy. Besides graduates of these schools, a few graduates of the École Centrale des Arts et MIanufactures and of the École Polytechnique are employed as ]nine managers or engineers; however, most of the latter have taken a graduate course at one of the mining schools.

Jan 1, 1939

By J. B. Clemmer, P. E. Churchward, C. Rampacek

A cyclic method for processing manganese ores using sodium sulphate as the basic reagent is described. Sodium sulphate is electrolyzed in a diaphragm cell to give an anolyte-containing agentisdescribed.Sodiumsulphuric acid and a catholyte-containing iselectrolyzedincaustic soda, a part of which is carbonated in a cyclic manner to form soda ash. The reduced ore is leached with the anolyte to dissolve the manganese and the impurities are precipitated by addition of catholyte. Manganese in the pregnant todissolvethemanganeseandtheimpuritiessolution is precipitated as synthetic rhodochrosite with a carbonated catholyte, and sodium sulphate is regenerated. Calcining the manganese carbonate gives a high grade product and the carbon dioxide is returned to the carbonation step. The results of laboratory tests using cells equipped with synthetic-fiber diaphragms and permselective membranes, which permit transfer of anions or cations during electrolysis, are described. A METHOD which has been considered for pro-cessing manganese ores under emergency conditions to recover a product suitable for smelting to ferromanganese involves reductive roasting of the ore for leaching with dilute sulphuric acid followed by precipitation of the manganese from the purified pregnant solution with sodium carbonate. Although the process is operable and involves no novel or untried steps, it is noncyclic in regard to reagents. Research seemed warranted to determine if a cyclic process could be developed by electrolyzing the sodium sulphate formed during precipitation of the manganese with soda ash to regenerate sulphuric acid and sodium hydroxide. Reduced ore would be leached with acid anolyte to dissolve the manganese. The iron, alumina, and other dissolved impurities would be precipitated with the caustic catholyte, and the manganese in the purified pregnant solution would be precipitated as artificial rhodochrosite with carbonated catholyte to regenerate simultaneously sodium sulphate for electrolysis. Waste boiler gas and CO, from calcining the manganese precipitate would be recycled for carbonation of the caustic catholyte. There is a surprising lack of data in the technical literature on diaphragm electrolysis of sodium sulphate. One of the more comprehensive papers, by Atwell and Fuwa, describes the problem involved in electrolyzing byproduct sodium sulphate from the viscose process with particular regard to the design and operation of asbestos diaphragm cells. Frisk' also investigated electrolysis of sodium sulphate from viscose-spinning baths to recover caustic soda and sulphuric acid. The objective in these investigations was to produce, by electrolysis and evaporation, a concentrated caustic-soda solution and a sulphuric-acid solution low in sodium sulphate. Because of these requirements, the process was not too attractive despite a favorable yield of caustic and acid with a reasonable power consumption. Because strong acid and base are not required for processing manganese ores and nonelectrolyzed sodium sulphate is not objectionable in either reagent, the present problem was somewhat simpler than that of these investigators. The purpose of this report is to summarize briefly the results of laboratory electrolysis of commercial sodium sulphate in diaphragm cells of different types and the application of the acid and caustic for processing manganese ores in a cyclic manner. Electrolysis in Permeable Diaphragm Cells The principal problem in electrolyzing sodium sulphate in a permeable diaphragm cell is to prevent mixing of the acid and base formed in the anode and cathode compartments. It is not enough to separate the anolyte and catholyte by a single diaphragm. A three-compartment cell in which the sodium-sulphate solution is fed to the center compartment and flows through the permeable diaphragms to the anode and cathode compartments is more efficient electrically. Diaphragms should be porous enough to allow flow of solution to outer compartments but tight enough to prevent gross mixing of the anolyte and catholyte. In addition to being resistant to acid and alkali, the diaphragms should offer minimum resistance to the flow of current. It is also important that the electrolyte contain a high concentration of sodium sulphate to furnish an abundance of sodium and sulphate ions and thereby decrease the current carried by hydrogen and hydroxyl ions. A practical limitation of sodium-sulphate concentration is imposed by the decreased solubility of sodium sulphate with decreasing temperature. At 20°C, a concentration of 200 g per liter sodium sulphate can be maintained. Little is gained in conductivity by using a concentration greater than 200 g per liter. The small-scale continuous electrolysis tests were made in a 12x12 in. open-top bakelite cell equipped

Jan 1, 1956

By W. Geo. Waring

THE growing need of better methods for the recovery of zinc and other elements from complex sulfide ores has suggested an inquiry respecting a possible group separation of the elements by the aid of volatilization at more or less elevated temperatures. It 'is evident that if the zinc content of such ores can be completely separated, for instance, as pure oxide, by a volatilization 'method, there should be no difficulty in recovering the other elements by smelting and refining. Zinc burning" as applied to zinkiferous ores has advanced but little in practice since the invention of the wetherill grate-furnace process in 1852, as may be seen by reference to papers on the subject.' In other words the thermochemical reaction employed in effecting the volatilization of the zinc is essentially one of reduction by means of carbon, whether the ores treated contain their zinc in an oxidized form, or as the sulfide. The zinc vapors, liberated from the ores at a temperature above that required for the reduction of ZnO by C (about ,1100° C.) or for the volatilization of ZnS per se, (about' 1300°-1400° C.) are subsequently burned to ZnO or to ZnO + SOz, by contact with' atmospheric ,oxygen in the upper or posterior parts of the furnace chamber, or in a so-called "combustion chamber" after leaving the .furnace proper.

Jan 1, 1925

By I. H. Pratt

The results of a study on the preparation of thin-film capacitor structures are discussed. The dietectric source material was quartz which was sputtered and deposited onto aluminum electrodes and counter-electroded to complete the metal-oxide-metal structures. This configuration was utilized to evaluate the dielectric, the device characteristics, and related process parameters. The effect of gas sputtering pressure, magnetic field strength, source-to-substrate distance, and power density on the rate of deposition is shown. Increased film thickness uniformity over a 3 by 3 in. area by optimum substrate positioning is indicated. Dielectric constant, dissipation factor, dielectric breakdown strength, insulation resistance, heat treatment, capacitance, and dissipation over the range 400 Hz to 5 MHz are reported. In the fabrication of silicon-integrated circuits, silicon dioxide has found use as a material suitable as a diffusion mask, for surface passivation of the silicon, and for protection of conductive films used for interconnections. Its use as a dielectric for thin-film capacitors in film hybrid circuits has been limited, to a degree, for lack of a compatible processing technique and because of its relatively low dielectric constant. With the recent advent of practical metal-oxide-semiconductor (MOS) field effect devices, the material is now being used to insulate the gate electrode from the conducting channel in the silicon. In this latter application, more stringent requirements have been imposed on .the oxide. A comprehensive resume of the use of silicon dioxide in integrated silicon device technology has been compiled including oxide film and bulk properties, method of oxide formations, and their applications.' A relatively new process to deposit SiO, and other dieIectrics is by rf sputtering, and the purpose of this paper is to describe the behavior of capacitors fabricated with a dielectric which has been sputtered from a quartz target and to indicate the relative effect of several of the process parameters on the film deposition. Work on rf sputtering of SiO2 and other dielectrics has been reported utilizing a triode type of sputtering system as described herein or a diode self-sustained glow discharge system. 2-8 SPUTTERING The process occurs during an electrical discharge in a gas plasma which provides the ions for acceleration to the target to produce the desired sputtering. The necessary plasma can be generated by a dc glow discharge through application of a high potential between two electrodes at approximately 2 to 10 x 10-2

Jan 1, 1969

By G. W. Healy

Activities of oxides in the ternary FeO-MnO-SiO system are calculated from data on the binaries, using the Gibbs -Schuhmann method. These activity data are used, together with thermodynamic relations, to calculate the contents of oxygen, silicon, and manganese in liquid iron, and the composition of the corresponding oxide phases in equilibrium with it. Excellent agreement was found between calculated and experimental metal compositions, indicating that thermodynamic methods, such as those presented, can supply useful data on slag-metal equilibria, and are therefore capable of wider application. When molten steel containing oxygen is treated with a deoxidizer, the product of the reaction is composed of the oxides of the deoxidizing elements together with more or less iron oxide. This assemblage of oxides is presumably very close to equilibrium with the melt since it is formed directly from elements dissolved in it. Therefore, it is likely that metal analyses corresponding to a given oxide phase composition are calculable with considerable precision where sufficient information is available on activities in both phases. The present study was made to test this hypothesis in the case of deoxidation by silicon and manganese. Here experimental data on the relationship among oxygen, silicon, and manganese in the metal phase are available, as are activity data for the MnO-SiO2, FeO-SiO2, and FeO-MnO binary systems. A further objective was to demonstrate in a specific example how gaps in the data may be filled by judicious interpolation, and how the Gibbs-Schuhmann method is applied to obtain activities in ternary systems. The rigorous derivation of the latter, requiring considerable facility in handling partial differential equations, tends to mask the real simplicity of the method, and repel the very engineers and experimenters who would benefit the most from its use. I) GENERAL PROCEDURE Deoxidation of steel with silicon and manganese results in the formation of two phases, metal and oxide. The number of components is four—Fe, Mn, Si, and 0. The phase rule then gives the number of degrees of freedom: If temperature and pressure are fixed, 2 deg of freedom remain. Consequently, it suffices to fix the concentration of two of the components of the system for all the concentrations to be determined and, at least in principle, calculable. The practical problem is then to discover a straightforward method of calculation with a minimum of trial and error solutions. The type of reactions to be dealt with are like the following: Si (in steel) + 2 O(in steel) = SiO2(in oxide phase) The standard free energy of this reaction is readily obtained from the literature, so that the equilibrium constant can be calculated by the expression: Since the metallurgist is concerned with percentages rather than activities, a real solution requires information that will permit activities to be converted to concentrations. This information is fairly adequate for the elements dissolved in molten steel, but is not available for the FeO-MnO-SiO2 oxide system. Therefore, the first step in this study was to find the relation between activity and concentration for the three oxides making up the system. The next step was the calculation of slag and metal compositions that are in equilibrium with one another. As shown by the phase rule, it is sufficient to assume the values of two composition variables in order to calculate the rest. But which two are picked makes a vast difference in how difficult the calculation turns out to be, so that it is necessary to make preliminary trial of several routes to find the easiest one. A convenient method is to begin with the slag, and to pick FeO concentration and that of one of the other oxides. Starting with the relation between oxygen dissolved in the liquid steel and FeO in the slag permits a good first estimate to be made of the oxygen content of the steel in equilibrium with FeO, because the iron content being fairly close to 100 pct, Fe has an activity close to unity. Using this first estimate of oxygen activity, approximate values of the manganese and silicon contents of the melt are readily calculated from the appropriate equilibrium constants. A minor correction for the depar-

Jan 1, 1963

By George F. Beardsley

The silver-fields of Zeehan and Dundas are located on the "West Coast" of Tasmania, 30 miles from the port of Strahan on the Macquarie Harbor. This harbor is 17 miles long, from 4 to 5 miles wide, and completely landlocked. Its only drawback is a shallow bar with 9 feet of water on it. The hills on the western side of the harbor vary from 200 to 300 feet in height, and are all composed of quartzite or a quartz grit. From 15 to 20 miles back from the eastern shore of the harbor is a conglomerate-capped range of mountains, rising to the height of 4700 feet. The immediate eastern

Jan 1, 1893