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By Paul Beck

IT is well known that the hardness of metallic single crystals, like that of polycrystalline metals, increases during deformation (hardening by cold-work). It is also known that, as a consequence of deformation, the metallic material acquires an evident thermodynamic instability, revealed, for example, by the fact that the increased hardness gradually decreases with time, especially at elevated temperatures (softening by annealing). The temperature at which the stabilizing process begins is different for various metals, and for any metal it depends on the amount of deformation. Such stabilization of deformed metals may proceed in two different ways: through recovery, and through recrystallization. The former process allows the unstable deformed metal body to approach stability gradually and without visible change in the grain structure; the latter process, like an allotropic transformation, yields directly the undeformed stable "phase" in the form of new undeformed crystals, which, starting out of a certain number of nuclei, grow into and' consume' the deformed hard material. The extent of stability attainable through recovery is limited, espe-cially if the deformation of the metal crystal or crystals involves not only the gliding along slip planes, but also the bending of the slip lamellae, or at any rate the bending of comparatively large parts of the crystal lattice. In such cases, for instance in bent single crystals or poly-crystalline metals subjected to any deformation, recovery will not as a rule be able to restore the "straight" undeformed lattice, and stability can be attained only by recrystallization; that is, by the consumption of the bent crystal lattice parts by new, undeformed crystals-a much more drastic process. It is evident that the part of the surplus free energy stored in deformed crystals, which is present in the form of the elastic energy of the bent lamellae, is in these instances not considerably involved

Jan 1, 1937

By H. P. Willard, Conrad Martin

SINCE the deposits were found in 1927 in the Paradise Range of western Nevada, more than 1 mil- lion tons of magnesite and half a million tons of brucite have been mined and processed into a variety of granular refractory materials used as furnace linings by the steel industry. An additional million tons of magnesite were used during World War II to produce magnesium metal, and some magnesium oxide from the area is going into magnesia cements. Located near Gabbs, Nev., on the west flank of the Paradise Range, the principal bodies occupy an area a mile long by half a mile wide, and lesser occurrences have been found in a belt more than four miles long and in places almost two miles wide. Magnesite reserves containing less than 5 pct lime are estimated at more than 25 million tons. Reserves of better grade material are considerably less.

Jan 4, 1957

By C. W. Davis, R. S. Dean

AMONG naturally occurring inorganic compounds, magnetite has many unusual and interesting properties, and it is the purpose of this paper to call attention to these properties and review possible uses of magnetite that might be based on them; in other words, to see what uses may be found for magnetite as a physical rather than as a chemical entity, as a mineral rather than as an iron ore. The Mineral Physics Studies initiated in the Metallurgical Division of the U. S. Bureau of Mines a few years ago gathered together much information on mineral properties, and they are therefore the principal source of material for this paper. Magnetic Properties Of Magnetite And Possible Uses As A Magnetic Material Magnetite is unique among minerals for its great magnetic susceptibility, approximately one-third that of soft iron, and some magnetites are permanent magnets, or lodestones. The literature contains many measurements of magnetic properties of individual magnetite crystals, but no systematic survey of the effect of mechanical preparation and heat-treatment was available until the recent investigations of the Bureau of which included not only susceptibility but coercive force and remanence as well. For the purpose of orientation, Table 1 gives the magnetic properties of several samples of magnetite and of a few other substances3. This table indicates that when ordinary magnetite is powdered it decreases in susceptibility and increases in coercive force and remanence, approaching the properties of lodestone. The properties of lodestone are in fact probably due to the development of very large internal surface on fine grain size4.

Jan 1, 1937

By W. L. Prehn, Adele Chambers, R. L. Slobod

The centrifuge has been found to be an extremely useful tool for determining capillary pressure curves and for establishing connate water and residual oil in small core plugs. The use of the centrifuge for determining the properties of small core plugs has been discussed in the literature,',' but practically no experimental evidence has been presented justifying the use of this method in preference to other methods (mainly disc method) now in use. Data have been accumulated and are now presented demonstrating the advantages of the centrifugal method, some of which are: (1) rapid establishment of equilibrium, (2) excellent precision yielding very reproducible results, (3) availability of high pressure differences between phases, (4) simple operational procedure, and (5) ability to establish connate water, residual oil, or to obtain complete capillary pressure curve in one day or less. A commercially available centrifuge capable of speeds up to 3,800 rpm, and a high speed attachment providing a maximum rate of rotation of 18,000 rpm were used in this work in conjunction with core holding tubes designed specifically for this application. In view of the outstanding advantages associated with the use of the centrifuge the conclusion has been drawn that this method should be used in place of the more tedious, slower, and less reliable disc method for determining capillary pressure curves and for establishing connate water and residual oil in small core plugs. INTRODUCTION The need for accurate values of connate water, residual oil, and capillary pressure curves in reservoir engineering has been recognized for many years, and the extent of the effort devoted toward solving these problems is reflected in the large number of papers3-" which have appeared in the literature during the past decade. Most of the methods discussed in the recent literature employ a porous disc as a semi-permeable membrane to separate two immiscible phases and make pos-ible the application of an explicit difference in pressure between two phases in the core. Thus, in the determination of the capillary pressure curve the wetting phase (water) is displaced by the non-wetting phase (air or oil). Several investigators1,2 have used centrifugal forces to develop pressure differences between phases. As a result of the first work' in this field the conclusion was reached that "the more rapid centrifugal method for measuring irreducible saturation may have equal value, (compared to use of discs) but more work is required to establish this point." This work was followed in 1945 by a more detailed study2 in which the concepts of this experimental work were more clearly enunciated. A method for calculating saturation for any given speed of rotation based on the observed volume of water displaced was developed and a wider application of the method was suggested. The absence of any subsequent pertinent literature on this subject is interpreted as indicating that no additional work has been completed to substantiate or deny the earlier claims and suggestions of promise contained in the original papers on this subject. One purpose of this report is to provide evidence designed to establish the practical value of centrifugal methods in determining core properties such as connate water and capillary pressure curves. It is also our purpose to suggest a broadening of the scope of this tool to include determinations of residual oil by gas or water drives. THEORY AND PRACTICE IN USE OF CENTRIFUGE Hassler and Brunner2 have clearly presented the basic concepts involved in the use of the centrifuge by relating the performance of a small core in a field of high acceleration to the

Jan 1, 1951

By R. L. Slobod, W. L. Prehn, Adele Chambers

The centrifuge has been found to be an extremely useful tool for determining capillary pressure curves and for establishing connate water and residual oil in small core plugs. The use of the centrifuge for determining the properties of small core plugs has been discussed in the literature,',' but practically no experimental evidence has been presented justifying the use of this method in preference to other methods (mainly disc method) now in use. Data have been accumulated and are now presented demonstrating the advantages of the centrifugal method, some of which are: (1) rapid establishment of equilibrium, (2) excellent precision yielding very reproducible results, (3) availability of high pressure differences between phases, (4) simple operational procedure, and (5) ability to establish connate water, residual oil, or to obtain complete capillary pressure curve in one day or less. A commercially available centrifuge capable of speeds up to 3,800 rpm, and a high speed attachment providing a maximum rate of rotation of 18,000 rpm were used in this work in conjunction with core holding tubes designed specifically for this application. In view of the outstanding advantages associated with the use of the centrifuge the conclusion has been drawn that this method should be used in place of the more tedious, slower, and less reliable disc method for determining capillary pressure curves and for establishing connate water and residual oil in small core plugs. INTRODUCTION The need for accurate values of connate water, residual oil, and capillary pressure curves in reservoir engineering has been recognized for many years, and the extent of the effort devoted toward solving these problems is reflected in the large number of papers3-" which have appeared in the literature during the past decade. Most of the methods discussed in the recent literature employ a porous disc as a semi-permeable membrane to separate two immiscible phases and make pos-ible the application of an explicit difference in pressure between two phases in the core. Thus, in the determination of the capillary pressure curve the wetting phase (water) is displaced by the non-wetting phase (air or oil). Several investigators1,2 have used centrifugal forces to develop pressure differences between phases. As a result of the first work' in this field the conclusion was reached that "the more rapid centrifugal method for measuring irreducible saturation may have equal value, (compared to use of discs) but more work is required to establish this point." This work was followed in 1945 by a more detailed study2 in which the concepts of this experimental work were more clearly enunciated. A method for calculating saturation for any given speed of rotation based on the observed volume of water displaced was developed and a wider application of the method was suggested. The absence of any subsequent pertinent literature on this subject is interpreted as indicating that no additional work has been completed to substantiate or deny the earlier claims and suggestions of promise contained in the original papers on this subject. One purpose of this report is to provide evidence designed to establish the practical value of centrifugal methods in determining core properties such as connate water and capillary pressure curves. It is also our purpose to suggest a broadening of the scope of this tool to include determinations of residual oil by gas or water drives. THEORY AND PRACTICE IN USE OF CENTRIFUGE Hassler and Brunner2 have clearly presented the basic concepts involved in the use of the centrifuge by relating the performance of a small core in a field of high acceleration to the

Jan 1, 1951

By Sherwin F. Kelly

THE principal interest in the meeting sings arranged by the Geophysical Committee this year centered around the many papers dealing with the practical applications of geophysical methods to solving geological problems in many other parts of the world. The program Wednesday morning dealt with work in South Africa, Poland, and South America. Rudolph Krahmann's first paper gave a perspective of the geophysical investigations upon mineral deposits in South Africa. A striking point in his story was the tremendous increase in magnetic work during the last two or three years. This is largely accounted for by the intensive exploration for the extension of the Witwatersrand gold mining area. The author mentioned many surveys in which other methods were used for the search for ores of copper, lead, and zinc, and in the study of water-bearing and oil-bearing structures.

Jan 1, 1935

By G. C. Fryburg, H. M. Murphy

ThE rates of oxidation of metals are usually obtained by heating the metal specimens in furnaces. Such a procedure is satisfactory for most metals. However, there are several metals that oxidize according to the reaction.

Jan 1, 1959

By Herbert Ives

THE incandescent gas mantle is of considerable interest from the standpoint of temperature measurement because it presents a series of apparent contradictions to the established laws of radiation on which are based some of our best methods of temperature determination. One of these contradictions is that the mantle of least brightness (of the commercial thoria-ceria group) is the one having the highest temperature; this, though explicable without any violation of radiation laws, was long a stumbling block to the understanding of the performance of the mantle. Another anomaly is that the energy radiated by the mantle decreases with the rise of temperature, thus apparently invalidating total radiation methods of pyrometry, based on the fourth-power law. The discussion of methods of measuring mantle temperature which follows, is largely taken from an extensive study of the physics of the Welsbach mantle. 1 The incandescent gas mantle consists of a skeleton of refractory oxide of very light weight and open structure, formed by the ignition of a cotton or silk "stocking" previously thoroughly impregnated with salts of certain rare earths. The mantle of commerce is a mixture of approximately 99 parts of thorium oxide with 1 part of cerium oxide. This mixture, discovered largely by accident, gives luminous radiation many times greater than that from either of the constituents taken alone. It is customary to speak of the thoria as the "base" and the ceria as the "colorant," and the commercial mantle represents one of a family in which an oxide of low emissive power is employed as a base, which will assume a high temperature, while a small amount of some other oxide of high visible emissive power is added, which will reduce the temperature of the mantle but little. This is, in general, the most efficient- way, from the standpoint of visible emission, to utilize a substance of high emissive power in the visible spectrum. But it is not necessary. that two substances should be employed to produce a radiator

Jan 9, 1919

By Harry J. Morgan

One of the greatest improvements in drilling equipment has been the development of hard facing metals which are welded by electricity or by acetylene to form a facing which protects the steel of the bit from abrasive wear. The main desirable characteristics of hard facing metals are resistance to abrasive wear, resistance to shock and perfect bond with underlying metal. Resistance to abrasion offered by various metals shows many anomalies. Compounds containing carbon, silicon and boron are the most important hard substances. Carbon, as diamond, silicon carbide and especially the carbides of iron, chromium and tungsten are the outstanding hard products in common use. Tungsten carbide is probably the most commonly used. It is made in the electric furnace and it is important to get the right amount of carbon and the correct crystalline structure in order to obtain the greatest hardness and greatest resistance to abrasion. It may be obtained in three main divisions: wrought, cast and casehardened. Insert hard metals are common. The method of application varies, but it is generally welded to the bit, placed in channels or in drilled holes and covered with a hard surfacing metal. Robinson' has given a very complete article on the use of inserts. Gregg and Küttner2 has discussed the metallography of tungsten carbides and given a good bibliography of the subject,. The time and expense of large-scale testing, together with variations in results, led to the development of a laboratory testing machine for determining the abrasive-resisting qualities of different metals. This machine consists of a motor-driven 40-grain, alumina-base corundum wheel, 8 in. dia., rotating at 30 r.p.m. It is run wet and dressed with

Jan 1, 1930

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 G. W. Reimers, S. E. Khalafalla

A colloidal solution of a ferrimagnetic material, such as magnetite, in a liquid that is immiscible with and lighter than water is projected for use in selective separation of particles according to their density spectrum. Magnetic levitation forces can be created as an antigravity field when the fluid is properly placed in an inhomogeneous magnetic field. When the gradient of the magnetic field is directed downwards, the levitation force in the fluid will be in an upward direction to float sinking nonmagnetic bodies by counterbalancing their density mismatch with the magnetic fluid. Several nonmagnetic objects with densities ranging from 2.50 to 11.35-g cm' were made to float or submerge at will in a 0.96-g cm' density fluid placed in vertical magnetic field gradients ranging from 0.1 to 1 kilo-oersted cm-'. The magnetic levitation force in dyne cm' was found to vary linearly as a function of the object-fluid density mismatch with a slope equal to one g, the acceleration due to gravity.

Jan 1, 1974

By Prince Gelasio Caetani

PRESIDENT DWIGHT'S invitation to be a guest of the American Institute of Mining and Metal-lurgical Engineers was the first of the subsequently very numerous invitations to dinner I have received from my American friends. When I received his telegram I had not yet been even formally appointed Ambassador. I cannot tell you how deeply I appreciated it. It was a hearty welcome in returning to your country which has been for me a second home and it came from the American mining brotherhood which has been my second family.There are two distinct periods of learning in life. The first one are the years spent in school where we learn many things we after-wards forget; the second one are the years of prac-tical apprenticeship which engrave indelible signs in a man's character and shape his life. These latter years I spent in the United States and they have influenced the whole course of my life. I owe very much to my American friends who trained me. The earliest was Prof. Robert Peele, of Columbia University. At the Daly West mine, in Park City, Utah, he curbed my futuristic English spell-ing and had a hard time at it. Prof. James F. Kemp taught me that geology is a guess work just as unre-liable as the prediction of international events; he taught me also that a frank, honest and loyal character will lead a man equally straight through a mining report and through public life.

Jan 3, 1923

By Alvin Kaufman

The industrial revolution of the early 1800's and the subsequent remarkable progress in raising American living standards are based not only on a constantly improving technology but on an ever increasing use of energy from mineral fuels and waterpower. Industrial nations require inexpensive energy sources in order to grow. The more complex the economy, that is, the more intensive the processing of raw materials, the greater the energy needs of that economy. As a result of the current international economic expansion, the worldwide search for sources of low-cost energy has accelerated. As a part of this search there is considerable interest in the potential for commercial development of geothermal power, particularly abroad and in the western United States. This interest is indicated by the fact that 40 exploratory wells have been drilled in the California thermal areas alone during the 1955-62 period. Of these, 24 were drilled in The Geysers, Casa Diablo, and Salton Sea areas.

Jan 9, 1964

(Members are urged to send in for this column any notes of interest concerning themselves or their fellow-members..) Members and guests who registered at institute headquarters during the period Dec. 10, 1915 to Jan. 10, 1916: A. R. Fletcher, Palo Alto, Cal. H. L. Hollis, Chicago, Ill. R. G. Hall,. St. Louis, Mo. Howland Bancroft, Denver, Colo. Walter E. Koch, Terlingua, Tex. G. D. B. Turner, Butte, Mont. George A. Macready, Searchlight, Nev. H. A. Wheeler, St. Louis, Mo. H. W. Edmondson, Concheno, Chili., Mex. George B. Rodgers, St. Francois, Mo. Arthur F. Taggart, New Haven, Conn. Paul S. King, Wilmington, Del. H. V. Winchell, Minneapolis, Minn. G. H. Clevenger, Palo Alto, Cal. Frank A. Ross, Spokane, Wash. J. W. Beard, Syracuse, N. Y. W. D. B. Motter, Jr., Benson Mines, N. Y. Albert De Deken, Louvain, Belgium. S. Le Fevre, Forest Glen, N. Y.. James H. Smith, Jr., Mount Carmel, Pa. E. H. Hamilton, formerly manager of the Virginia Smelting Co., West Norfolk, Va., has become consulting metallurgist to the Consolidated Mining and Smelting Co., of Canada, Ltd., Trail, British Columbia.

Jan 2, 1916

The following additional notes about prices of coal in the early days were collected from the sources shown. Several data about canal tolls and labor conditions are also included. 1796, November: "The inhabitants lay it (coal) in at about 3;d. (83¢) sterling per bushel." (Ref. 73: p. 147.) 1804, March: "In March, 1804, I sent a person accustomed to mining to open the vein of coal, and to load the ark, which was accomplished, and early in the month of April the ark, with the first cargo of bituminous coal passed safely the Conewago falls, and landed her coal at Columbia, Lancaster County. The coal was sold at 31¢ per bushel at Columbia." ($7.75 per ton). This was the first coal from Clearfield County near the town of that name. (Letter from William Boyd: Pa. Senate Jour., 1833-1834, vol. 2, p. 561.) 1807: The following notice appeared in the Bedford Gazette: "Huntingdon, June 4. "Stone Coal.-Such of the farmers as wish to make experiment with stone coal as a substitute for plaster, in manuring their Indian corn, may be supplied with coal gratis upon application to Peter Hughes, at Mr. Riddle's mines, on the Raystown Branch. The proprietor of the mines offers not only to refund the carriage, but to pay the expenses of applying the coal, if upon a fair experiment it is found to be inferior to plaster, which now sells at two dollars per bushel." (Ref. 735: p. 708.) 1809: Coal was delivered in Pittsburgh at 5¢ per bushel or $1.25 per net ton. (Ref. 444: p. 50.) Coal was delivered in Connellsville at 4¢ per bushel or $1.00 per net ton. (Ibid.: p. 185.) 1810: Pittsburgh.-"Coal may be obtained of a good quality, ready delivered at 5¢ a bushel." ($1.25 per net ton.) (Ref. 315: vol. 2.) 1811: "It (coal) costs 6¢ a bushel at your door." ($1.50 per net ton.) (In Pittsburgh.) (Ref. 277: 1811, p. 68.) 1814: At Columbia, now part of Donors, Washington County, Pa., an original sale of lots in 1814 gave the purchaser of each lot the right to mine stone coal gratis from a bank on the property. (Ref. 410: vol. 1, p. 547.) "A laborer is able to dig upwards of 100 bushels per day." (4 tons.) (Ref. 277: 1814, p. 109.) A paper about the early newspapers in West Virginia says: "Collier Wanting. From 10 to 20 steady and industrious men, who understand digging coal, may obtain high wages in Kenhawa for that business, if immediate application is

Jan 1, 1942

By Herbert Banks Johnson

DURING the past 10 or 12 years very little information has been made generally available concerning the commercial possibilities of separating materials by means of static electricity; and yet during that same period important improvements have been made in various branches of the science of electricity, which, when taken together, and applied to electrostatic separation, have resulted in important improvements in that art as well. For example, much improvement has been made in high-voltage electrical equipment such as full-wave vacuum-tube rectification and improved mechanical rectification. Great strides have likewise been made in the development of insulators for high-voltage work, not only in the materials used but also in the design of the insulators themselves. Again, in another field, the development of air-conditioning equipment has improved the technique of controlling the surface condition, through drying or humidifying, of the various materials that are passed through the electrostatic separator. In many authoritative publications and textbooks, the electrostatic separation process is declared to require a balance far too sensitive for general commercial application. For example, one publication1 in the past has referred to an unfavorable effect on the process caused by varying atmospheric conditions such as humidity. Some2 have even gone so far as to state that sunlight and shadows may seriously affect the separating efficiency of the process. Such statements may have been true in the early development of the art, when the source of static electricity was derived from a friction disk machine, such as the Wimshurst. The Blake Mosher equipment and the work of Huff in applying motor- generator sets, transformers and mechanical rectification overcame much of this kind of objection to the commercial application of the electrostatic separating process. Another objection made periodically is that it is generally considered necessary to feed the particles into the electrostatic field in a stream that

Jan 1, 1938

Executive SIDNEY .J. JENNINGS, Chairman GEORGE D. BAR HON .I. E. JOHNSON, JR. EDWIN LUDLOW ROBERT M. RAYMOND Membership KARL EILERS, chairman LEWIS W. FRANCIS .1. E. JOHNSON, JR. LOUIS D. HUNTOON ARTHUR. L. WALKER Finance GEORGE D. BARRON. Chairman. CHARLES F. RAND BENJAMIN B. THAYER Library E. GYBBON SPILSBURY1 Chairman ALEX C. HUMIPHREYS3 GEORGE C. STONE .J. H. JANEWAY4 BRADLEY STOUGHTON Papers and Publications BRADLEY STOUGHTON, Chairman

Jan 10, 1918

By P. W. George

THE rapid increase in cost of discovering new orebodies by churn drilling in the Tri-State district has led to some attempts to lessen the expense by using geophysical methods. Electrical prospecting was tried three or four years ago, but no successful results were recorded. In 1926, the Federal Mining and Smelting Co. engaged the North American Exploration Co., of Houston, Texas, to make some tests with the torsion, balance. At first, it was thought that the most favorable conditions for discovery of ore deposits with the torsion balance would be in locations where the ore was known to occur at rather shallow depths, FIG. 1.-CROSS-SECTION OF DUENWEG LEASE. therefore the first trial was made at Duenweg, east of Joplin, where some zinc ore had been developed at a depth of 130 ft. The gravity gradients at 61 stations on a tract of about seventeen acres indicated plainly one large zone of maximum gravity and a smaller narrow zone of minimum gravity. Fourteen churn-drill holes, half of which struck .ore, show that all the ore found was located outside the zones of maximum and minimum gravity. In the zone of maximum, gravity the limestone beds were closest to the surface, and the first chert beds encountered were at the greatest depth. The results (shown in Table 1) indicated that the gravity of the limestone was greater than the gravity of the fractured chert together with its orebodies, and probably also greater than the bouldery soil and clay on top of the limestone. A cross-section of the Duenweg lease is shown in Fig. 1.

Jan 1, 1928

By J. A. Roberson, Robert A. Rapp

From the observation of platinum wire marker movement in the oxidation of columbium at high lemperatures and low oxygen pressures, predonzinant cation diffusion in CbO, has been demonstrated. The Cu,0 molecule was used as an oxidizing species to study the nature of the porous scale and the location of the reduction site in the oxidation of colum-bium. The Cb205 scale contains microporosity and forms by alternate ionic diffusional growth and fracture. The oxidation of columbium at high temperatures and very low po, results in a relatively compact and protective Cb205 layer. THE observation of marker movements during oxidation is one means for the identification of the mobile ionic species in an oxide lattice. Previous marker experiments in the oxidation of columbium have all resulted in the markers being found on the outside surface of the Cbz05 scale. The Cr203 powder markers of Klopp et a1.,' the gold film marker of Kofstad and ~jijllesdal,' and the platinum wire marker of Cathcart et a1 .3 were found at the oxide/gas interface for oxidation temperatures ranging from 450" to 120O0C. However, in all experiments relatively high oxygen pressures were used. As discussed by Mrowec, even the interpretation of marker experiments in simple scales containing only one compound is not without ambiguities. In brief, it can be said that a marker may be found almost anywhere in the scale layer if the metal oxidizes by cation diffusion through the scale; the position of the marker depends upon morphological happenings in the scale. When considering marker movement in a polyphase scale one must proceed with extreme caution. For example, in the past (and present) work markers have never been found at the columbium-scale interface, and one might infer that the oxygen ion is mobile in CbO and CbO,. However, only trace quantities of CbO and CbOz have been present on any of the specimens, so no firm statement is justified on this basis. Despite previous experimental work, considerable doubt still exists concerning the role of the oxides CbO and CbOz in the oxidation of columbium. The identification of the mobile ionic species in CbO and CbOz from the observation of platinum wire markers was one goal of the present investigation . The linear kinetics of columbium oxidation at high temperatures (T - 1000°C) suggests that the Cbz05 scales which form on columbium are porous. From mercury absorption measurements on a Cbz05 scale formed at 500"C, Aylmore et al.' reported a minimum volume fraction of connected voids equal to 0.15. While these scales often appear to be quite porous when viewed in metallographic cross section, they are so brittle that metallographic preparation is likely to exaggerate any porosity originally present. In this investigation, porosity developed during the oxidation of pure columbium and present at the high temperature was detected by oxidizing specimens in sealed evacuated capsules containing large compacts of mixed copper and CuzO powders. wooda has demonstrated that the CuzO, or (CuzO),, molecule is volatile and that oxygen is transferred by the CuzO molecule from a Cu/CuzO mixture to materials having a greater affinity for oxygen. For each molecule of CuzO that is reduced at a sink for oxygen, two atoms of copper are deposited. Quantitatively, essentially all of the oxidation carried out by a Cu-Cu20 compact results from a displacement reaction involving the CuzO molecule. When a metal which oxidizes to form a porous scale is exposed to the CuzO vapor, the CUZO molecules are reduced in the pores leaving a deposit of metallic copper to mark the site of the reduction. This technique has the rather unique advantage that any copper-coated pores found in the scale are unambiguously related to the reduction site in the growth of the scale under consideration. Pores or cracks which form in a msition*- external to the reduction site or which occur as a result of cooling or handling of the specimen will not exhibit the copper deposit. EXPERIMENTAL PROCEDURE Marker experiments were made on columbium metal, and on pellets of CbO which had been pressed and sintered. Platinum wire markers (0.001 and

Jan 1, 1968

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