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DAVID COLE, El Paso, Tex. (communication to the Secretary*).-I notice that Mr. Callow takes issue with me on certain points I have previously contributed to the Transactions, to which I would reply," follows: Regarding Inspiration: Mr. Callow's refinements of gravity methods made just prior to the advent of flotation in the Southwest were intended to be "down to the minute," and the gravity flow sheet for Inspiration ores which he brought out at that time as the result of his long campaign of experimentation was regarded by many as the last word in wet gravity work. It was not my intention to discredit this good work when I said "he threw small light on slime treatment." "Minus 200 mesh," however, is not-synonymous with "real slime." Repeated treatments by gravity methods will result in the separation of a very large percentage of the fine granular sulphides in sizes much finer than 200 mesh, and I gave him due credit for that. The unavoidable losses were made in the "real" slime which I mentioned in the paragraph which Mr. Callow refers to as my "statements on page 1871," and his refinements were not a solution to the real slime problem. Mr. Callow has called attention to the fact that his best results at. Inspiration in gravity work were obtained on Joe Bush ore and he presents a table, viz., Tests Nos. 68, 71, and 72; and asks us to consider and compare these results, made by his refined gravity methods, with the results obtained by 'flotation methods in the new mill "during the second half of 1915 and in August, 1916." Of course, the ore treated in the mill was what happened to come. It was not Joe Bush ore, and therefore comparisons of detail figures are of no value. In regard to Mr. Callow's statements under the caption "Callow Cells Adopted by Arizona Copper Company," I would say that those who have been sufficiently interested to read my paper and' his remarks will notice what amounts to contradictory statements on several points which I cannot allow to go unchallenged. I was on the ground constantly and got my information at first hand. The tables published were the official ones. Mr. Callow was not present during the period and has been laboring under that disadvantage.

Jan 5, 1917

By A. G. McGregor

IN THE Southwest a number of large steel chimneys discharge the gases from the copper smelting furnaces. Some of these chimneys show no deterioration after twenty years, others show serious deterioration after tour years service. A steel stack 20 ft. 7 ½ in. (6.3 m.) in diameter by 279 ft. (85 m.) high, Fig. 1, used for roaster gases only at the Calumet & Arizona Mining Co.'s plant at Douglas, Ariz., was lined to the top of the bell, 40 ft. (12 m.) from the base, with common brick placed on end, lime and cement mortar being used. Above the bell, the stack was lined with 4 by 4 by 8 in. (10 by 10 by 20 cm.) building tile, placed on end, making a lining 4 in. thick. The tiles were supported on angle-iron rings, riveted to the inside of the chimney shell about 15 ft. apart. The chimney was put into use in the latter part of 1913. Four years later, considerable of the tile lining had fallen out of place and mixed with the flue dust at the bottom of the chimney. About a year later, several . flattened and distorted sheets were noticed about 70 ft. below the top. An investigation showed that the thickness of these distorted sheets, which was originally ¼ in., had been reduced one half. One year later, or six years after the chimney went into use, several holes, a square foot and smaller in area, appeared near the flat spots mentioned. Soon afterwards, when the chimney was shut down for repairs, it was found that most of the tile lining for 125 ft. from the top had fallen out and that the steel shell was badly corroded; but where the lining remained in place the shell was undamaged. Many of the tile which had fallen out of place had become soft or flaky and crumbling, others were as hard as when placed. An analysis of the hard and soft tile is shown on p. 2. These tile were of a fireclay mixture, and were used instead of common brick on account of lower cost. The steel forming the upper 125 ft. (38 m.) was replaced, and a 4 ¼ -in. (11-cm.) lining of firebrick was laid from the bell to the top of the chimney. The brick were placed on end, wedges and keys being used. After each 8-in. course was set, keyed, and wedged tight, thin mortar -water, sodium silicate, and finely ground silica-was worked into the joints. The brick are supported on angle-iron rings, every 15 ft., in the same way as the tile.

Jan 1, 1921

By James H. Allen

The development of large diameter rotary drilling techniques and equipment in the last nine years has been the main factor for the rapid advancement made by this method of shaft construction. In 1959, less than 5000 ft of large diameter hole was drilled in the United States for the mining and construction industries. By 1967, large diameter hole footage had increased to 117,000 ft. Part of the increase in footage for holes drilled represents AEC requirements due to the discontinuance of atmospheric testing of nuclear devices. The increase in footage for holes drilled for the mining industry can be attributed to cost savings of shaft construction by rotary methods as compared to conventional blasting methods. Until the late 1950's most large diameter holes were drilled with positive displacement rig pumps or air compressors, direct mud or air circulation, conventional sized oil well drilling strings, and multipass reaming techniques. In some very soft formations it was possible to run a pilot bit with one or more hole openers in tandem to drill the hole in a single pass. The main problem with single pass drilling using tandem hole openers was in providing sufficient circulation fluid for proper hole cleaning through conventional sized drill pipe.

Jan 11, 1968

By Frank A. Hill

A visitor to the Northern anthracite coal-field in 1844 wrote: " History and song have hallowed the valley of Wyoming, and everything pertaining to it seems wrapped in an atmosphere of romance." Song and history have since been almost forgotten in the rush of enterprise and business energy, while the invested capital which has built 160 colliery plants, producing last year 17,031,826 tons of coal and giving employment to 50,000 men and boys, lends an atmosphere the inspiration of which is the very sustenance of prosperity and progress. The fundamental cause of this great valley's financial strength, however, rests on the fulness of its mineral wealth. Its mountains surround and its cities are built upon anthracite coal. Its foundation, physically, financially and socially, is coal. Its geology has governed its growth and developed its greatness. In 1768, ten years, prior to the celebrated Wyoming massacre, two Connecticut Yankees, named Gore, settled near Wilkesbarre, Luzerne County, and, burning Pennsylvania anthracite in their blacksmith's forges, were the first to utilize it as a fuel. Its first use in the household was also at Wilkesbarre, where, in 1808, Judge Fell burned it in an open grate. Carbondale, Wilkesbarre, and Scranton were early recognized as the coal centers of the field.

Jan 1, 1887

By Tell Ertl

The term oil shale is defined. Foreign oil-shale developments are outlined briefly. The richest and most extensive oil-shale deposits in the United States lie in western Colorado. The Bureau of Mines is opening two adjacent areas for underground mining. in western Colorado. From the first area the oil shale is mined selectively as required by the retorting plant. The second area is being developed as a unit of a full scale oil-shale mine to ascertain the most practical methods of mining oil shale and to determine costs. In both of these mining areas, research will be carried on to develop new and improved practices for mining oil shale. Introduction Oil shale is a sedimentary rock containing a solid mineraloid of indefinite composition known as kerogen. On heating oil shale, the kerogen undergoes thermal decomposition and some of the vapor products of the decomposition can be condensed as shale oil. Oil from shale can be a major source of liquid fuels since extensive deposits of oil shale are known to exist throughout the world. The United States considers the establishment of an oil-shale industry only when doubt exists of the adequacy of the domestic supply of crude petroleum. On the other hand, oil shale is not strange to foreign oil men. The industry is an old one in other parts of the world. The French industry has been in existence since 1838, the Scottish since 1859, the Australian since 1860, the Estonian and Swedish The since World War 1, and the Manchurian industry since 1929. The most highly exploited oil-shale deposits are the Carboniferous shales of Scotland. About 20 seams ranging from 4 to I2 ft in thickness are worked. The yield during recent years in scotland has been 18 to 25 gal of shale oil per ton, from 3&"30'000 tons per year' The French and Swedish oil-shale deposits are of lower grade than the Scottish. The Estonian oil-shale deposits are 7 ft thick, and the oil yield averages 50 gal per ton. Over 1,000,-ooo tons are mined each year, half of which is used directly as fuel to substitute for coal and the other half is used for the production of oil. Immense deposits of oil shale that will yield 10 to 15 gal per ton exist in Germany. Because of the impending loss of the Rumanian and Polish oil fields and the bombing of synthetic liquid fuel plants, the Nazis in 1943 started a large-scale oil-shale program in Germany. By V-E Day, it is said, oil-shale production had reached the rate of 2500 tons per day and rapid expansion of the industry was imminent. Australian oil shale, known as torbanite, occurs in beds 2 to 6 ft thick. It is of a very high grade and on retorting yields 80 to 160 gal per ton. The oil-shale industry of Manchuria was the largest in the world during the past decade. The well-known Fushun coal deposit in Manchuria has an overburden of 500 million tons of oil shale about 450 ft thick that will yield 10 to 15 gal of shale oil per ton. The oil shale is

Jan 1, 1949

By S. Brunauer

The hydration of portland cement is treated as a chemical reaction and the changes in matter, in energy and the rate of change of the process are discussed, Portland cement is a mixture of four major and at least as many important minor constituents. In the hydration process, the four major compounds (trical-cium silicate, dicalcium silicate, tricalcium alumi-nate and tetracalcium aluminoferrite), plus gypsum and water form five or six new compounds. In spite o the great complexity of the reaction, considerable progress has been made in its understanding, primarily with the help of such research tools as X-ray diffraction and electron microscopy. The rate of the reaction can be followed by direct and indirect methods of measurements. The effects o composition, particle size (or specific surface), temperature and water-cement ratio on the rates of hydration are discussed. The hydration of portland cement is a chemical reaction accompanied by such highly important physical phenomena as heat evolution, setting and hardening. It is a vast and complex subject, on which hundreds of papers have been published. At the time of the writing of this paper, in October 1962, a two-volume book, which alone contains dozens of papers pertaining to cement hydration appeared in print.' The present paper deals with a few aspects of this vast subject, and the selection was not easy. The work reported here deals with some of the most recent investigations in the field. In any chemical reaction, the physical chemist is primarily interested in three things: changes in matter, changes in energy and the rate of change of the process or the speed of the reaction. This is true also of the chemical reaction between portland cement and water, and all three aspects of the reaction will be discussed. These three aspects are of vital interest to the engineer as well. Portland cement is not a cementing material — the hydration products, the new materials which form in the reaction, have the cementing action. The energy changes manifest themselves in a considerable evolution of heat, which may be useful or harmful. It is useful, for example, in winter concreting, but in very large concrete structures like dams, a large evolution of heat, which cannot be easily dissipated, may produce distress in the structure. Primarily for such a purpose was the Type IV or low heat portland cement developed. The speed of the chemical reaction is important because it determines the time of setting and hardening. The initial reaction must be slow enough to permit placing of the concrete before setting occurs. On the other hand, after the placing of concrete it is often highly desirable to obtain as rapid chemical reaction as possible. For this purpose the Type 111 or high early strength portland cement was developed. CHANGES IN MATTER Portland Cement: In a basic investigation, before one begins to study a reaction, one either knows the quantities and compositions of the starting materials, the reactants, or one determines them. This is obvious; the chemist expresses the changes in matter that occur in a reaction by a chemical equation, which has the quantities and compositions of the reactants on the left side of the equation and the quantities and compositions of the reaction products on the right side. The first question is then what to put on the left side of the equation in the reaction between portland cement and water? It is not very easy to answer this question. Portland cement is not a single chemical compound but a mixture of many compounds. Four of these are considered the major compounds, and at least four of the minor compounds also play important roles in the hydration reaction. In order to avoid complicating matters, the present discussion will be restricted primarily to the four major compounds, which constitute usually more than 90% of a portland cement. The relative amounts of these compounds vary from cement to cement. Actually not only the amounts but the compositions of these constituents also vary to some extent, but the variation in composition of the individual components will be neglected for simplicity.

Jan 1, 1963

By Stuart Croasdale

NOT long ago I was called upon to conduct some experiments on the treatment of ores from the New Cornelia copper mine, Ajo mountains, Arizona, for the Calumet & Arizona Copper Co. The problem was a very interesting one and contained some unusual features. Incidental with this problem was the utilization of a large amount of low-grade pyrite in the Bisbee mines of the company, provided this could be accomplished by any feasible method. The New Cornelia mine is situated 45 miles south of Gila Bend, the nearest railroad point, on the Southern Pacific Railroad. It is about 160 miles, almost due west, from Tucson. This section is one of the most arid in the United States. The normal annual precipitation, as given by the United States Weather Bureau covering a period from 1870 to 1901, is 3 to 5 in. During June and July, 1913, the records kept by the company gave the following results. These are all I have available, but they show the enormous evaporation that can be expected, which may be a factor in leaching operations on a large scale.

Jan 8, 1914

(Under this heading will be published notes sent to the Secretary of the Institute by members or other persons introduced by members.) Mining Geologist. Age, 34; wide experience in all Lake Superior iron-ore districts and Arkansas bauxite district. Examinations, tonnage estimates, reports, direction of prospecting, geologic mapping, churn and diamond drilling. Excellent references. A-2681. Mine Superintendent or Manager. Graduate mining engineer, age 31, married, 10 years' experience, now in government employ as metal-lurgist, desires employment with reputable mining company. New York interview if desired. A-4219. Research Engineer, now in Chile on erection of 50-ton mill with modern machinery for treatment of Chilean nitrate, desires connection, from the first of next year, with firm operating in South or Central America. A-4915. Mining Engineer. Young graduate of Michigan College of Mines; capable of handling men, conscientious worker; desires a position that will lead to assistant superintendency. Any place in the United States. Initial salary relatively unimportant. A-5195. Metallurgist, married, age 25; technical graduate; 3 years' experience in blast and open-hearth furnaces, blooming mills, metallographic, and heat treatment work; desires position as sales engineer in the Pittsburgh district. A-5196.

Jan 12, 1919

By H. E. Nold

THE raw materials of the ceramic industry are mostly clays. This raw material is ground, water is added and the mixture pugged into a moist, plastic, rather stiff mass. From this mass the desired units of manufacture are made (bricks, hollow building tile, sewer .pipe, etc.). These units are dried; then placed in kilns and heated until the desired degree of vitrification is obtained.1 For firing ceramic ware, two distinct types of kilns are used; namely, periodic and continuous tunnel. PERIODIC KILNS Periodic kilns are those ordinarily seen in a brick plant. They are either round or rectangular. The raw, dried, formed ware is piled or set in the kilns to depths frequently exceeding 10 ft. The kiln is heated until the ware is matured, then gradually cooled sufficiently to allow men to remove the ware; then the cycle is repeated. The time duration of the cycle may be more than two weeks.

Jan 1, 1933

By J. J. Jakosky

ALL electrical geophysical methods depend for their operation upon the effects produced by the flow of an electric current. By studying these effects it is possible to predict the general axis of current flow. The greater flow of current is in the path of greatest, effective conductivity; and since the effective conductivity of a mineralized zone is different from that of its surrounding envelope (usually much greater), it is possible to locate such a mineralized zone by the distribution of current. Due consideration must be given, of course, to geological structure, to type of mineralization, and to other factors. A number of methods are used to cause this flow of current, and various methods are available for detecting the presence of such current flow and for studying its effects. In a rather detailed way, this paper will discuss the theoretical and practical phases of the inductive methods of geophysical prospecting. ELECTROMAGNETIC GENERATION OF AN ELECTROMOTIVE FORCE The inductive method is so named because the current flowing in the conductor is obtained by electromagnetic induction, instead of by the use of ground electrodes through which a current is passed as in the applied potential systems, or by direct contact with the orebody. An alternating current flowing in a coil will create an electromagnetic field around the coil. This field will have the same frequency as the current and will radiate or travel outward from the coil in closed magnetic or flux circuits: These flux circuits (in air or a homogeneous medium) will be perpendicular to the plane of the coil and will extend or travel outward with uniform velocity in every direction. Maximum field exists in the plane of the coil. Such a coil used for transmitting or as the "energizer" will exhibit similar figure-eight characteristics to those exhibited by the direction-finding coil which will be described in detail later.

Jan 1, 1928

By John Hall

THE recently announced run of three years, nine months and eleven days made by a. crucible steel melting furnace of the Columbia Tool Steel Co., which is claimed as a. world's record, brings forcibly to our attention the great improvements that have been made in the design, construction and operation of the Siemen's regenerative crucible- melting furnace since its introduction in this country. Credit for this advance should be given to the furnace designer, the manufacturer of refractories, and the operators of the furnaces, whose persistent efforts and intelligent co-operation in attacking the problem have resulted so satisfactorily. There are three factors that determine the life of a crucible furnace, or any other furnace for that matter : Design, nature of refractories and conditions of operation; (including the nature of steel melted) and to some extent these factors are interdependent. Thus, for instance, if a crucible furnace is to lie operated single turn and allowed to cool off considerably at night, in order to save fuel, the use of clay-brick melting holes may be advisable, since silica brick is not well adapted to endure rep eated heating and cooling. But the total life of a clay-brick melting hole is necessarily short. Again, if local conditions such as danger of flood make necessary the building of the furnace largely above ground, so that the radiation of beat is promoted, the cooling down of the furnace over the week ends, when no steel is melted, will be considerable-and the contraction of the furnace that results tends to wrack it to pieces. The character of the metal being melted affects the life of the furnace to a great extent. Low-carbon steels and steels made from iron and charcoal require higher temperatures and much longer melting tune than high-carbon steel or steel made largely from scrap; the life of the furnace will be shorter, and the number of heats melted will be much less, when such materials are melted.

Jan 9, 1913

W. O. OWEN,* Washington, D. C. (written discussion?). Few people appear to realize that the time to reach the crippled soldier is when he is first hurt. In my own judgment, the best time to reach him is before he is hurt, by showing him what other cripples have themselves clone of their own initiative, without Government-support, rendering themselves self-supporting, able to bear a little bit more than their own weight, so that they may lay aside a little bit for a rainy clay and some for a little fun in

Jan 5, 1918

By Erwin S. Sperry

The oxidation of metals melted in contact with air takes place with dissimilar results. Tin, lead or zinc are examples of a class, the oxides of which float on the surface of the melted metal. First a film is produced, which covers the surface; then, if agitation from any cause exposes new metal to the action of the air, additional oxidation takes place, and the film is increased in volume. This change goes on until a considerable quantity of oxide (or " dross," as it is technically called) is formed; depending, of course, upon the duration of the exposure of the metal to the atmosphere. When such metals are poured, the dross may be skimmed off; and clean metal will be left underneath. The removal of such oxides is, therefore, merely a mechanical process. In the case of copper, however, the result is quite different. The sub-oxide of copper (Cu2O) is readily soluble in molten copper; and therefore, instead of the formation of a film of oxide, to be finally removed as dross, the surface of the metal remains bright and clear, because the oxide has been dissolved as soon as it was produced. It is customary in the process of copper-refining to leave a small quantity of oxide in the metal, in order to oxidize any traces of bismuth, arsenic or antimony which have not been entirely removed. As a result, these metals exist in the commercial product as oxides, and not as metals, which would form an

Jan 1, 1901

By P. Somasundaran, D. W. Fuerstenau

Adsorption isotherms for dodecyl sulfonate on alumina were determined at 45°C and 25°C and the data was used for calculating the partial molar heat and entropy of adsorbed ions under various concentrations. Changes in OH and AS observed at certain concentrations agree with the postulate of interaction of surfactant ions to form two-dimensional aggregates at the solid-liquid interface. Values of the total OH and AS for the aggregation process calculated using the Clausius-Clapeyron equation is used to interpret the interactions of surfactant ions with each other as well as with the solvent molecules.

Jan 1, 1973

By Lawson P. Entwistle

SUMMARY ONE of the important reserves of manganiferous iron ore is at Boston Hill, near Silver City, New Mexico. The area consists of a faulted block of gently dipping Lower Paleozoic shale, dolomite, limestone and sandstone, which have been intruded by a roughly circular mass of quartz-bearing monzonite porphyry and subordinate dikes. From a noselike protuberance of the intrusion radiate many premineral faults, which have localized much of the hypogene mineralization. Three important stages of hypogene mineralization can be recognized: (1) mesitite, a manganiferous iron magnesite, (2) quartz sulphides, and (3) barite-galena. The carbonate stage is widespread but stronger near the intrusion. The quartz may have been derived from hydrothermal alteration of the igneous rocks. Barite-galena is most important in the Chloride Flat mining district, about one mile north, where argentiferous galena provided silver for the supergene ore. The hypogene carbonate, lean in iron and manganese, has been oxidized and consequently enriched by meteoric waters containing an excess of oxygen and carbon dioxide to form ore bodies of intimately mixed hematite and pyrolusite. The ore bodies, at one place attaining a length of 1600 ft., a width of 300 ft., and a thickness of 25 ft., are largely confined to areas of brecciation and to spreads from faults in Silurian dolomite beneath soft Devonian shale.

Jan 1, 1944

By E. W. Newman

During 1943 and 1944, there was an urgent need for certain grades of optical calcite (Iceland spar) for instruments for ' military uses. To find a supply of this material, prospecting was carried out in Montana, California and Colorado. Although some production was obtained by the work in California, the best results were from prospecting the large calcite veins of south central Montana. The bulk of the optical calcite mind during World War II has come from that area. The Bureau of Mines took an active part in the search for optical calcite in Montana. It examined most of the known calcite veins in the 70-mile distance between Wilsall, on the Shields River: and Absarokee, on the Still water River, and conducted exploration on several of the deposits. The Geological Survey also took an active part by mapping many of the veins. Actual mining of the calcite was performed at first by Calcite Operators, Inc., and later by the Metals Reserve Co., through an agent. A sorting plant was established at Clyde Park, where custom material could be sold. These activities stimulated mining by private operators. To be suitable for military uses, the calcite mined had to meet rigid specificstions as to both size and quality. Individual crystals had to be clear and transparent and if in the form of rhombs had to measure at least 7/8 in. on each edge. Some color and a few inclusions in the calcite were allowable, but material with incipient or developed cleavages, or showing twinning other than parallel to the base, was unacceptable. History of Deposits The existence of large veins of calcite in south central Montana has long been known, and for many years the farmers of this region have used the common vein calcite for producing grit for chicken feed. According to reports, the fist optical calcite produced from Montana came from the Cartwright deposit near Grey-cliff,' but until recently the mining of optical calcite in Montana has been limited to spasmodic searching for small crystals suitable for making nicol prisms for saccharimeters and microscopes, or for mineral specimens. The possible need of substantial amounts of optical calcite for military uses began to appear late in 1942 and early in 1943, therefore the Polaroid company began searching for a source of supply in Montana and California. Work on the Wade property near Clyde Park was started on a small scale in the fall of 1942, by .4. H. Hansen, of Clyde Park. During the winter and spring of 1943, a modest quantity of optical calcite was mined and shipped to the Polaroid Corporation, Cambridge, Mass. Most of this was produced from the "Hansen vug," which was found close to the surface. Early in the summer of 1943, mining on the Wade property was undertaken by Calcite Operators, Inc., a company organized for mining optical calcite from the

Jan 1, 1948

By E. W. Newman

During 1943 and 1944, there was an urgent need for certain grades of optical calcite (Iceland spar) for instruments for ' military uses. To find a supply of this material, prospecting was carried out in Montana, California and Colorado. Although some production was obtained by the work in California, the best results were from prospecting the large calcite veins of south central Montana. The bulk of the optical calcite mind during World War II has come from that area. The Bureau of Mines took an active part in the search for optical calcite in Montana. It examined most of the known calcite veins in the 70-mile distance between Wilsall, on the Shields River: and Absarokee, on the Still water River, and conducted exploration on several of the deposits. The Geological Survey also took an active part by mapping many of the veins. Actual mining of the calcite was performed at first by Calcite Operators, Inc., and later by the Metals Reserve Co., through an agent. A sorting plant was established at Clyde Park, where custom material could be sold. These activities stimulated mining by private operators. To be suitable for military uses, the calcite mined had to meet rigid specificstions as to both size and quality. Individual crystals had to be clear and transparent and if in the form of rhombs had to measure at least 7/8 in. on each edge. Some color and a few inclusions in the calcite were allowable, but material with incipient or developed cleavages, or showing twinning other than parallel to the base, was unacceptable. History of Deposits The existence of large veins of calcite in south central Montana has long been known, and for many years the farmers of this region have used the common vein calcite for producing grit for chicken feed. According to reports, the fist optical calcite produced from Montana came from the Cartwright deposit near Grey-cliff,' but until recently the mining of optical calcite in Montana has been limited to spasmodic searching for small crystals suitable for making nicol prisms for saccharimeters and microscopes, or for mineral specimens. The possible need of substantial amounts of optical calcite for military uses began to appear late in 1942 and early in 1943, therefore the Polaroid company began searching for a source of supply in Montana and California. Work on the Wade property near Clyde Park was started on a small scale in the fall of 1942, by .4. H. Hansen, of Clyde Park. During the winter and spring of 1943, a modest quantity of optical calcite was mined and shipped to the Polaroid Corporation, Cambridge, Mass. Most of this was produced from the "Hansen vug," which was found close to the surface. Early in the summer of 1943, mining on the Wade property was undertaken by Calcite Operators, Inc., a company organized for mining optical calcite from the

Jan 1, 1948

By C. E. Lesher

THIS paper reports a study of the reactivity of 950°F and 1650°F cokes as measured by relative rates of reduction of iron oxides at temperatures up to 2200°F. Previous work cited shows general acceptance of the theory that reduction by carbon is a gaseous reaction, and that kind and character of carbon as well as particle size have measurable effect on the velocity of reaction. As will be shown, the data obtained in this study con firm those conclusions. The work was not designed to examine iron oxide reduction equilibrium, but if reaction velocity be defined as the speed with which "a reaction tends to approach conditions of equilibrium," the data here presented may be considered as a study of reaction rates, and the relative degree of reduction to metallic iron as the measure of reactivity.

Jan 7, 1950

By Thomas Leonard Watson

Sulphide ore-bodies of more or less lenticular shape occurring in metamorphic crystalline schists, gneisses, and slates, and conforming closely in strike and usually in dip to the inclosing rock, have been recognized and described along the Atlantic seaboard from Quebec to Alabama. The ore-bodies do not entirely conform, in all cases, to the structure of the inclosing schists, but they sometimes cut across the foliation in dip, though conforming more closely with the direction of strike. In composition the principal sulphide mineral is usually py-rite or pyrrhotite, or both, accompanied by copper, frequently gold, and almost always some sphalerite and galenite. Other metallic ores are, so far as these sulphide bodies have been investigated, less common; silver is not uncommon, and in some of the pyrrhotite masses nickel is present in quantity sufficient to be commercially valuable. Cobalt frequently accompanies the nickel, usually in smaller amount, and the two vary much in relative proportion. Quartz and calcite are probably the most common of the non-metallic minerals. A number of silicate minerals are frequent representatives in one place or another ; garnet, am phi-bole, biotite, pyroxene, zoisite and others. The sulphide bodies of Virginia, comprising both pyrite and pyrrhotite, are among the most extensive along the Atlantic seaboard. Among the pyrite bodies may be mentioned the well-known and extensively worked mines of Louisa and Prince William counties, located on the main pyrite belt (A, Fig. 1) of the middle and northern, eastern Piedmont region in Virginia, and among the pyrrhotite bodics is the famous " Great Gossan Lead" (13, Fig. 1) of the Floyd-Carroll-Grayson coun-

Jan 1, 1908

By Robert A. Rapp, Ronald L. Pastorek

Solid-state electrochemical measurements by three alternative experimental procedures were made with the cell FeO, Fe3O4 |Zro.85Cao.15O1.85 |Cu| Zr0.85CaO.15O1.85 | FeO, Fe304 to establish the solubility and diffusivity of oxygen in solid copper in the temperature range 800" to 1030°C. The solubility of oxygen in solid copper and the diflusivity of oxygen in solid copper Dgu = 1.7 X 10-2 exp(-16,000/RT) Cm2/sec were determined and confirmed in alternative experiments. The enthalpy of solution of oxygen in solid copper equals —10,000 cal per mole; the partial excess entropy of the oxygen atoms in the Cu-O dilute solution is approximately the same as that found for interstitial atoms in other metals. The diffusivity of oxygen in solid copper is consistent with that expected for an interstitial atom. RELIABLE values for the saturation solubility N(s) and diffusivity DO of oxygen in solid copper have not been unambiguously established in the literature. Following three early determinations by others,1"3 Rhines and Mathewson4 reported that the solubility of oxygen in solid copper increased from 0.007 at. pct 0 at 600°C to about 0.015 pct at 1050°C. Phillips and skinner,, using essentiially the same analytical procedure, reported that the solid solubility increases from 0.0018 at. pct 0 at 550°C to about 0.0075 pct at 1050OC. The only previous value for the diffusivity of oxygen in solid copper was reported by Ransley.6 Ransley deoxidized Cu-Cu2O alloys in an atmosphere of carbon monoxide gas to yield a solubility-diffusivity product. He used the solubility data of Rhines and Mathewson to calculate the diffusivity values. Another method for obtaining the solubility-diffusivity product (N(s) DO) is by measuring the widths of internal-oxidation zones in copper alloys as reported by Verfurth and Rapp.7 However, the calculated N(S)Do products depend upon the alloy content of the specimen, so that the internal oxidation of copper alloys does not follow ideal internal oxidation kinetics. As a result, unequivocal values for the N(s) DO product were not obtained by this procedure. A solid-state coulometric titration technique similar to that employed in this work was introduced by C. Wagner8 to study the dependence on silver activity of the Ag/S ratio in silver sulfide in the temperature range of 160" to 300°C. Similar experiments have been carried out by C. Wagner and co-workers9-11 to study the stoichiometry range of silver and copper tellurides, cuprous sulfide, and cuprous selenide. Numerous authors have carried out electrochemical measurements with a solid oxygen-ion-conducting electrolyte to determine the solubility and/or diffusivity of dissolved oxygen in several liquid metals.12-l6 Rickert and Steiner17,18 have used solid-state electrochemical measurements to determine the diffusivity of oxygen in solid silver from 760" to 900°C. Two different cell geometries were used. In the cell of linear geometry Fe, FeO | ZrO2 + (CaO) | Ag + [0 (dissolved)] [1] oxygen diffused from the interior of the silver electrode to the silver/electrolyte interface where the oxygen activity had been lowered from a fixed initial value to practically zero by the application of voltage to the cell. The diffusivity of oxygen in solid silver was determined from the solution of the diffusion equation and the time dependence of the cell current. However, this determination of the diffusion coefficient depended upon a knowledge of the solubility of oxygen in solid silver. A cylindrical geometry was used for the cell Pt, O2(Po2 = 0.21 atm) | ZrO2 + (CaO) | Ag + [0 (dissolved)] [II] which also allowed the diffusivity of oxygen in solid silver to be determined. These values were in agreement with other available data.l9 Recently, Raleigh20,21 used a method involving the measurement of diffusion-limited currents in a cell involving the AgBr solid electrolyte to determine the diffusion coefficient of silver in Ag-Au alloys at 400°C. Diffusivity values on the order of l0-14 sq cm per sec were measured in the alloy composition range 10 to 60 at. pct Ag in a single experiment. From numerous electrical conductivity and galvanic cell measurements,9'22"26 the solid solution Zr0.85 Ca0.15 O1.85 has been established as an electrolyte with predominant oxygen ion conduction over a wide range of intermediate and high oxygen activities. For interrelating the thermodynamics and the kinetics of the dissolution of oxygen in solid copper in this investigation, a galvanic cell was constructed with FeO-Fe3O4 as the reversible reference electrode, the Zr0.85Ca0.15 O1.85 electrolyte, and a pure copper specimen under-saturated in oxygen as the other electrode. THEORETICAL ANALYSIS Three variations of a high-temperature electrochemical technique were used in this study to provide two determinations each of the solubility and diffusivity

Jan 1, 1970