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By K. M. Kolobova, E. Z. Kurmayev, A. Z. Menshikov, S. A. Nemnonov, V. A. Trapeznikov

The present work represents a review of our intestigations into the X-ray spectra of solids, which have been carried out by us along two lines of upproach: 1) St@ of the electronic structure of high -rnelting compounds of transition metals; 2) stzddy of the interatomic binding forces by the fine structure of absorption spectra under varying temperature and concentration conditions. With this in mind, int>estigations hare been made into the emission and absorption spectra of the K-series of atoms of transition elements in alloys and compounds. In the problem concerned with the electronic structure of high-melting compounds of transition metals, considerable importance is attached to the question of ascertaining the role played by 3d4sp electrons of metal and 2p electrons of metalloid in the formation of chemical bonds and of giving, on the strength of this data, an explanation of the properties which seem to be contradictory at first sight: good conductivity inherent in metals and high brittleness and high-melting characteristics typical of covalent compounds. Over the last few decades this question has attracted the attention of many investigators whose studies were devoted to this type of compound. Many works, both of theoretical1-3 and experimental4- l5 nature , have contributed much to the elucidation of the physical character of the phenomenon referred to. Alongside the investigations in the field of electric resistance, Hall effect, paramagnetic susceptibility, electronic heat capacity, and the temperature of transformation into a superconducting state, we should particularly emphasize the studies on X-ray spectra, which have played a significant role in the development of the zonal theory for high-melting compounds. This fact has become highly evident after the theoretical calculation of the energy spectrum has been made and the density of states curve in Tic, TiN, and Ti0 has been plotted by Ern and Switendick3 who used the method of augmented plane waves. Correlation of the results of the theoretical calculation of the band structure in the compounds listed above with the data obtained by X-ray spectroscopy studies showed that X-ray spectra can be a source of valuable information on the electronic structure of high-melting compounds within a wide range of ener- gies. It is well known that X-ray emission spectra basically give a direct picture of the occupied excited states above the Fermi level of a solid (valence band, conduction band) and that the absorption spectra (region of initial absorption) give a similar picture of states corresponding to the unoccupied levels near the Fermi surface. Full information on the density distribution of electronic states by energies can be obtained by combining the emission and absorption spectra. Such an opportunity arises from investigation

Jan 1, 1970

By Michael Tenenbaum, T. L. Joseph

Recent researches on the reduction of iron ores have stimulated interest in the effect of increased pressures within the iron blast furnace. From a physicochemical viewpoint, it seems logical to suppose that the increased pressure would increase the rate of reduction of the iron ore within the furnace. This increased reaction velocity would in turn be reflected in an increase in the output of the blast furnace. Any substantial effect of elevated blast-furnace pressures should accordingly be of both technical and economic interest to the operator. It is doubtful whether it is possible to increase the pressure in the stack of the blast furnace beyond two or three atmospheres without incurring severe mechanical difficulties. The benefits to be procured by elevations in pressure must therefore be restricted to pressures below two, or at the most, three atmospheres. Within this range it would seem both economically and mechanically feasible to modify the present design of the upper portion of the blast furnace to accommodate these more stringent operating conditions. This investigation was undertaken to study the effect of moderate pressures on the rate of reduction of iron ore with hydrogen. The use of carbon monoxide is contemplated for later work. Although any results that are obtained in the laboratory cannot be interpreted directly in terms of large-scale commercial operations, it is possible, through such an investigation, to ascertain the order of magnitude of the effects of higher pressure. A more quantitative conception of the effects that would result from the use of increased pressures in the modern blast furnace is needed. In some recent work, Diepschlagl found that, all other factors remaining constant, the degree of reduction of iron ores was much greater when carried out under pressure. Pressures as high as seven atmospheres were used. The degree of reduction was determined from the ferrous and ferric iron in the sponge iron. Results were obtained using both carbon monoxide and hydrogen at temperatures of 400°, 600° and

Jan 1, 1939

By Michael Tenenbaum, T. L. Joseph

Recent researches on the reduction of iron ores have stimulated interest in the effect of increased pressures within the iron blast furnace. From a physicochemical viewpoint, it seems logical to suppose that the increased pressure would increase the rate of reduction of the iron ore within the furnace. This increased reaction velocity would in turn be reflected in an increase in the output of the blast furnace. Any substantial effect of elevated blast-furnace pressures should accordingly be of both technical and economic interest to the operator. It is doubtful whether it is possible to increase the pressure in the stack of the blast furnace beyond two or three atmospheres without incurring severe mechanical difficulties. The benefits to be procured by elevations in pressure must therefore be restricted to pressures below two, or at the most, three atmospheres. Within this range it would seem both economically and mechanically feasible to modify the present design of the upper portion of the blast furnace to accommodate these more stringent operating conditions. This investigation was undertaken to study the effect of moderate pressures on the rate of reduction of iron ore with hydrogen. The use of carbon monoxide is contemplated for later work. Although any results that are obtained in the laboratory cannot be interpreted directly in terms of large-scale commercial operations, it is possible, through such an investigation, to ascertain the order of magnitude of the effects of higher pressure. A more quantitative conception of the effects that would result from the use of increased pressures in the modern blast furnace is needed. In some recent work, Diepschlagl found that, all other factors remaining constant, the degree of reduction of iron ores was much greater when carried out under pressure. Pressures as high as seven atmospheres were used. The degree of reduction was determined from the ferrous and ferric iron in the sponge iron. Results were obtained using both carbon monoxide and hydrogen at temperatures of 400°, 600° and

Jan 1, 1939

By W. J. Reagan

THE problem of increasing output and decreasing percentage of rejections is a vital one in the manufacture of steel of any kind. The making of basic open-hearth steel for use in rolled steel wheels, tires for locomotive and car wheels, and forgings of various kinds, is a highly specialized industry. The increase in weight of railway rolling stock of all kinds, and the high speed that the public demands of transportation facilities, make it imperative that steel for use in this class of material shall be of the highest quality obtainable. During the past few years it has been the writer's good fortune to have opportunity-to study the defects in basic open-hearth steel, and also the results obtained by various changes in open-hearth practice, on such defects. The opportunity for study and the details available are rarely found in the manufacture of steel of any kind. It seems reasonable to assume that many of the results determined here can be applied to the production of steel of other types with a decided improvement in quality, a decrease in the percentage of rejections and an increase in output. All of the material described is basic open-hearth steel with the following range of analysis: carbon, 0.50 to 0.85 per cent.; phosphorus and sulfur, 0.04 coax.; silicon, 0.15 to 0.35; manganese, 0.50 to 0.75. All of this material is bottom-cast, therefore tapping and pouring temperatures are higher than in top-cast production. Ingots used in this type of work are of standard length with varying diameters. The ingot is known as duodecagonal, or twelve-sided. The standard body length is 88 in. and the hot top length, 14 in. Fig. 1 shows a typical ingot of this type. The diameter varies from 13 to 30 in. Ingots for special forgings, which cannot be made in molds of standard size, are made in molds of various sizes and designs. These ingots are sliced cold, into blocks of various lengths, depending upon the weight of the forging to be made. Fig. 2 shows the ingot-after coming from the slicing lathe. Just sufficient metal remains between blocks to hold the ingot in one piece while it is being removed from the lathe; then steel wedges are inserted between the blocks and the blocks are broken apart. This affords abundant opportunity for inspection, as the interior of the

Jan 1, 1930

By J. Parke Channing

THESE days of great industrial and social problems in America produce many suggested solutions and great changes. The practical engineer and employer of labor views these problems differently from the labor leader or the social reformer, but as never before he is sincerely interested in solving them in a way that will be just to all. The inevitable tendency of the day is toward "industrial betterment," "safety," "industrial education," "efficiency," and the many other things' which have become so familiar to progressive employers. There is no longer any question that these things are worth while from both the hu¬man and economic standpoints. They "pay" in dollars and cents. The very center of final success in improving conditions and increasing the efficiency of workingmen must be the spirit of fairness and a knowledge on the part of the employer of how to deal sympathetically and intelligently with his employees. Every progressive employer knows how greatly he desires foremen, superintendents, managers and others who possess these qualities. On the other hand, we are all familiar with serious mistakes made by young graduates of engineering schools who have had no opportunity to develop these qualities, and who have no real appreciation of the worth of the workers. Indeed, one wonders whether much ill-feeling, labor difficulties, and many strikes could not be avoided if such men had the right attitude. Is there any way of remedying this condition? If this particular difficulty can be solved, if these young engineers, many of whom are our coming leaders of industry, can be given the right perspective and the right understanding of these other problems in addition to fair, sympathetic methods of handling men, many of our other problems will be solved-not at once, but gradually and permanently, as these men make good and become influential in paths of industrial righteousness and industrial peace. Many progressive employers of to-day have enlarged their own perspective and realize the great importance of enlarging the perspective of those who shall follow them.

Jan 3, 1915

By H. Reiss

The zone-melting process in which redistribution of solute in a solid bar is effected by the passage of a molten zone is considered mathematically. Simple approximate techniques are developed for computing the manner in which redistribution occurs as molten zones continue to pass. The introduction of the "zone-melting flux" provides valuable insight into the nature of the phenomenon, as well as a central mathematical theme in terms of which the process can be discussed. Curves are presented for typical and general cases. AN extremely efficient purification technique was described recently by Pfann.1 Known as zone refining, it consisted of the slow passage of a series of molten zones, produced by external heaters, through a long solid ingot of the substance to be purified. Equations were given for the maximum separation attainable, and a numerical computation method was described for obtaining the concentration in the ingot after a given number of zone passes. The present paper offers an interpretation of the physical nature of zone melting in terms of a transport process in which formal diffusive and convec-tive flows occur. This interpretation, in addition to providing insight into the physical nature of the process, also provides a basis for its mathematical treatment. From this basis, useful equations are developed for the solute concentration in the ingot as a function of the number of zone passes. These are applicable particularly where large numbers of passes are necessary and where numerical computational methods might be laborious. All considerations will deal with the limiting form of the process, described by Pfann,' in which: 1—Diffusion in the solid is considered negligible. 2—Mixing in the liquid is supposed, complete. 3—The distribution coefficient, k, measuring the ratio (at equilibrium) of solute concentration in the solid to that in the liquid is supposed, independent of composition. In general, this paper will be concerned with a bar of uniform (actually unit) cross section, ex- tending in the x-direction from x = 0 to x = L, where L may be infinite. Zone melting is a transport process, and as such must admit of interpretation in terms of a flux of transported quantity. However, the progress of operation is not measured in units of time but in terms of the number of completed zone passes. Consequently, the zone-melting flux will be a rate, per unit pass, rather than per unit time. The description of this flux and the examination of its properties is given below. Zone-Melting Flux Fig. 1 represents an intermediate stage of the nth pass. Concentration C is plotted against distance, x. The molten zone with its back at the point x and front at x + I moves in the direction indicated by the arrow. As it moves, it leaves behind the nth

Jan 1, 1955

By Carl L. Renzoni

INTRODUCTION This paper defines equity as the issuance of a permanent interest in the business on a broadly distributed basis. As such, it excludes the issuance of equity to either a merchant bank or to another corporation. Nearly twenty years ago the equity markets were very simple: The instruments used were primarily common shares, convertible debentures or convertible preferred shares. Another equity-type option often used, especially by junior companies, was the sale of joint venture interests. Issue sizes were generally in the order of $25 - $100 million and issues were syndicated primarily in North America and Europe by one or two investment dealers. Mining corporations today benefit from a market with much more depth. Issues are syndicated by dealers on a truly international basis, and issue sizes now often range up to $300 million. Moreover, dealers are now willing to take significant risk in buying the issues for redistribution. This discussion of trends in equity markets will encompass: 1) common shares 2) warrants to buy common shares 3) convertible debentures 4) commodity backed instruments A review follows of events that affect the mining industry and investment dealers as they have a bearing on the equity markets for the metal producers. FACTORS AFFECTING THE MINING INDUSTRY The current business cycle, up to October 1987, had been characterised by a buoyant stock market and depressed base metal prices. Mining companies entered this period with weak balance sheets and little prospect of cash flows meeting capital needs. The issuance of equity and the sale of assets were used extensively to reduce debt to manageable levels. During this period, the relative high price for gold, and more important, the very high earnings and cash flow multiples afforded to gold producers, caused companies to target gold as the only game in town. The need for capital to acquire and develop gold properties prompted an unprecedented volume of equity issues. (Burns Fry led or co-managed over $1 billion of mining equity issues per year during this period). This high demand for equity capital by the industry prompted an increase in the use of equity instruments, such as commodity backed instruments. In addition, government tax incentive programs in Canada, such as flow-through shares, allowed smaller companies to raise significantly more equity than would otherwise have been possible. Over $1 billion in flow-through equity was raised in 1987 alone. The abundance of flow-through capital in Canada made it easy to form a new company. One flow-through share fund developed a system of providing the working capital required for a company to be eligible to receive flow-through share capital so that an entrepreneur required only a mining property to get started. Many new companies were formed and several flourished in a buoyant stock market environment to the point that market capitalizations grew to $100 million or more. The current period is in stark contrast to that before October 1987. The equity markets are generally available to the resource industry only on a window basis and only for senior companies and for special situations. The industry is benefitting from buoyant metal prices, and bankers are anxious to provide debt capital. Investment dealers previously processing several equity issues

Jan 1, 1990

By Courtenay de Kalb

REVISION of the United States mining law is needed. chiefly because of the following reasons: 1. The conceptions as to the characteristics of orebodies that were held at the time the statute of 1872 was enacted have since proved to be in many respects erroneous. 2. The operation of the existing law has been found to work unnecessary hardship upon many claimants to mineral land. 3. The existing statute fails in large degree to encourage development of mineral resources. 4. The existing law often produces conflict between placer and lode-claim rights, working unnecessary injustice to placer claimants. 5. The methods of establishing the rights of locators on United States mineral land are defective, and are not uniform throughout the States within which such lands exist. LAW OF THE APEX The objections to the so-called "law of the apex" are so well known as to require no detailed statement. It is sufficient to point out that the apex rule was based upon the notion that ore deposits consisted of well-formed veins included between definite walls, like the slice of ham in a sandwich. The fact is that veins conforming to that simple type are rare. Irregularity is the rule, and the chief metal production of the United States comes from masses which bear no resemblance to the tabular form of vein. Manifestly the law of the apex fails completely in such cases. Moreover, the tendency is constantly toward the exploitation of ores of lower grade than could formerly be worked, and such deposits exist mainly in the form of large irregular impregnated zones and masses, so that the future. development of our mineral resources would be continuously embarrassed by shadowy claims to extra-lateral rights by the locators of so-called apexes

Jan 2, 1915

By D. V. Carter, Dan C. Williams, John R. Coombs

Exploration was active in East and East Central Texas during 1944. Ten oil fields were discovered during the year, of which four show promise of development. The discovery wells of the Sand Flat and Tyler, South fields were drilled to a depth greater than 10,000 ft., and the latter field now produces from the Pettit at a depth of 9890 ft. The Sand Flat well was plugged back to the Paluxy. The other two fields are Glen Rose producers near 8000 ft. The Pickton field produces from the Bacon Lime and Winnsboro from the Rodessa section. The Eylau field, Bowie County, was significant as the first Smackover production in Texas. Magnolia drilled a test in the Concord field, which topped salt. The most extensive and significant development in the district was the Carthage gas-condensate field. It expanded from the 8000 acres of last year to an estimated 190,000 acres, or about 300 sq. miles, and is not defined as yet. The first oil production in the Carthage area was made from the Travis Peak in 1944 in the Rogers Lacy's Cameron Lumber Company well No. I, on the northwestern side of the field. The New Hope field, Franklin County, scored the largest number of completions during 1944 with 24, bringing its total number of wells to 27. Two more pays were opened and produced as dual completions with the older horizons. The Manziel field, Wood County, had 19 new wells added during the year, for a total of 29, while the Pittsburgh field, Camp County, reached a total of 23 wells by completing 14 new ones. Material shortages and drilling restrictions dropped the total number of producing wells completed in the district from 171 during 1943 to 141 for 1944. Abandonments increased from 531 during 1943 to 609 for 1944. Of this number, 479 were in the East Texas field. Subsidy payments had very little effect in the district and it was mostly a few of the old fault-line fields that had any wells to fall within the requirements for subsidy payments. The prices of crude oil remained constant in the district except for increases as a result of subsidy payments. Production and Probation Wartime demands called for increased allowables for many fields, consequently the condensate and oil production for 1944 increased to 190,016,180, which is up 6.9 per cent over 1943. The East Texas field, of course, remained the principal producer of the district, accounting for 134,768'499 bbl. during the year, or 71 per cent of the district total production of condensate and oil. The field topped its own 1943 production by 4.8 per cent and became the first field in the world to produce 2 billion barrels of oil. The Hawkins field remained the second largest oil producer in the district, with 13,317,088 bbl. for the year, a drop of 6.8 per cent from 1943, while Van field was third with 11,635,708 bbl. The

Jan 1, 1945

By C. S. Blair

THE development of a geological department as an integral part of the Tennessee Coal, Iron & Railroad Co. in the Birmingham district, Ala-bama, in 1908 was an innovation probably unique for any mining organ-ization south of the Ohio River, At that time a few of the oil companies were starting geological departments, but there were no geologists among the larger industrial organizations. The Tennessee Coal, Iron & Railroad Co. had been a substantial producer of pig iron for many years and was just getting a start in the manufacture of steel products from the pig iron. It had large acreages of coal land, ore land and timber land, but there was lacking the detailed knowledge of the possible mineral resources of much (of its territory, and this territory at that time covered an area in the neighborhood of 500,000 acres in the states of Alabama, Tennessee and Georgia. Those responsible for the operations of the mining properties, not being familiar with the kind of help that might be expected from geologic work, were decidedly skeptical of the utility of the work. Therefore it was necessary to develop cooperation with the mining organization, by not infringing upon its functions, and by developing the work in such a manner as to demonstrate to the mining department its practical utility. In the first instance the man responsible for a mining operation is apt to assume the attitude that the geologist is a blockader, because the geologist, unfortunately, is obliged to point out difficulties in the carrying out of mining operations in the way originally planned. He points out the dangers of mining out one coal or metal seam at the ultimate expense of an upper or lower seam, and he develops structural features, such as faults and folds, which call to the attention of the mining operator diffi-culties in his future operations, which the latter had not anticipated. Eventually, however, -the value of having these data became ap to the Tennessee Coal, Iron and Railroad Co., and the operators not only welcomed the geological work and cooperated fully in its acquisition of essential information, but reached the point of asking assistance and advice; and complete coordination of the two activities has existed for many years.

Jan 1, 1933

By E. T. Turkdogan, P. Grieveson

It is shown experimentally that, by making use of the coupled S-O reaction in ionic melts, it is possible to transfer slclJur or oxygen from a lozv to a high chemical potential through an ionic nzenzbrane. This uphill transfer of sulfur is accompanied by a counter downhill transfer of oxygen and vice versa. The Materials balance shows that the amoulits of sul -fur and oxygen lost or gained by one system are the same as those gained or lost by the other systenz — the two systejns being separated by an iofzic membmne. The systems used in these experi?nents were solid Mn-MnS-Mno and liquid Fe-S-0. Sufficient results were obtained Lo study the kinetics of the transfer and the indications are that the counter diffusion of sulfide and oxide iojzs in the membrane is the rate controlling process. WHEN an ionic oxide-melt reacts with an atmosphere containing sulfur and oxygen-bear ing gases the following reaction occurs: 1/2 S2 (gas) +O2- (melt) = S2- (melt) + 1/2 0, (gas) [1] Under the restrictions that i) electric conductance in the melt is purely ionic and ii) each constituent element in the melt does not change valence, the solution of an atom of sulfur in the melt will result in the evolution of an atom of oxygen, so that the electric neutrality is maintained. For a given temperature and melt composition, the equilibrium concentration of sulfur in the melt is determined by the ratio, po2 /ps2 , in the gas phase and not by the individual partial pressures of oxygen and sulfur. This has been demonstrated by a number of investigators, for example by Richardson and withers', Fincham and Richardson,la by St Pierre and Chipman,' and by Turkdogan and Darken.3 In his Howe Memorial Lecture for 1961, Darken discussed the possibility of uphill pumping of sulfur through an ionic membrane at the expense of oxygen. TO test the validity of this concept associated with coupled reactions, experiments were carried out in the following manner. A presintered mixture of Mn-MnS-MnO and prefused mixture of Fe-S-0, contained in platinum and iridium crucibles, respectively, and separated by a thin layer of soda-glass (to act as an ionic membrane), were placed side by side in an evacuated silica capsule and sealed. This was then kept at 1400°K for a required time to allow Reaction [11 to occur via the ionic membrane. When partial equilibrium is reached, the ratios Po2 /pS2, for systems on either side of the membrane, are equal and the flux of sulfur and oxygen through the membrane becomes zero, although the individual partial pressures po2 andp,, in these two systems may differ considerably.

Jan 1, 1962

By Louis J. Demer, Paul A. Beck

As reported in a previous publication,1 isothermal grain growth in high purity aluminum and in an aluminum alloy with 2 pct magnesium can be adequately described by means of the empirical relation: [ ] or in some cases, by the simpler relation, [ ] Here, D is the average grain size after an annealing period t. The annealing period includes the time for complete recrystallization R, and the time for grain growth [to]. DA is the grain size as recrystallized, n is a parameter depending on the temperature and on the material. The effect of 2 pct magnesium in solid solution was to decrease D, and to increase R, A and n at a given temperature. The present work was undertaken in order to investigate the above listed effects of magnesium in solid solution, as functions of the magnesium content. The work also includes the study of certain anomalous effects observed in the recrystallization and grain growth of the 2 pct magnesium alloy at 350°C. EXPERIMENTAL PROCEDURE The method of producing the ingots used in this work was described in detail1 and need not be reproduced here. The materials used were high purity aluminum, furnished by the Aluminum Co. of America, of lot analysis shown in Table I and magnesium from a high purity distilled stock of magnesium crystals. [ ] Ingots were prepared for a series of binary aluminum-magnesium alloys of increasing alloy content. The numbers used to designate these ingots and their magnesium contents by chemical analysis are given in Table 2. [ ] The analyses showed no difference in composition between the top and the bottom of the ingots. Spectrographic analysis of the ingots for elements other than magnesium showed, within the limits of accuracy of the method, no increase in impurities over the amounts given in the lot analysis for the high purity aluminum in Table I. Careful microscopic study of ingot 21 in the as-cast condition, at magnifications up t0 1500X, revealed a cer-

Jan 1, 1948

By W. H. Adams

Shortly after becoming one of the van-guard of mine-developers in the State of Virginia, during the year 1883, I called the attention of the Institute to certain deposits of pyrites, which have been largely worked since. In all cases these deposits are covered with iron-ore (limonite), extending 40, 50 or 60 feet from surface to water-level. The several classes of brown iron-ores are found almost continuously along a prominent ridge of mineral-bearing slates, which can be traced from the James river northeasterly to the North Anna, the Rappahannock and the Potomac rivers, crossing the counties of Louisa, Spottsylvania and Stafford. Outcrops are plainly discoverable from end to end of this belt, also, in places, to the right and left of it, and at intervals there are evidences of workings, some of them for known purposes and others of unknown age and meaning. These old workings have an interest aside from the minerals they may contain or may have yielded. I have been engaged during the past five years in the collection of facts concerning them, which might determine definitely the site of those iron-furnaces, placed by tradition within reach of " the towne called Germanna," which were the first ever built in this State or on this continent. The events which led to the establishment of this important industry are sufficiently narrated in a paper written by Mr. R. A. Brock, Secretary of the Virginia Historical Society, and printed in the Proceedings of the National Museum, 1885, page 77, from which I quote the following : " To Virginia, the first of the English settlements in America, belongs the honor of inaugurating within her limits, as a colony, that most important industry, iron manufacture. "The London Company contemplated a variety of manufacturing enterprises from the very beginning of its authority; prominent among them was that of iron. In 1610 Sir Thomas Gates testified before the council of the Company at London, that in Virginia ' there were divers minerals, especially iron-oare,' lying upon the

Jan 1, 1892

By L. S. Darken

IT has been known for sometime that in an ionic lattice, such as that of Ag2S or FeO, the migration velocity of the anion may differ markedly from that of the cation, the cation being usually the more mobile. It has been shown, for example, that during the formation of silver sulfide tarnish on silver, the tarnish layer grows principally by the motion of silver cations through an essentially stationary silver sulfide lattice. Similarly, the growth of wüstite scale on iron proceeds principally by motion of iron ions, this being accomplished with the aid of vacant iron lattice sites into which the iron may readily move. Likewise investigations of solid solutions of various salts show that there is usually considerable difference in the mobility of the different cations. Measurements of the mobility of various metals in liquid mercury indicate that the various metals move at different rates relative to the mercury. In view of the foregoing it seems reasonable to suppose that when any single phase solution is acted upon by a field, the atoms of different elements respond in different ways; in particular, that the force arising from a particular concentration gradient in a binary alloy would cause the atoms of one component to move with a drift velocity which is in general different from that of the atoms of the other component. The recent experiments of Smigelskas and Kirkendall1 support this viewpoint, since they found, in essence, that during diffusion in alpha brass zinc moves appreciably faster than copper. This was evidenced by the relative motion of inert molybdenum wires. Such a phenomenon is incompatible with the place interchange theory of diffusion proposed by several authors, most recently by Birchenall and Mehl.2 This theory has, however, also been questioned3.4 for other reasons, principally because of the high energy required for direct atomic interchange. The rather large difference between self-diffusivity, as determined by tracer technique, and mutual diffusivity, as determined with the aid of another element at low concentration, might also be interpreted as favoring the above idea; however, Birchenall and Mehl have pointed out that there is another possible interpretation of this difference; this is discussed later. A rather interesting and pertinent observation was made by Schwartz,5 who noticed that tungsten lamp filaments, heated by direct current, commonly fail by necking down in the region at the temperature gradient near the positive end, with a concomitant swelling at the corresponding position near the negative end. He introduces considerable auxiliary evidence to show that this phenomenon is occasioned by the motion of tungsten cations which migrate in the high temperature region from the positive end toward the negative end. The mechanism of this migration is not clearly understood. If, however, this experimental evidence be accepted, we are forced to conclude that alloying elements in the tungsten may migrate by the same or a similar mechanism, whatever it may be, at a greater or lesser rate, thus giving rise

Jan 1, 1948

By HENRT M. HOWE

IN my original paper, Piping and Segregation in Steel Ingots, I pointed out1 among other things that, in view of the slighter stretching (virtual expansion) of the crust, and greater opportunity for sagging, there should be less piping in broad than in narrow ingots, and less in slowly-cooled ingots, e.g., those cast in pre-heated sand molds, than in those which cool quickly, e.g., those cast in iron molds. A. A. Stevenson2 said that neither of these predictions agreed with his own experience. In particular, in a picture which he showed of a wide and of a narrow ingot cast from the same ladleful of steel,, the wide ingot had certainly piped much more deeply than the narrow one. At the time I did not see the explanation of these discrepancies, but further reflection makes it evident. One of the most important elements in determining the depth of the pipe is the degree of " top-lag," that is, the degree to which the solidification of the top of the ingot lags behind that of the bottom. 'Through this lagging the steel of the upper part of the ingot is able to run down and fill the pipe below as fast as it forms. To the importance of this lagging I called attention in my original paper.' Sand vs. Iron Molds.-If we compare two like ingots, one cast in an iron and the other in a sand mold, we see that the top-lag' is much greater in the former than in the latter, be¬cause in the former the lower part of the ingot is cooling off fast while the metal is running into the upper part. It is perhaps easier to look at this as a case of the solidification of the hot-

Dec 1, 1909

By H. J. Gluiskoter

The chlorine content of the coals in the Illinois Basin ranges from 0.00% to more than 0.60%. The chlorine content of the Herrin (No. 6) Coal has been mapped on a regional scale and, in general, increases with the depth of the coal. The depth-chlorine correlation exists because the coal is in apparent equilibrium with the composition of the ground water associated with it, and the salinity of the ground water generally increases with depth. At least part of the chlorine can be easily removed from the coal in the laboratory. In a natural weathering experiment, chlorine values decreased markedly during an 8-week period. Results to date indicate that none of the coals studied has a sufficiently high chlorine content to make it unusable in high-temperature steam boilers, although special steps may be necessary in the preparation or utilization of some of the highest chlorine coals. Investigations into the occurrence and distribution of chlorine in Illinois coals have been in progress at the Illinois State Geological Survey for over 35 years. Since 1948, chlorine analyses of face channel samples and of drill core samples of coal have been made routinely. The increased interest in chlorine and alkalies in coal in the U.S. followed that in Europe, where power plants during World War II were called upon to produce at higher levels than previously and with less down time for maintenance. Higher steam temperatures were reached, resulting in increases in the amount of fouling of external heating surfaces and in corrosion of boiler tubes when high chlorine coals were used. Early studies of the problem showed that coals with high chlorine content were more likely than those low in chlorine to cause difficulties in installations fired with powdered fuel. Crossleyl reported that the first rule of thumb developed for British coals was that coals considered to be high in chlorine (more than 0.30%) caused the most trouble, those intermediate in chlorine content (0.15% to 0.30%) were less likely to cause difficulties and those low in chlorine (less than 0.15%) generally were not associated with alkali bonded deposits and corrosion. However, this relatively simple picture was not adequate to characterize the difficulties that could be expected during the utilization of a large number of coals and Crossley1 developed another scheme for assessing the chances of superheater corrosion. This scheme took into consideration the observation that coals high in sulfur as well as chlorine are more likely to cause corrosion and fouling than coals low in sulfur and high in chlorine. Crossley also considered the ash content. When two coals had the same chlorine and sulfur contents, the one with the greater amount of ash would be the less likely to cause difficulties. Knowing only the amount of chlorine in a coal obviously will not give all the answers. Indeed, the significance of the chlorine content has been much discussed and it has been suggested that perhaps the total alkalies are a better indicator of possible troubles. The observation that the deposits that form

Jan 1, 1968

By V. B. Tare, H. Schmalzried

The use of solid electrolytes for determining kinetic paraneters at elevated tevnperatures is pointed out. The reaction rate constant k1 of the phase-boundary reaction during oxidution of iron to wiistite by CO2-CO gas mixtures has been deternined between 850 nnd 975C, using ZrOz(+CaO) as an electrolyte. Values are between 1.4 x 10-a and 5.2 x 10 ole per sq ctn atm. The tzain difficulty is due to mixed potentials arising from side reactions at the electrolyte inteyface. In a number of papers the calcium-doped zirconia electrolyte has been used for the determination of thermodynamic data from measured differences in oxygen activities (or potentials) between two electrodes. The purpose of this note is to suggest the use of this solid electrolyte for kinetic measurements as well. The principle can be seen from Fig. 1. A thin and compact phase II (electron conductor) is fixed on a plate of gas-tight, polished ZrO2(+CaO) (I), which separates two compartments with different oxygen potential. p, is a constant reference pressure of oxygen (1 atm). The electromotive force of this galvanic cell is given by E = RT5 In pep, and pe is the oxygen partial pressure at the interface electrolytephase 11. If phase I1 is in equilibrium with the surrounding gas phase, p, = DR. If pg changes sud- denly to a value pi, p, and therefore the electromotive force, E, change as a function of time according to the phase-boundary reaction rate at the gas phase I1 interface and the transport processes inside phase 11. It is assumed that local equilibrium is established at the boundary electrolytephase 11, that the gas phase shows no concentration gradients, and that the con-

Jan 1, 1967

By Harold Markus, Gerhard Derge

THE first paper1 of this series described a technique of careful surface preparation by means of which reproducible results may be obtained from potential measurements of the behavior of tin in carbonate solutions with a pH range from 8.4 to 11.2. It then went on to establish the behavior of pure tin electrodes under these conditions and showed that the metal remains active at all times, though the steady potential attained after several hours decreases from I.I2[t] volts at a pH of 12.6 to 0.6 volts at a pH of 8.4. This behavior may serve as a norm with which all other data can be compared. In the second paper,2 small amounts of other anions were added to the carbonate solutions and the conclusion was reached that the common impurities encountered in alkaline materials packaged in tin do not increase corrosion. In fact, in some cases these anions may actually promote the formation of protective films. The present paper rounds out this survey by presenting data on the influence of cations added to the carbonate solutions, as well as the effect of alloy additions to the tin. In many cases the potential data are supplemented with weight-loss measurements. Information is also presented on the effects of some additional anions, the influence of gases above the electrolyte, the behavior of high-purity tin, and the effect of atmospheric oxidation on the corrosion resistance of the above-named alloys. Analysis of the entire body of data discloses some general rules applicable to corrosion in carbonate solutions. The experimental methods used are the same as those previously described. EXPERIMENTAL DATA Cations.-The carbonates of the cations K+, Li+, NH4+, which are soluble, were studied in the same way as the anions, by adding 0.01 mol of the metal carbonate to one liter of 0.2 M sodium carbonate solution, pH 11.2, or to 0.1 M sodium bicarbonate, pH 8.4. The other metallic carbonates are only slightly soluble, of the order of 0 7-3 mols per liter or less, and the sodium carbonate solutions were saturated by adding excess reagent several days before the experiment, shaking frequently, and filtering just before use. The chemicals were c.p. grade in each case except the indium salt. This salt was prepared by solution of the metal in hydrochloric acid and precipitation by addition of Na2CO3. These cations may be divided into two classes, according to their effect on the potential behavior of the tin: (I) normal, (2) passive. To offer a basis of comparison, curves I of Figs. I and 2 are given to illustrate the behavior of tin in carbonate solutions saturated with CaCO3. These curves are the

Jan 1, 1941

By Basil B. Zavoico

The symposium on production for the year 1942 contains no papers on the foreign situation except those on Argentina and Mexico. It has always been the policy of officers in charge of the symposium to refrain from publishing information that might possibly injure national or private interests. At the close of the war we hope again to publish full and accurate records of production abroad. Excerpts From Circular to Authors In order to facilitate interpretation of the data in this chapter, we print the following excerpts from the Circular to Authors. The field is the unit in this tabulation. In cases of fields extending across State boundaries, such as Rodessa, it is suggested that each State author treat the section of the field in his State as a unit, and by a footnote indicate that the field extends into an adjacent State. Each space in Table I may represent one of four possibilities; either it is not applicable to the particular field, or the proper entry is not determinable, or the proper entry may be determinable but is not determinable from data available to the author, or the proper entry is determinable. When spaces are not applicable, leave blank; in spaces where the proper entries are determinable but not determinable from data available to the author, please insert y; in spaces where the proper entries are determinable by the author, make such entries. y implies a Rope that in some future year a definite figure will be available. The entry of a zero is a positive declaration, and it is an important declaration where it is in order. Inability to determine precisely the correct entry for a particular space should not lead the author to insert merely y. Contributions of great value may be made by the author in many cases where entries are not subject to precise determination. In such cases the author should use his good judgment and make the best entry possible under the circumstances. For many spaces the correct entries represent the opinion of the author (for example, "Area Proved") and in such cases the entry need not be hedged to such extent as when the quantities are definite yet can be ascertained only approximately by the author. In cases under definite headings but where figures are only approximate, the author may use x. It is thought that the nearest whole numbers are sufficiently accurate for our purposes except as to percentage of sulphur in oil. If an author desires to report any other figures to tenths, he may do so. The quantity of gas produced should include, where possible, gas sold or otherwise marketed, and gas blown into the air, burned as flares or otherwise wasted. Segregation of these figures would be interesting if the authors can make such segregation. In any event, the figures should represent as nearly as possible the total quantity of gas removed from the reservoir. Under the columns on "Depth," the average depth to the top of the productive zones and to the bottom of the productive wells, when subtracted, should give the approximate thickness of the productive zone. For fields where this is not true because of unusually high dip or for some other reasons, it is suggested that the authors indicate in their text the approximate average thickness of the productive zone.

Jan 1, 1943

By Henry M. Howe

In my original paper, Piping and Segregation in Steel Ingots, I pointed out1 among other things that, in view of the slighter stretching (virtual expansion) of the crust, and greater opportunity for sagging, there should be less piping in broad than in narrow ingots, and less in slowly-cooled ingots, e.g., those cast in pre-heated sand molds, than in those which cool quickly, e.g., those cast in iron molds. A. A. Stevenson said that neither of these predictions agreed with his own experience. In particular, in a picture which he showed of a wide and of a narrow ingot cast from the same ladleful of steel: the wide ingot had certainly piped much more deeply than the narrow one. At the time I did not see the explanation of these discrepancies, but further reflection makes it evident. One of the most important elements in determining the depth of the pipe is the degree of " top-lag," that is, the degree to which the solidification of the top of the ingot lags behind that of the bottom. Through this lagging the steel of the upper part of the ingot is able to run down and fill the pipe below as fast as it forms. To the importance of this lagging I called attention in my original paper.' Sand us. Iron Molds.—If we compare two like ingots, one cast in an iron and the other in a sand mold, we see that the top-lag is much greater in the former than in the latter, because in the former the lower part of the ingot is cooling off fast while the metal is running into the upper part. It is perhaps easier to look at this as a case of the solidification of the hot-

Jan 1, 1910