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By N. A. Gokcen

EQUILIBRIA in the reactions between gases and liquid metals have been the subject of many interesting investigations. The experimental realization of true equilibrium, however, is questionable in certain cases due to the lack of conclusive studies in reaction rates. It -will be shown here that a systematic interpretation of rate studies with the analysis of prevailing experimental conditions leads to valuable practical information. The reactions of particular interest are: H2(g) +S(inFe) - H2S(g) [1] H2(g) +O (inFe) =H2O(g) [21 2H2(g) + SiO2(s) = 2H2O(g) + - (inFe) [3] The usual and perhaps the most convenient method of investigation may be illustrated with reaction 1. A stream of gas mixture consisting of H2 + H2S is passed over or bubbled through the liquid metal at constant temperature. The ratio of H2S/H2 in the entrant mixture is fixed in each experimental run, and, therefore, the composition of melt varies until the establishment of equilibrium. The purpose of this paper is to derive a formula expressing the minimum time required for the establishment of equilibrium and to compare the calculated values from such a formula with the available data. Equations Reaction 1 is used for the purpose of illustrating the derivation. Let E represent the equilibrium and X the nonequilibrium sulphur in weight percent at any time t in minutes. For the sake of simplicity, it is first assumed that E > X although the results are of general applicability without restriction. It has been shown by Morris and Williams' that within a difference of 1 pct S or less, i.e., E-X5 1.00, the value of K'1 = Ph2s/Ph2.S% is very nearly constant. The maximum ratio of available Ph2s/Ph2 = H,S/H,, from which sulphur can be absorbed by metal, is equal to H2S/H2 in equilibrium with E (which equals H2S/H2 in the entrant gas), minus H,S/H, in equilibrium with X. Thus: Available H2S/H2 = EK'1 - XK'1 [4] Eq. 4 expresses that sulphur can be absorbed by metal from the H2S/H2 in the entrant gas until the gas leaving the metal assumes a value of H2S/H2 which is in equilibrium with the dissolved sulphur X at that time. H,S constitutes up to approximately 1 pct of the gas mixture. Its disassociation into H2 and SL is about 1 pct at 1600°C, hence, the H2S/H2 impinging on the surface of metal is very close to that in the entrant gas. The rate of flow of hydrogen entering the reaction chamber is kept constant experi-

Jan 1, 1954

By Alan D. Smith

Mine roof fall characteristics of 250 falls in 5 different room-and-pillar coal mines, located in Pike, Martin, and Floyd counties, were investigated to determine the relationship of selected parameters associated with roof failure and the assumed condition of the mine roof before failure. The selected parameters used in the study included: presence of cracks and water before the occurrence of fall, sloughing of coal ribs, floor heave condition, type of roof support (resin or mechanical anchor bolts), distance to coal face, and time of occurrence of fall after initial coal extraction. In addition, research hypotheses, utilizing multiple linear regression techniques, were generated to test the relationship among the selected parameters and mine roof condition. The results indicated that the vast majority of falls portrayed some presence of water before the actual fall, occurred in less than 30 weeks after initial coal excavation, located usually greater than 30 meters from nearest coal face, gave evidence of cracks in mine roof before occurrence of fall, generally portrayed a good roof condition before the fall, showed presence of sloughing of coal ribs, and gave no occurrence of floor heave before occurrence of fall. In terms of the characteristics of the original support systems in the mine roof falls studied, most roofs were either supported by mechanical-anchor bolts or resin or full-column bolts; very rarely did the roof appear to fail if supported by posts or cribs. A detail inspection of the hypothesis and model comparison results gave supporting evidence that the condition of the roof is not dependent on the usual indicators of potential failure, such as presence of cracks and moisture. In fact, in most cases of mine roof failure, the immediate roof condition was rated as good or better, which gives little or no indication of pending failure and collapse. Hence, a combination of factors that are not easily accessible to measurement, are the dominant factors in the determination of roof fall-potential areas.

Jan 1, 1984

CONTENTS PAGE FULTON, CHARLES H., and READ, J. BURNS-A New Roasting Furnace for Zinc Flotation Concentrate. Discussed by Charles H. Fulton, Arthur S. Dwight, B. M. O'Harra, Kurt Stock 1 STOCK, KURT.-Redistillation of Zinc. Discussed by G. E. Dalbey, Kurt Stock.. 3 BEASLEY, F. E.-High Zinc in Lead Blast-furnace Slags. Discussed by R. C. Canby, R. L. Lloyd, C. R. Haywood, G. E. Dalbey, A. S. Dwight, E. P. Mathewson, A. L. Walker, B. M. O'Harra, and C. P. Linville 4 STEELE, E. W.-Application of Pulverized Coal to Copper Refinery Furnaces. Discussed by F. R. Pyne, E. P. Mathewson 11 LINVILLE, C. P.-Recovery of Arsenic and Other Valuable Constituents from Speiss. Discussed by C. R. Hayward, C. P. Linville, G. E. Dalbey, A. S. Dwight, Edward F. Kern, Karl Eilers, E. P. Mathewson 12 A New Roasting Furnace for Zinc Flotation Concentrate Discussion of the paper of CHARLES H. FULTON and J. BURNS READ, presented at the New York Meeting, February, 1925, and issued, as Paper No. 1362-D, with MINING AND METALLURGY,. October, 1924. G. E. DALBEY, East Berlin, Conn. What would be the, effect on the formation of sulfates of an increased water vapor content in the roasting gases? CHARLES H. FULTON.-I cannot answer that from our experience. The question of the formation of sulfate in the roasting of zinc is mainly one of temperature and the concentration of S02 and S03 in the gases. We found we could roast almost completely to sulfate if the concentration was kept at the proper point. We, however, did not care to do this because we wished to make a 5 to 6 per cent. S02 gas for sulfuric-acid work. The sulfating of the zinc oxide in the proper concentration of gases goes on very rapidly. There are certain places in the furnace system such as the Cottrell and in a part of the dust chamber in which the roasted

Jan 6, 1925

By John Henderson

Densities of melts 0f the lime-iron oxide-silica system in contact with solid iron have been measured by the maximum bubble pressure method in the temperature range 1250° to 1440°C and the composition range 0 to 40 mol pct lime, 15 to 100 mol pct iron oxide, and 0 to 55 mol pct silica. Densities range from 4.65 g cm 3 for wustite at 1440°C to 2.75 g cm-&apos; at 1350°C for a melt containing 30 mol pct lime, 20 mol pct iron oxide, and 50 mol pct silica. The results are interpreted in terms of a postulate that the melts can be regarded as a random array of oxygen ions in which regions of local order exist to satisfy the coordination requirements 0.f the cations. An understanding of the nature of metallurgical slags is basic to the development of a sound theoretical description of heavy metallurgical extractive and refining processes. Because these liquids are complex, direct measurements of their properties has not thrown much light on their structure. This has led to the approach of measuring the properties of simpler liquids, and building up their complexity until slag compositions are reached. In this way the density of liquid iron silicates was measured in a previous study1 and the present work represents a further stage in this synthesis. EXPERIMENTAL The technique used in the measurement of density was the maximum bubble pressure method. Details of the apparatus and procedure were similar to those previously reported,&apos; with the exception that a constant voltage transformer was used to supply the power input to the furnace and six silicon carbide resistance elements were used in place of the molybdenum winding. With these modifications melt temperature could be maintained within 1 centigrade degree during the course of a run. The silica used to prepare the melts was washed natural quartz ignited at 1000°C; wustite was prepared by air-melting A.R. grade ferric oxide in an iron crucible and lime was prepared by air ignition, at 1000°C, of weighed quantities of A.R. grade calcium carbonate, previously air-dried at 110°C. The finely ground constituents were intimately mixed in a glass ball mill prior to melting. Temperatures quoted are accurate to * 5°C and the standard deviation of the density values, calculated by the method of least squares, ranged from 0.5 to 1.8 pet. However, replicate determinations of density on different melts of the same nominal composition at the same nominal temperature did not vary by more than 1 pct, Table I, and this figure has been taken as an estimate of the accuracy of the density results. The density of carbon tetra-chloride was also measured as a check on the absolute performance of the experimental method. At 20°C a value of 1.593 * 0.002 g cm"3 was obtained; this compares with the literature value2 of 1.595 g cm"3. Results of experiments designed to measure the dependence of the density of lime-iron oxide-silica melts, in contact with solid iron, on composition and temperature are shown in Table I. Because iron sometimes precipitated in the sample during quenching, the Fe203 chemical analyses were only poorly reproducible and should be taken as a guide rather than as absolute values. Fig. 1 shows the data from various sources for the density of liquid iron silicates and Fig. 2 shows isodensity contours at 1410°C for lime-iron oxide-silica melts, calculated by graphical interpolation of smoothed curves drawn through the experimental results, together with the 1400°C results of Adachi and ogino3 and Pope1 and Esin.4 Fig. 3 shows the isothermal variation with composition of the volume of melt per gram ion of oxygen at 1410°C and Fig. 4 shows regions in which the temperature coefficient of this volume is negative, positive, or negligible (<0.005 cm3 deg-I). DISCUSSION a) Disparity Between Reported Density Results. Consider the system iron oxide-silica, the results for which are summarized in Fig. 1. Although there is some difference in the temperatures at which the various densities apply, this difference is not sufficiently large to account for the observed discrepancies. The reliability of the present results for the low-silica region has been confirmed by measurement of the density of liquid wustite by three different techniques. At 1410°C the density measured by a balanced-column method was 4.55 g cm"3, by a combination balanced-column and gas-densitometer method 4.59 g emd3, and by a pycnometer method 4.53 g cm"3. Schenck, Frohberg, and Hoffermann&apos; have also reported a value of 4.55 g cm"3 for the density of liquid wustite at 1400°C. It must be concluded, therefore, that neither Pope1

Jan 1, 1964

By G. W. Gross

A commercial deposit of white kaolinite clay contained in the sandy overburden of the Cambrian Gatesburg formation in Central Pennsylvania was successfully mapped by combined SP and resistivity methods and results were checked by drilling. Resistivity minima in the range between roughly 2000 and 3500 ohm-meters coupled with second-order SP maxima of 50-60 mV contrast were found to characterize commercial white kaolinite clay beneath not more than 30-40 ft. of sandy overburden in the area stdied. This investigation supports the hypothesis, established previously, that certain SP phenomena may reasonably be ascribed to diffusion and membrane potentials produced by interaction of clay lenses, sandy matrix, and ground waters. The success of this test proves that this prospecting technique can assist in locating clay deposits in sandy overburden derived from the weathering of sandstones and carbonate rocks such as the Cambrian formations of Central Pennsylvania. In a recent paper, Gross and Moore (1959) described broad self-potential minima above the outcrops of the Cambrian Gatesburg formation. These "first-order" SP anomalies, of 220-350 mV contrast (Figure 7), are related to the peculiar sandy residual soil covering the Gatesburg formation. Small positive ("second-order") peaks of 50-60 mV contrast are superposed on the bottom or flanks of the first-order troughs. They appear to be related to lenses and layers of kaolinite clays within the sandy Gatesburg overburden. Both first-order and second-order anomalies show a characteristic inverse relationship with apparent resistivity profiles in most cases. An explanation in terns of liquid-junction and shale potentials was advanced. According to this working hypothesis, shale potentials are generated: 1) at the contact of the sandy Gatesburg overburden with the more argillaceous soils of surrounding formations; 2) at the boundary of clay lenses contained in the sandy matrix of that overburden. Concentration gradients between interstitial infiltration waters and perched water tables within the Gatesburg overburden are believed to give rise to the liquid-junction potentials. In order to test this hypothesis further, a detailed study was carried out of a second-order positive anomaly on the property of the Woodbury Clay Co. at Mines (Blair County, Pa., Hollidaysburg folio of the U.S. Geological Survey). A second aim was to establish if combined SP and resistivity surveys are suitable as a practical method for delimiting favorable areas in which commercial kaolinite clay de~osits may be found by drilling. Drilling control was provided by the Woodbury Clay Co. PROCEDURES Instrumentation used for SP measurements was the same as described in the paper mentioned. For resistivity surveys, a direct-current voltmeter-ammeter device built by Georator Gorp. of Manassas (Va.) was used in combination with non-polarizing electrodes from the same manufacturer. Power was supplied by one to six 45-volt, heavy-duty B-batteries

Jan 1, 1961

By J. B. Mackintosh

In a recent paper read before the Institute on this subject, Mr. G. C. Stone advances the theory that the precipitate obtained in Williams&apos;s volumetric process,* by treating the boiling nitric acid solution of a manganese salt with potassic chlorate., is not pure MnO2, but approximates more closely to the composition 10Mn02+Mn0. As the value of the process and the accuracy of our results mould depend on whether this was the fact or not, it has seemed to me, and to my associates, Messrs. Beebe and Colly, that it would be of importance to ascertain the composition of this precipitate, and to that end the following series of experiments has been undertaken. These experiments have all been based on the considerations: 1. That potassic permanganate has an oxidizing power equivalent to five atoms of oxygen for every two of manganese : K2Mn2O8 = K2O.2MnO.O5. 2. That the same amount of manganese in the state of binoxide has an oxidizing power equivalent to two atoms of oxygen : 2MnO2 = 2MnO.O2. If, then, we take a solution of permanganate of unknown strength, and reduce it to binoxide, the oxidizing power of the binoxide formed will be equal to that of two-fifths the quantity of the permanganate solution originally taken. While, if the precipitate obtained should not be binoxide, but an indefinite or definite mixture of bin- and mon- oxides, then, from its equivalent oxidizing power, we can calculate its composition. The analyses were conducted in the following manner. The amount of permanganate taken was decomposed with hydrochloric acid, and concentrated to expel the excess of water. Sufficient excess of nitric acid was now added, and the solution was boiled until all the hydrochloric acid was destroyed. The manganese was then precipitated by potassic chlorate; and, after standing some time to cool—a pre-

Jan 1, 1884

By C. G. Dunn, F. Lionetti

W. G. BURGERS*—It seems almost certain that this investigation shows the way which finally, when more analogous data have been obtained, must lead to the understanding of many features of preferential growth-directions of crystals and of the occurrence of recrystallization textures. In this connection I should like to mention that Mr. Tiedema in my laboratory succeeded in developing an analogous method for preparing crystals in aluminum plates with a chosen crystal-lographic plane and direction parallel to the surface of the plate (to be published in Cryst. Ada). If such crystals were grown in high purity aluminum and test-pieces containing a few crystals such as the authors describe were prepared for this metal, it might be possible that due to the absence of growth obstructing particles, even in this low-melting point metal boundary displacements approaching equilibrium positions might be realized. With regard to the apparently marked drop in surface energy for orientation differences approaching zero degree, and orientation differences approaching those existing between twins, it seems of interest to remark that in aluminum a crystal growing at the expense of fine grained material cannot (or can only very reluctantly) absorb grains in either ap- proximately (within 5—10°) parallel or spinel twin orientation (May, Tiedema and Burgers, Nature (1948) 162, 740 and Cryst. Ada in press). Consequently with aluminum the method of preparing a crystal with a definite orientation does not succeed when the new crystal has to absorb its own texture; for example it is not possible to grow in a polycrystalline wire with a [lll]-texture a crystal with a [11 Indirection parallel to the wire axis (Tiedema: Cryst. Ada, in press). Finally I should like to mention the well-known fact (Burgers: Proc. Acad. Amsterdam (1947) 50, 723) that prolonged annealing of recrystallized nickel-iron sheet with cube-texture never succeeds in transforming this into one single crystal of the same orientation; if, by "secondary re-crystallization," large crystals are formed

Jan 1, 1950

By H. R. Page, A. E. Jr Lee

A. E. LEE, JR. (author)—In addition to the paper we should like to make a few remarks. First, the seriousness of bending of the clay retort cannot be overemphasized. Not only did bending limit the length of the vessel, but it permitted corrosive fluid slags to concentrate in the belly of the retort and thus increased the possibility of boring. Bending also practically prohibited the use of cleanout machines and increased the danger of excessive fume losses by allowing furnace gases to escape around the top of the retort mouth. It will be noted that the Blackwell pottery practice places considerable emphasis on careful drying of retorts. Perhaps it is another smelter superstition, but traditionally the aging of retorts beyond a reasonable drying period has been considered important to long life. We are unable to give a good explanation of why aging should improve retorts. During the past fall in an attempt to prove a theory that the combined water in the clay decreased during aging, about 50 samples of wet retort collars were placed in a dry room when it was closed. Loss of weight, combined water and free moisture were measured each week over the 100 day drying period. The affinity of the dried retort for moisture makes difficult the accurate measurement of free water; however, there was a clearly defined free moisture change from about 12.5 pct when freshly made to about 2 pet at the end of 18 days, then a gradual loss to about 0.25 pet at 70 days and an apparent equilibrium near this figure through the 100th day. There was no appreciable change in the combined water. The change in weight of the average sample was, however, rather unusual, there being consistently a loss of weight throughout the entire 100 days. From the 63rd day on this leveled off to about 0.03 pet per week. These were small samples and certainly should have dried

Jan 1, 1950

By William P. Blake

In my short " Contribution to the Early History of the Industry of Phosphate of Lime in the United States,"* mention is made of the erection by Dr. Emmons and myself of a magnetic machine for the removal of iron-ore from the so-called "red sand," a granular form of apatite. At the time of writing, it was not possible to refer to my diary and notes, and the general statements were made from recollection. The subject seems to have special interest at this time, by reason of the many forms of machines now being introduced and patented for similar purposes; and, having received letters of in quiry for further details, I have availed myself of the opportunity, when recently at home for a few days, to refer to the original notes and records made by me in 1852, when living at Crown Point and Moriah, on Lake Champlain. The machine mentioned in my former communication mas pur chased of Ransom Cook, of Vermont. It arrived, and was un loaded from the boat and taken part way up to the nine, on October 18,1852. The weight was 1400 pounds and the cost $1200. It was constructed, not with permanent magnets but with electro-mag nets. It was set up and first turned by hand on October 28th, using twelve battery-cups or cells, the connections being made with wires in small cups of quicksilver. The magnets were not sufficiently strong, and the machine did not work well. More batteries were sent for, arid the machine was started with steam-power on Novem ber 6th. The ore was dried in kilns, then put through a coffee-mill crusher or grinder, and then fed upon the leather belt which carried it under the magnets. Many experimental runs were made, and some diffi culties were overcome, before December 21st, when the record states that the machine was working pretty well, using 24 cells and giving a product of from 3 to 5 tons a day of granular phosphate. The ori-

Jan 1, 1893

By J. B. Chatelain, M. F. Dufour

FLUID jet mills, employing a compressible fluid to grind materials to the subsieve range, was developed in the early 1930&apos;s, and the subsequent acceptance of these units was the result of their ability to pulverize solids that, because of physical properties, could not be processed by other attrition methods, such as ball, pebble, and hammer mills. Also, the fluid energy pulverizer is the only grinding device that will discharge continuously a 5-micron or smaller product. Simultaneous ultra-fine grinding and classification is the widest application of this unit. Jet mills may be used to advantage to reduce particle size of solids suspended in liquids, for coating one material with another, and effecting chemical reactions and changes in physical characteristics other than a reduction in size. Materials that can be processed by this grinding method include nonmetallic and metallic minerals, ores, metals, pigments, insecticides, fungicides, pharmaceuticals, plastics, dyes, and numerous other organic and inorganic products. Grinding principles utilized in the fluid mills available on the market are basically the same, the major difference being in the shape of the, grinding and classification chamber. Grinding in fluid jet pulverizers is accomplished by collisions between particles of the material being ground with the energy being supplied by compressed fluids entering the grinding chamber at high velocities. The "Micronizer" is a fluid energy mill employing a relatively flat cylindrical grinding chamber. Fig. 1 shows general construction details. The mill shown is equipped with a venturi type feeder using a compressed fluid to inject the feed into the grinding chamber. The energy consumed in forcing the feed into the grinding chamber against the mill pressure is, in some cases, as much as 40 pct of the total required for processing. Recent improvements, using a compression screw feeder as shown in Fig. 2, can reduce this to 1 or 2 pct of the total energy requirements. Grinding Grinding, as carried out in the. Micronizer involves the action of gaseous jets emerging from nozzles located in the peripheral wall of the grinding chamber. The axes, of the jets are tangential to a circle of smaller diameter than the grinding chamber as is shown in Fig. 1, and the gases entering the chamber maintain a high rotational velocity. The feed introduced into the mill is accelerated by the rotating gases and is thrown to the outside where a portion, coming in the zone of action of a nozzle, is further accelerated tangentially and inward. Violent collisions occur between the particles so accelerated and other particles circulating at a slower rate in a thin band near the periphery. It is estimated over 90 pct of the reduction in Micronizers occur as a result of impact within a fraction of an inch of the orifice. Observations also indicate that size reduction is independent of any interaction with the walls of the

Jan 1, 1952

By Richard J. Gonzalez

The petroleum industry includes varied and extensive operations required to supply increasing quantities of refined petroleum products and natural gas that are essential for the economic progress of an expanding population Petroleum has provided the power for the transformation from the "horse and buggy days" to the age of jets and space exploration, and for the remarkable improvement in productivity per worker in agriculture and manufacturing. Without increasing quantities of oil and gas, the world would face painful readjustments to more expensive forms of energy and lower standards of living Petroleum operations start with exploration, development, and production activities that supply the basic crude oil and natural gas Pipelines, ships, barges, and trucks first transport the raw materials to processing centers and then move the finished products to the ultimate consumers. Processing plants extract liquids from natural gas and refineries convert crude oil into a wide range of products These products include transportation fuels, feedstocks for conversion into numerous products (such as fabrics, rubber, and plastics), light fuels for heating, lubricants, and heavy residual materials (industrial fuel oil, asphalt, and coke) The final activity of wholesale distribution and retail marketing moves products into millions of homes, farms, industrial plants, and motor vehicles The use of coal exceeded that of oil and gas until 1946 in the United States and until 1968 in the rest of the world. However, oil and gas have proved to be such convenient and attractively priced fuels that they now supply three-fourths of the total commercial energy (including coal, hydroelectric, and nuclear power) used in North America and more than one-half in the rest of the world. LARGE SCALE OF OPERATIONS By the beginning of 1970, world crude oil production exceeded 43 million bbl daily, -equivalent to more than 2200 million tpy In addition, natural gas and the liquids recovered from processing natural gas supply about 40% as much energy as crude oil Production of oil and gas provide by far the highest value of all mining operations. In the United States, the value of oil and gas production in 1969 of $13 8 billion exceeded the $13 0 billion value for all other minerals The rate of expansion in use of petroleum has been extremely rapid since World War II World crude oil production doubled from 7,500,000 bbl daily in 1946 to more than 15,000,000 bbl daily by 1955 It doubled again to 30,000,000 by 1965, and will double again by 1975 The use of natural gas has increased greatly in the United States and also in Europe, as important discoveries in the Netherlands and the North Sea and technology for moving liquefied natural gas from Africa provided attractively priced supplies

Jan 1, 1976

By H. l. Burghoff, C. H. Mathewson

THE study of the creep of metals under conditions of prolonged loading has received the attention of many investigators for several years and almost innumerable papers have been published on the various aspects of the subject. As it appeared that much could still be learned from a study of single crystals, the present work was carried out to study the effects of temperature and conditions of loading upon the properties and deformation in tension of single crystals of alpha brass containing about 70 per cent copper and 30 per cent zinc. In particular, it was hoped to obtain information from tests below and above the recrystallization temperature of the material, so that properties such as elastic limit, yield point or critical stress, and manner of deformation might be compared for tensile tests at an ordinary loading rate and for prolonged. loading. Accordingly, short-time tensile tests and creep tests were made at room temperature, 300º, 500° and 700°F. The two latter temperatures are above the lowest possible recrystallization temperature of polycrystalline 70-30 brass. PREVIOUS WORK Clarke and White1 have made creep tests of some copper-zinc alloys, including 70-30 brass, and copper-zinc-tin alloys at temperatures both below and above the recrystallization temperature of the materials considered. Hanson and Wheeler have studied the flow and fracture of single crystals of aluminum for short-time and prolonged tensile loading over a range of temperature extending from room temperature to 400°F., their experiments being made without consideration of the orientations of the test specimens. Extensive creep and fracture tests on single crystals of lead at room temperature have been made by Betty3 and by Baker, Betty & Moore.4 Results of the last-named investigation were published while the present work was in progress. Millers examined the elastic limit of zinc single crystals at and above room temperature by means of creep tests, while Miller and Milligan6 reported the results of tests designed to show the influence of temperature on elastic limit of single crystals of aluminum, silver and zinc. The behavior, of iron crystals under static tensile loading at room temperature was reported by Gensamer and Mehl7 while the present investigation was in progress. Their specimens exhibited a well-defined yield point, below which no appreciable creep could be detected. The manner of yielding proved interesting, as the shape of the creep-time curve for the iron crystals differed from the common type of creep curves. Elongation did not begin immediately, or at least was initially very slow. The rate of elongation then increased continuously and finally decreased to zero. This S-shaped type of elongation-time

Jan 1, 1941

By Walter Miller

BY the beginning of 1945 the output of petroleum products for war had reached a volume and a rate of growth which practically assured all requirements so long as war continued. The programs for making gasoline, lubricating oils of required quality, toluene for T.N.T., and chemicals for manufacture of synthetic rubber, as well as numerous other lesser petroleum products, were all well in hand, and unless catastrophic developments occurred there was no doubt of the ability of the industry to meet all demands. The end of the fighting found the refining industry working at top capacity on war commodities, but also in position to convert quickly into peacetime civilian production. 100-octane Aviation Gasoline Production of the vital 100-octane aviation gasoline, starting with approximately 44,000- bbl. daily capacity at our entry into the war, reached a top of 525,000 bbl. a day in the United States by the end of hostilities. With 75,- bbl. from other Allied sources, the grand total was 600,000 bbl., or 25,000,000 gal. each 24 hr. available to the armed forces had fighting continued. At times it was a close race between requirements and production, but never were any important military operations involving the use of high-octane aviation gasoline held up or delayed for lack of sufficient output of such material. The undivided effort of the entire refining industry in full cooperation with the Government made this record possible. Little diminution in output followed the German surrender on May 7. Plans called for a correspondingly greater activity for the Japanese war and possibly for well into 1946. But when the Japanese sued for peace on Aug. 10 most contracts were quickly canceled. Substantial stocks, reputed to be somewhere between 20,000,000 to 30,000,000 bbl., built up largely between V-E and V-J day pending organization of the larger Japanese war program envisaged after Germany gave up, were in the Government&apos;s hands in this country, in addition to working stocks in the war areas. Toluene and Lubricating Oil Requirements for toluene for T.N.T. increased rapidly as bombing speeded UP with increasing control of the air by the Allies in Europe and Asia. Production in excess of T.N.T. requirements which had been going into 1000-Octane aviation fuel blending during 1943 and 1944 was again drawn into explosive manufacture early in 1945. In anticipation of the war continuing into 1946, two new plants were ordered constructed, the decision being announced in April, plans calling for one of them to get into production about the end of 1945, the other in the first quarter of 1946. Both of these projects were later canceled as victory made it evident that the additional supplies would not be needed. Production was

Jan 1, 1946

By Walter Miller

BY the beginning of 1945 the output of petroleum products for war had reached a volume and a rate of growth which practically assured all requirements so long as war continued. The programs for making gasoline, lubricating oils of required quality, toluene for T.N.T., and chemicals for manufacture of synthetic rubber, as well as numerous other lesser petroleum products, were all well in hand, and unless catastrophic developments occurred there was no doubt of the ability of the industry to meet all demands. The end of the fighting found the refining industry working at top capacity on war commodities, but also in position to convert quickly into peacetime civilian production. 100-octane Aviation Gasoline Production of the vital 100-octane aviation gasoline, starting with approximately 44,000- bbl. daily capacity at our entry into the war, reached a top of 525,000 bbl. a day in the United States by the end of hostilities. With 75,- bbl. from other Allied sources, the grand total was 600,000 bbl., or 25,000,000 gal. each 24 hr. available to the armed forces had fighting continued. At times it was a close race between requirements and production, but never were any important military operations involving the use of high-octane aviation gasoline held up or delayed for lack of sufficient output of such material. The undivided effort of the entire refining industry in full cooperation with the Government made this record possible. Little diminution in output followed the German surrender on May 7. Plans called for a correspondingly greater activity for the Japanese war and possibly for well into 1946. But when the Japanese sued for peace on Aug. 10 most contracts were quickly canceled. Substantial stocks, reputed to be somewhere between 20,000,000 to 30,000,000 bbl., built up largely between V-E and V-J day pending organization of the larger Japanese war program envisaged after Germany gave up, were in the Government&apos;s hands in this country, in addition to working stocks in the war areas. Toluene and Lubricating Oil Requirements for toluene for T.N.T. increased rapidly as bombing speeded UP with increasing control of the air by the Allies in Europe and Asia. Production in excess of T.N.T. requirements which had been going into 1000-Octane aviation fuel blending during 1943 and 1944 was again drawn into explosive manufacture early in 1945. In anticipation of the war continuing into 1946, two new plants were ordered constructed, the decision being announced in April, plans calling for one of them to get into production about the end of 1945, the other in the first quarter of 1946. Both of these projects were later canceled as victory made it evident that the additional supplies would not be needed. Production was

Jan 1, 1946

By J. S. Koehler, F. Seitz

THE dislocation theory of plastic flow originated in 1928, when Prandtl1 suggested that the internal damping of metals of plastic origin might arise from the motion of a crystalline imperfection. Following this, Dehlinger2 employed a similar imperfection in a theory of recrystallization. The first detailed theoretical discussions were those of E. Orowan3 and G. I. Taylor4 in 1934. The resulting theory was gen- eralized by J. M. Burgers5 in 1939. Mott and Nabarro, in England, and Seitz and Read,6 in the United States, started an extensive examination of the atomic theory of dislocations in the period between 1939 and 1941. However, this development was arrested by the mar and was not taken up again until after 1945. Since 1946, the field has been the object of very intense activity, particularly in the United States and England. Dislocations are beautiful and intricate imperfections; they are sufficiently complicated to account for the great variety of phenomena encountered in the field of plastic flow. Above all, the dislocation concept enables us to understand how a metal or other plastic solid can deform inelastically under very small stresses at temperatures far below the melting point. Suppose we attempt to shear a perfect crystal plastically. This can be done by sliding one entire atomic plane simultaneously through one atomic distance with&apos; respect to the near-

Jan 1, 1954

By A. C. Losekamp, J. B. Conway

Thermal-expansion data for, tungsten, rhenium, tantalum, .molybdenum, niobium, W-25 pct Re, Ta-10 pct W, ant1 Mo-50 pct Re are presented covering the range from room tempature to 2500°C. In these measureMents, made in a resistively heated tungsten tube furnace operating in a helium atmosphere, data for rod and sheet specimens were found to be identical; in addition, arc-cast and sintered tungsten were found to yield essentially identical results. Optical rneasurenlents of thermal expansion .made in any atmosphere other- than vacuum are subject to a refraction error which can be quite substantial. Specimens tested in helium appear shorter than when tested in racuum and hence a special correction factor must be applied to the helium data in order to obtain accurate results. WHILE it is true that linear thermal-expansion data for many of the refractory metals have been measured to very high temperatures, it is also true that except in a few instances the data from various investigators are not in good agreement. This is particularly evident in the case of tantalum and niobium although some tungsten data have been reported which differ by as much as 40 pct from the data of other investigators. Due to the sensitivity of both tantalum and niobium with respect to impurity absorption during exposure to high temperatures, it is probable that this single factor accounts for the majority of the discrepancies in the thermal-expansion data for these metals. However, this same factor can probably not be employed to explain the existing differences in the tungsten data. In all probability, these are due to errors in the measurement technique, to material composition variations, or to changes which take place in the material during the heating process (e.g., additional densifica-tion resulting from heating a sintered specimen above the original sintering temperature). In view of the discrepancies which exist in the linear expansion data reported for many of the refractory metals, the current study was initiated in an attempt to resolve such differences. Also, no high-temperature linear thermal-expansion data were found to be available for several refractory metals. Providing such data was another objective of the current investigation. MATERIALS In this study test specimens were employed in either rod or sheet form and in several instances both arc-cast and sintered material were employed. Material compositions are presented in Table I. Helium gas was fed to the furnace at a rate of about 0.5 SCFH and no special purification procedures were employed. However, the helium contained less than 50

Jan 1, 1967

By G. Sachs, E. J. Ripling, S. I. Liu, J. J. Lynch

INTRODUCTION IT is a generally recognized fact that by repeated straining the fracture stress of any metal is reduced to a fraction of its value for static loading. The value of this fatigue strength depends upon numerous factors, such as the states of strain and stress, the limits of straining, and the number of repeated loadings or cycles.1.2,3 The large volume of previous investigations on fatigue is concerned entirely with large numbers of cycles, say exceeding 10,000 and up to 500,000,000. However, the changes in fracture stress and fracture strain occurring after a small number of repeated loadings have attracted little attention. Apparently the only investigations of this type are those byLudwik4,5 who subjected steel, copper, and aluminum wire to repeated torsion. In each test the torque was varied between identical values in the two directions of twisting. Depending upon the magnitude of the moment, fracturing occurred after a number of cycles, up to 10,000. The results of Ludwik&apos;s tests will be discussed later. Such torsion does not readily yield actual stress and strain values. Therefore a preliminary study was made of the effects of repeated direct stresses, i.e., tension and compression stresses. Because such tests are considerably more tedious than torsion tests, only high stresses were used in the preliminary work, yielding definite changes in metal properties after a few cycles. It was found in these tests that strains could be controlled more readily than stresses in the investigated range of high stresses. This paper, consequently, deals with the effects of strains of equal magnitude but different signs. The metal was first prestrained in static tension by a certain amount then subjected to compression to yield the same amount of strain after unloading. This loading cycle was repeated up to a maximum of seven times. After various cycles, the stress-strain curves in tension were determined, up to fracturing. As material for these tests, the aluminum alloy 24ST was selected because it exhibits a comparatively small amount of necking in the tension test. This alloy permitted, therefore, rather accurate control at the high strains necessary to produce fatigue failures at less than seven cycles. The results of this investigation appear sufficiently interesting to extend the method of attack in various directions. It is intended to study (I) the effects of cycles up to a few thousands and (2) the effects of strains of different magnitude in tension and compression, respectively. The latter variable also includes as a special case the effects of compressive strains.

Jan 1, 1948

By R. S. Wagner, C. E. Miller, H. Brown

A dc field was applied to liquid BI-Sx or Au-Ge alloys of eutectic composition. The liquid alloys were kept at a temperature slightly above the eutectic. The concentration changes due to electrodijfusion are large enough to cause nuclcation and growth of the primary phases at the respective electrodes. Nearly complete separation of Bi-Sn eutectic was obtained as well as substantial separation of Au-Ge eutectic. The effect of an electric field on the solute distrihn-tion was itluestignted itt tlirectiortally solidified rods of a dilute Bi-Sn (0.5 al. pc,t Bi) alloy. Field-freezing was carried out in small-diameter cupillay tubes to avoid cotuectice mixing -of the liquid. The relative sollcte corzcentratioi, Cs/Co , was rneusred by n radioac1il.e tracer netlod. Cs/Co can be made both largev than unity or srialler than the equilibiuwz distvibrrlion c.oejyicienl, k, , oiler a substattiul portion of the soliclifi&apos;erl rocls. A direct current, passed through a liquid-metal solution, can cause substantial concentration changes by electrodiffusion. The magnitude of the change depends on the difference in ionic mobilities of the atomic species in solution. Electrodiffusion has been studied in many binary and ternary liquid alloys.&apos;y2 It was found that the rate of material transport decreases with time for a constant applied field, as a concentration gradient is established in the solution. A steady-state concentration profile is achieved when electro-diffusion is compensated by chemical diffusion. This may seem to limit the use of electrodif fusion for metallurgical application. However, a way of utilizing the effect of electrodiffusion is to combine it with crystallization or controlled freezing. rakin was first to propose this as a new method of separating metal alloys of eutectic composition at temperatures slightly above the eutectic temperature. It was possible by this method to separate Bi-Sn and Bi-Cd eutectics into their component phases. Angus et al discussed the possibility that the effective distribution coefficient, keff, could be varied by proper application of an electric field during solidification. The combination of electrodiffusion and solidification, called field-freezing, was discussed in detail by Pfann and aner. It was shown that field-freezing can be used as a crystal-growth process, an efficient method for eutectic separation, and a new means of changing the effective distribution coefficient. k,ff, beyond the usual range of ko < k,ff < 1. The liquid layer adjacent to the solid-liquid interface can be either increased or depleted in solute due to

Jan 1, 1967

By Charles S. Barrett, F. W. Steadman

DEFORMATION bands of surprising regularity are found in large-grained polycrystalline copper after cold-rolling (Fig. I). Individual bands frequently are large enough to permit a determination of their orientation by means of etch pits and an optical goniometer. Measurements have been made on 21 areas in seven different grains, and these, combined with X-ray studies of nine single crystals that had been cold-rolled after mounting in a polycrystal-line block, have contributed to a better understanding of the preferred orientations in rolled copper just as similar studies have for rolled iron&apos; and brass.2.3 Particular attention was given to determining orientations that are stable during rolling and to the manner of fragmentation and rotation of unstable grains. The possible role of twinning was also carefully investigated. The texture of polycrystalline copper after cold-rolling is well established by the pole figures that have been plotted by Schmid and Staffelbach,4 Iweronowa and Schdanow,5 and Brick and Williamson,3 all of which are in substantial agreement. There has been some divergence in the list of individual "ideal" orientations that have been used to describe the texture by these observers and others,6 although the orientation (110) [112]-that is, (110) parallel to the rolling plane and [112] parallel to the rolling direction-is generally recognized as the most prominent orientation and (I12) [111] one of the lesser orientations. Other orientations have been given by some observers as (236) [533], (100) [001], and (I 10) [001]. The texture of copper has also been described as (135) [533].6.1 The sum of these orientations provides a reasonable approximation to the complete pole figure, but it does not follow that these specific orientations are necessarily of fundamental significance, for the choice of indices is arbitrary, within limits. Furthermore, a detailed investigation of the ideal orientations in cold-rolled iron discloses continuous ranges of equally favored positions rather than definite positions of high stability,1 and similarly Brick&apos;s observations in a single crystal of a brass2 suggest that all orientations in the range between (110) [113] and (110) [117] are about equally stable. MATERIALS AND METHODS The material used was vacuum-cast electrolytic copper kindly supplied by L. L. Wyman, of the General Electric Co.* Slices 1/2 in. thick and 2 1/2 in. square, cut from the ingot, were rolled with 50 per cent reduction per pass to final thicknesses between 0.02 and 0.04 in., and etched to develop cube-face etch pits suitable for goniometric work.8 The etch was light on some strips and deep in others.

Jan 1, 1942

By E. T. Turkdogan, P. Grieveson, J. F. Beisler

Experimental results are given for the rate of reduction of silica from silicate melts by paphite-saturated iron in the presence of carbon monoxide. It is shown that, when gas bubbles are present at the slag-metal interface, the interfacial chemical reaction is the rate-controlling process in the transfer of silicon from slag to metal. From the silicon-concentration profiles in the metal sample, the diffusivity of silicon in paphite-saturated iron is found to be (5.4 * 0.4) x 10 sq cm per sec at 1600°C. Some consideration is given to the transport of oxygen from the slug-metal interface to the walls of the gvaphite metal container as becoming the rate-controlling process in the absence of gas bubbles at the slag-metal interface. ATTEMPTS were made by Fulton and chipman1 to investigate the kinetics of reduction of silica from calcium alumino-silicate melts by graphite-saturated iron in an atmosphere of carbon monoxide. In these experiments with 400 to 500 g of metal and slag, both phases were stirred in such a manner that the interface was essentially undisturbed. Initially, the graphite-saturated iron contained about 15 pct Si and, after about 8 or 10 hr of reaction time at 1600°C, the silicon content of the metal in- creased by about 0.2 pct. In a written discussion on this paper of Fulton and Chipman, schuhmann2 pointed out the possibility that this observed slowness of the reduction of silica could be due to the transport of oxygen across the liquid metal boundary layer at the slag-metal interface. Although this explanation of Schuhmann is quite feasible for the experimental data of Fulton and Chipman on silica reduction, such a reasoning should not be extended to other rate data on slag-metal reactions unless sufficient evidence is available satisfying the boundary conditions for such a transport process. The hydrodynamics of stirred liquids are very complex and even for a simple method of stirring there is no exact mathematical solution which will predict the mass transfer coefficient accurately. The best available solution of this problem is that given by Lewis&apos; and later modified by mayers~ for a two-liquid system where liquids are stirred by counter-rotating stirrer blades without disturbing the interface. In such a system the mass transfer coefficient is estimated from an empirical relationship using the data on viscosity and density of the two liquids, rate of revolution, the length of stirrer blades, and the diffusivity of the element which is transferred from one phase to the other. It was found in these investigations&apos; that the estimated and observed mass transfer coefficients, in systems containing two immiscible aqueous solutions, agreed within *40 pct. Although this is not considered to be an unreasonable error for the study of industrial processes, uncertainties of this magnitude cannot be tolerated in any theoretical study of reaction kinetics. In view of the complexity of the

Jan 1, 1963