Search Documents

By M. King Hubbert

In 1856 Henry Darcy described in an appendix to his book, Les Fontaines Publiques de la Ville de Dijon, a series of experiments on the downward flow of water through filter sands, whereby it was established that the rate of flow is given by the equation: q= - K(h2- h2)/I1 in which q is the volume of water crossing unit area in unit time, I is the thickness of the sand, h1 and h2 the heights above a reference level of the water in manometers terminated above and below the sand, respectively, and K a factor of proportionality. This relationship, appropriately, soon became known as Darcy's law. Subsequently many separate attempts have been made to give Darcy's empirical expression a more general physical fornzulation, with the result that .so many mutually inconsistent expressions of what is purported to he Darcy's law have appeared in published literature that sight has often been lost of Darcy's own work and of its significance. In the present paper, therefore, it shall be our purpose to reinform ourselves upon what Darcy himself did, and then to determine the meaning of his results when expressed explicitly in terms of the pertinent physical variables involved. This will be done first by the empirical method used by Darcy himself, and then by direct derivation from the Navier-Stokes equation of motion of viscous fluids. We find in this manner that: q = (N4(p/p)[g - (l/p) gradPI = WE, is a physical expression for Darcy's law, which is valid for liquids generally, and for gases at pressures higher than about 20 atmospheres. Here N is a shape factor and d a characteristic length of the pore structure of the solid, p and IL are the density and viscosity of the fluid, a = (Nd2)(pip) is the volume conductivity of the system, and E = [g - (l/p) grad p] is the impelling force per unit mass acting upon the fluid. It is found also that Darcy's law is valid only for flow velocities such that the inertial forces are negligible as compared with those arising from viscosity. In general, three-dimensional space there exist two superposed physical fields: a field of force of charucteristic vector E, and a field of flow of vector q. The force field is more general than the flow field since it has values in all space capable of being occupied by the fluid. So long as the fluid density is constant or is a function of the pressure only, curl E = 0, E = - grad F where F = gz + dp/p The field of flow, independently of the force field, must satisfy the conservation of mom, leading to the equation of continuity div pq = — f ap/at , where f is the porosity, und t is the time. For steady rnotion ap/at = 0. and div pq = 0 .

Jan 1, 1957

All the TECHNICAL PUBLICATIONS and CONTRIBUTIONS published in 1941 are available at Institute headquarters, unless otherwise noted They are also on file in many public, university and technical libraries and, when so indicated in the list, may be found in the TRANSACTIONS TECHNICAL PUBLICATIONS in Classes A-Metal Mining, 13-Milling and Concentration, H-Industrial Minerals, and I-Mining Geology are distributed in MINING TECHNOLOGY, which is issued every other month Technical Publications in Classes C-Iron and Steel Division, D-Nonferrous Metallurgy and E-Institute of Metals Division are distributed in METALS TECHNOLOGY, which is issued twice quarterly TECHNICAL PUBLICATIONS in Class G-Petroleum Division are distributed in PETROLEUM TECHNOLOGY, which is issued every other month TECHNICAL PUBLICATIONS in Classes F-Coal Division, J-Mineral Industry Education Division, K-Mining Administration, and L-Geophysics, are issued as separate pamphlets An Institute member is entitled to one copy of any printed TECHNICAL PUBLICATION or CONTRIBUTION Copies of TECHNICAL PUBLICATIONS listed have been mailed to members of the Institute according to their registration by classes CONTRIBUTIONS and other TECHNICAL PUBLICATIONS will be sent upon request A member may purchase an additional copy of a TECHNICAL PUBLICATION or a CONTRIBUTION at one cent a page, minimum charge, 25¢ Nonmembers may purchase any CONTRIBUTION or a TECHNICAL PUBLICATION of the F, J, K, or L classes at the same rate, but the nonmember price per copy for METALS TECHNOLOGY, MINING TECHNOLOGY or PETROLEUM TECHNOLOGY is $1 25 domestic, $1 35 foreign countries. TECHNICAL PUBLICATIONS (separate pamphlet form), $2 per annum domestic, $2 50 foreign. METALS TECHNOLOGY, $7 per annum domestic, $7 80 foreign (Iron and Steel Division and Institute of Metals Division ferrous and nonferrous papers) MINING TECHNOLOGY, $6 per annum domestic, $6 60 foreign (metal mining, milling and concentration, Industrial Minerals Division, and mining geology papers) PETROLEUM TECHNOLOGY, $6 per annum domestic, $6 60 foreign Bound volumes have been mailed to members that have requested them, and MINING and METALLURGY Is mailed each month A member is entitled to one volume a year on his membership and he may purchase for $2 50 one copy of a volume not already received, additional copies of the same volume, $5 Nonmembers in the United States may purchase the volumes listed at $5 each, outside of the United States and its possessions, $5 6o Extra single copies of MINING AND METALLURGY, 25¢ current issue, back numbers 500 each to members, to nonmembers 50¢ current issue and $1 each, back issues Subscription price to nonmembers and to members for extra copies, $3 per annum domestic, $4 00 foreign.

Jan 1, 1941

By F. Weinberg

It has been suggested, for some time, that the behavior of metals under high-temperature creep conditions is strongly influenced by the behavior of the grain boundaries present in the material. This has led to a number of investigations1-6 in which attempts were made to measure the properties of the grain boundaries themselves, both to determine their contribution to the creep process and to obtain further knowledge of their intrinsic structure and properties. The present investigation was undertaken to extend the observed data under more closely controlled experimental conditions and to attempt to clarify sonie of the discrepancies in the literature. A brief report of the preliminary results has been published.7 EXPERIMENTAL PROCEDURE For the present investigation, controlled orientation specimens were used having plane boundaries which terminated at the specimen surface. Trierys-tal specimens were used instead of the bicrystal type of Puttick and King,' in order to simplify the gripping technique required to apply a shear stress along the boundary. The aluminum used was obtained from the Aluminum Francaise and was of 99.994 pct purity, containing 0.002 pct each of Cu, Fe, and Si. The aluminum tricrystals were grown horizontally from the melt, in graphite boats, and in an argon atmosphere, following the technique developed by Chalmers.' The orientation of the tricrystals was controlled by using seed crystals separated by mica inserts. Thermal conditions were adjusted to produce tricrystals having boundaries which were macroscopically straight, parallel to the growth direction, and perpendicular to the top surface. Following growth, the tricrystals were carefully cut with a jeweller's saw to the test specimen shapes shown in Fig. l(a) and l(b). In Fig. 1(a), the boundaries subjected to shear stresses are indicated AB and CD: Points A and C are the ends of the mica inserts separating the seed crystals; points B and D are at lateral cuts made in the specimen. It was found that the slots left by the mica inserts at A and C had to be enlarged slightly, by cutting, to ensure that the boundary terminated freely at these points. A shear stress was applied to the boundarks by gripping the upper two legs in file-faced Inconel grips and suspending a weight from the lower part of the specimen held in similar grips, as shown schematically in the diagram. The test specimens shown in Fig. 1(b) were cut from long

Jan 1, 1959

By G. W. Preckshot, J. W. Gorman

MOLTEN metals offer an excellent medium for the study of molecular diffusion and interphase transfer. In the absence of intermetallic compound formation, solutions of molten metals are solutions of elements. Therefore, complicating factors such as molecular structure, dissociation, association, polarization, and so on, are generally absent. Further, metals remain in the liquid state over a wide range of temperature. Thus, the effect of temperature on transport processes can be studied in more detail. Although some data are available for the diffusion of metals in the molten state at high temperatures,"""".'!' the most useful and accurate data are those for the diffusion of various elements in mercury at room temperature. The effective radius of diffusion for the various elements in mercury may be calculated from the Stokes-Einstein relation.'-These calculated radii are compared with the atomic and ionic radii calculated from X-ray data on crystals." The effective radii of diffusion of the alkali and alkali-earth metals correspond to those of the neutral atom; those of cadmium, silver, lead, zinc, thallium, bismuth, and tin correspond to ionic radii; and those of copper and gold indicate larger radii due to association with mercury or more likely, faulty diffusion data. Independent evidence"' supports the notion that alkali metals are uncharged in amalgams. The concept of metals moving free of their conductance electrons in the liquid state has been discussed by Eyring, et al,'" in connection with studies on the viscosity of pure molten metals. Considering the approximate nature of the tabulated atomic and ionic radii and the variance in the diffusion measurements, the application of the Stokes-Einstein equation to the diffusion of metals in mercury gives gratifying results. It is noted that a number of these metals have article radii eaual to or less than those of the solvent mercury.".'*,"' Soba1,'" sing the inaccurate Roberts-Austin20 data, indicated that the effective radius of diffusion might well be a function of temperature. Additionally in studies of mass transfer between phases, many conflicting opinions have been expressed concerning the assumption of equilibrium at the interface." ,","," The results of the present work on the diffusion of solid copper in molten lead throws light on the tempera- ture variation of the diffusion radius as well as the extent of the interfacial resistance. The theoretical background and experimental procedure are presented here in detail. Results on other systems will be presented in subsequent papers. Nomenclature The following nomenclature is used in the paper: A—cross-sectional area of diffusion column, sq cm C, C,—concentration of solution and saturated solution respectively, g per cc D,D'—-diffusivity, sq cm per sec e—Naperian base h—ratio, k/D k—mass-transfer coefficient, cm per sec L—diffusion column length, cm n—series index q—flux, g per sq cm-sec r—radius, cm or A R—-gas constant t—time, sec T—temperature, K V—volume, cc w—weight of copper-lead alloy on copper cylinder WT—-total copper transferred to lead diffusion, column, g Z—distance from top of diffusion column, cm 2'—distance from copper-lead interface, cm (2' = L-2) u,,—roots of diffusion equation Mathematical Apparatus The model shown in Fig. 1 applies to the diffusion of solid copper into molten lead. Here Fick's first law may be written where all terms are defined in the nomenclature. It is assumed that the volume of the lead column is constant. This is justified since experimental densities compared favorably with calculated densities based on perfect interstitial mixing. Thus there is no counter diffusion of lead. It is clear that 2 in Equation [I] should be measured relative to the interface which moves relative to the diffusion cell but not to the liquid phase. Hence, the frame of reference is the plane of the copper-lead interface. The diffusivity calculated at constant volume, D", is that defined by Hartly and Crank" and is designated herein as D. No Interfacial Resistance—The two situations of the presence and absence of interfacial resistance will be treated. The simplest is the latter which re-

Jan 1, 1959

By J. H. Bucher

The effect oj strengthening by the precipitation of CbC on the toughness offerrilic steel (0.11 pct C, 0.74 pct Mn, 0.02 pct Cb) was stlrdierl. A g-veater degree of pvecij~itatiotz strengthning is ohtaznable by aging the so11ution-treated steel rtt velaticely Low temperature was (1050" to 1l0O3F) than at higher temperatures (I150" to 1200°F). Tlzis ),eslrlts because a finer dispersion of CbC is obtained. However, the ductile-brittle transition te~ripertltlo.e is raised approximately tlzjeee tirues as IFLIIC~ perv a given yield stress increase) by aging in the lower tempareture range, as opposer1 to the Irigher temperaturee range. This is proposed to result pl-iir~avily because different precipitation distributions ar-e associated with the different aging -treaments. For tile steel aged at 1050" and 1100 F, heavy: precipitation on disloccctions occurs resulting in a high degree of rlislocution pinningh tl~us lowevirzg- the toilguiess. in tll c(.rise of the steel aged at 1150 'a?zd 1300"F, Pvecipitatiol~ is irzove g-enerally distributed throughout the matrix rather limn preferentially on dislocations.; and Ike detlsitj, oj mobile dislocations is not sttyong-ly affected. THE most effective means of strengthening hot-rolled ferritic steels are grain refinement and precipitation hardening. It is well-known that grain refinement increases both the strength and the toughness. However, the upper limit of yield strength obtainable by grain refinement alone is about 60,000 psi,'12 i.e., without the formation of acicular structures of lower toughness. The most economical means of obtaining higher strengths is the addition of small amounts of elements such as columbium, vanadium, and titanium which form carbonitrides. These precipitates are very effective in increasing the strength, but the ductile-brittle transition temperature is is Although it is agreed upon that precipitation decreases the toughness, there has been little effort to isolate the causative aspects of embrittlement. The purposes of this research are to assess quantitatively the embrittlement associated with different precipitate distributions and morphologies, and to correlate the degree of the embrittlement with the microstruc-ture. In this manner, a more fundamental insight into the mechanism of embrittlement may be gained. The steel selected for this purpose was a low-carbon, columbium-bearing steel which, after solution treatment, was aged in various time-temperature cycles while attempting to hold all other microstructural variables constant. MATERIALS AND PROCEDURE The composition of the steel used in this investigation is given in Table I. Starting with commercially hot-rolled material 0.074 and 0.280 in. thick, tensile blanks were cut from the thinner material and sub-size Charpy blanks from the thicker stock. The steel had been rolled using a low finishing temperature and rapid cooling after hot rolling to produce grain refinement. Also, chemical-extraction analysis and electron-microscopic examination revealed that the cooling was rapid enough to suppress any significant precipitation of CbC. Therefore, the as-rolled steel is essentially in the solution-treated condition in terms of the precipitation reaction, and it was used as the base material in this investigation. The room-temperature tensile properties of the as-rolled steel aged at 1100", 1150", and 1200°F for various time intervals were determined, see Table 11. The ductile-brittle transition behavior was studied for smooth and notched tensile specimens, and longitudinal half-size (0.200 in. thick) Charpy V notch specimens aged at 1100" and 1150°F for various times, also Table 11. In addition, tensile specimens aged for single times at 1050" and 1200°F were evaluated with respect to their ductile-brittle transition. Only one 1050°F treatment was used because of the extremely slow kinetics of precipitation at this temperature and because no significant difference between 1100°F aging was observed. Only one treatment at 1200°F was used because aging at this temperature alters the shape of the grain boundary cementite particles present in this steel and complicates analysis. The design of the tensile specimens is given in Fig.1.

Jan 1, 1968

By I. Lowthian Bell

THERE has been probably no improvement introduced into the manufacture of iron which created more surprise in the minds of practical smelters and of scientific men than Neilson's discovery of the hot blast. In 1829, Messrs. Dunlop & Co. consumed at the Clyde Works, near Glasgow, nearly 79 tons of coal to make a ton of pig iron, of which about 20 cwts. was employed under the boilers of the blowing engines, leaving nearly 7 tons for the consumption of the furnace itself. In the year 1833, by heating the air to 612' F. (322' C.), they redoccd the 79 tons to 3 tons by the mere burning of 8 cwts. of coal in the apparatus for raising the blast to this temperature. The statenlent just given is strictly true in a commercial sense, but when we come to consider the question as one of physical science, it is necessary to eliminate some of the conditions which conduced to so extraordinary a result. Anterior to Neilson's time the fuel employed in smelting iron was coke, and it was supposed at that period, erroneously, however, that coal in its raw state, when burned with cold air, was totsally unfit for the purpose in question. This mineral, as it was obtained from the Lanarkshire coal-field, contained about 35 per cent. of volatile matter, but the process of charring it was performed in so unskilful a manner that instead of receiving 88 cwts. of coke from 135 cwts. of coal, 60 cwts. only was the product of the operation. Again, the reduced colisumption of carbon in the furnace itself was accompanied by a corresponding diminution of blast, and this was followed by an economy of half a ton in engine coal. After making a proper allowance, however, for all these collateral circumstances, we are within the mark when we admit that in actual coke, which is really the form the fuel has to assume before it is burnt in the blast-furnace, not less than 30 cwts. was saved by heating the blast to 615° F. (322° C.). This unexpected economy, be it remembered, was obtained by the combustion of the 8 cwts. of coal, somewhat wastefully applied in the hot-air apparatus. Numerous have been the opirlions advanced by different authorities in the scientific world to account for the apparent anomaly, bat none,

NORTH AMERICA Number Members Alaska 31 Canada 302 Mexico 175 Newfoundland 3 United States Alabama 52 Arizona 131 Arkansas 9 California 723 Colorado 184 Connecticut 98 Delaware 19 District of Columbia 133 Florida 16 Georgia 6 Idaho 61 Illinois 241 Indiana 57 Iowa 7 Kansas 32 Kentucky 33

Jan 1, 1932

By Daniel Hanson

FoR most of their practical applications metals are required to withstand stresses of appreciable magnitude: indeed, it id because they possess the quality of resisting stress without becoming permanently deformed that they find such extensive use in the service of man. Metals and alloys must, in service, usually behave as elastic substances—or nearly so. It is not difficult to satisfy this condition at ordinary temperatures. Iron and its alloys, especially the steels, are at normal temperatures excellent elastic bodies, capable of satisfying most of the mechanical requirements of the engineer: where electrical, chemical or other properties are impor-tant, which cannot be met by steels, it is usually possible to find a non-ferrous alloy such as nickel, copper or aluminum, which will prove satisfactory. When the metals or alloys are not inherently sufficiently elastic, cold-working or heat-treatment may develop elastic properties to a sufficient extent for practical needs. By means of relatively simple, rapid tests we can measure such properties as elastic modulus, limit of proportionality and proof stress, upon which design can be based with confidence. The case of the soft metals, such as lead and tin, is well known to be exceptional. They possess no definite limit of elasticity, and the value of proof stress or tensile strength depends to a great extent on the speed with which the test is carried out. Design here must be based on other considerations than a well-established theory of the proportionality of stress and strain. It is now generally recognized that steels and non-ferrous alloys possess at temperatures not greatly exceeding that of the atmosphere, characteristics quite different from those existing at ordinary temperatures, and that they assume qualities similar to those of the soft metals. Not only have they no limit of elasticity, but the proof stress and the ultimate stress depend on the time of application of the load. Flow under load may persist for long periods of time, possibly indefinitely, and the determination of a true maximum stress becomes a matter of great difficulty.

Jan 1, 1939

By Daniel Hanson

FoR most of their practical applications metals are required to withstand stresses of appreciable magnitude: indeed, it id because they possess the quality of resisting stress without becoming permanently deformed that they find such extensive use in the service of man. Metals and alloys must, in service, usually behave as elastic substances—or nearly so. It is not difficult to satisfy this condition at ordinary temperatures. Iron and its alloys, especially the steels, are at normal temperatures excellent elastic bodies, capable of satisfying most of the mechanical requirements of the engineer: where electrical, chemical or other properties are impor-tant, which cannot be met by steels, it is usually possible to find a non-ferrous alloy such as nickel, copper or aluminum, which will prove satisfactory. When the metals or alloys are not inherently sufficiently elastic, cold-working or heat-treatment may develop elastic properties to a sufficient extent for practical needs. By means of relatively simple, rapid tests we can measure such properties as elastic modulus, limit of proportionality and proof stress, upon which design can be based with confidence. The case of the soft metals, such as lead and tin, is well known to be exceptional. They possess no definite limit of elasticity, and the value of proof stress or tensile strength depends to a great extent on the speed with which the test is carried out. Design here must be based on other considerations than a well-established theory of the proportionality of stress and strain. It is now generally recognized that steels and non-ferrous alloys possess at temperatures not greatly exceeding that of the atmosphere, characteristics quite different from those existing at ordinary temperatures, and that they assume qualities similar to those of the soft metals. Not only have they no limit of elasticity, but the proof stress and the ultimate stress depend on the time of application of the load. Flow under load may persist for long periods of time, possibly indefinitely, and the determination of a true maximum stress becomes a matter of great difficulty.

Jan 1, 1939

By R. E. Zimmerman, Michael Sokaski, E. R. Palowitch, M. R. Geer, H. F. Yancey, W. Deurbrouck, S. C. Sun

PART 1: DENSE MEDIUM SEPARATION by M. SOKASKI, M. R. GEER and H. F. YANCEY INTRODUCTION In the early days of coarse-coal treatment by the dense-medium process in Europe, loess was one of the materials used for medium solids. Newly developed cyclones were used to reclaim and thicken :he loess suspension. On occasion, when the cyclone thickener at the Maurits mine in the Netherlands plugged, the overflow was found to be filled with clean coal free of impurity. From this observation stemmed the concept of the cyclone as a cleaning device. Development took place during World War 11 in the laboratory of the Dutch State Mines under the direction of M. G. Driessen. A 15-ton-per-hour pilot plant was in operation in the laboratory by 1945, when, in September, Driessen made the first public disclosure of the process in a paper presented to the Institute of Fuel in London. In April 1945,2 operation of this pilot plant was observed by one of the authors, who was so impressed with the potential of the cyclone process that, on his return to the United States, a research program on the cyclone was started by the Bureau of Mines immediately. This work led to an AIME paper in 1946 in which the first details of cyclone operation on American coals was made available. Commercial adoption of the cyclone proceeded in Europe, initially in the Netherlands, Germany, and France. In the United States, where coal is less costly and most of the coals are so easy to clean they respond well to simpler cleaning systems, the first cyclone plant was not built until 1961.3 As of the spring of 1967, a total of 31 commercial cy- clone plants had been installed or were under construction in the United States; this does not include eight Dynawhirlpool plants. The capacity of the cyclone plants ranges from 50 to 1300 tons per hour and totals 6600. THEORY Before discussing the theory of a dense medium cyclone, a brief description may be helpful to some readers who are not familiar with its basic operation. In a typical dense-medium cyclone, illustrated in figure 10-1, the mixture of medium and raw coal enters tangentially near the top of the cylindrical section, thus forming a strong vertical flow. The refuse moves along the wall of the cyclone and is discharged through the under- flow orifice. The washed coal moves toward the longitudinal axis of the cyclone and passes through the vortex finder to the overflow chamber.

Jan 1, 1968

By O. H. Eschholz

THE electrostatic process of fume precipitation is an excellent example of the successful application of scientific knowledge to an industrial operation. Originally proposed for the precipitation of sulphuric acid mists, it has been extended until at present there is practically no fume carrying gas to which the method cannot be applied. Among the more common applications are: the recovery of non-ferrous smelter flue-dust, iron blast-furnace dust, cement dust, and potash fume. It should be borne in mind that the process is restricted to the precipitation of suspended particles, either liquid or solid, and does not separate gaseous constituents. However, -by proper temperature control, mixtures of vapors having different temperatures of condensation to either solids or liquids may he selectively precipitated. The process consists essentially of subjecting suspended particles, including those too minute to be effectively acted upon by centrifugal or gravitational forces, to such an electrical force that they are driven from the gas stream, acting as a conveyer, and deposited upon a suitable receiving surface. This directional impulse is obtained front the interaction of charged particles and an electrostatic field of definite intensity gradient existing between two dissimilar electrodes, known as discharge and receiving electrodes. In principle, the equipment is equally simple. As shown diagrammatically in Fig. 1, it consists of: (1) A source of high-potential direct current, requiring: (a.) Source of alternating-current energy. (b) Means of transforming from tow voltage to high voltage. (c) Means of converting alternating to direct current. (2) Precipitation chamber having: (a) Transmission tubes for fume-laden gases. (b) Suitably designed and disposed electrodes. (c) Means for affecting removal of deposited solids.

Jan 8, 1918

By G. L. Oldright, T. B. Brighton, C. M. Dice

The base bullion from the lead blast furnace contains varying amounts of the impurities left in the smelter feed by the concentrator, regardless of the method of smelter operation. These impurities may be held in part in mechanical suspension rather than being present as true alloys. However, usually there is little free space in the crucible in which to separate these drosses before the bullion is taken from the lead well. When such a dross is melted in a laboratory crucible and allowed to cool, the products obtained are lead bullion, speiss, and matte in well separated layers. Typical analyses of layers are: Analyses. Per Cent Element Bullion Speiss Matte Pb.............................................. 92.0 41.2 38.3 Cu.............................................. 2.4 36.3 40.6 As............................................... 4.0 16.5 4.3 Sb............................................... 0.7 0.2 0.4 S................................................ 0.6 1.9 13.1 Fe............................................... 0.0 0.0 0.0 Totals......................................... 99.7 96.1 96.7 The absence of iron in these products drossed from the blast-furnace bullion proves that the impurities for the greater part are not simply finely divided blast-furnace speiss or matte that has been dissolved or dispersed in the lead, but are held in solution by the liquid metal and rise to its surface as infusible compounds when the temperature of the bath is lowered. In general, the drosses made locally are metal sulphides and arsenides and not oxidized compounds. The large content of metallic lead also does not seem to be retained because of oxidized compounds

Jan 1, 1937

By Fred P. Dewey

Although coke is the acknowledged metallurgical fuel, and has been extensively used in this country for more than thirty years, yet the facts on record in regard to its physical properties are exceedingly meagre; and this is also true, but in a less degree, of its chemical composition. An investigation is being carried on in the National Museum which is intended to supply, so far as may be, this deficiency, and through the kindness of Professor Baird, Director of the Museum, I am permitted to present to the Institute a summary of a portion of the results already obtained. So far as I am aware, the credit for the first systematic investigation of the physical properties of coke belongs to Mr. John Fulton, Mining Engineer of Cambria Iron Co. The results of this investigation have been published in Report L, Second Geological Survey, Pennsylvania, 1875, and in a pamphlet setting forth the advantages of the Connellsville coke, the latter published also by the " Virginias"* His results are not altogether free from experimental errors, and the assumption that "the specific gravities of coke and water are very nearly alike "- is scarcely warranted. It has seemed to me, therefore, desirable to make an independent investigation of the physical properties of coke on a plan somewhat different from that adopted by Mr. Fulton. This is the investigation now being carried on at the National Museum.

Jan 1, 1884

By J. L. Tokich, A. R. Troiano

INTRODUCTION SINCE 1921, when Hull' discovered that cobalt can exist in the face-centered cubic and hexagonal close-packed modifications, the transitions that occur in cobalt have been extensively studied. It is generally agreed that on heating the hexagonal lattice changes to the cubic structure at temperatures ranging from 400 to 500°C although considerable doubt exists as to the exact temperature. Data concerning the temperature of the transformation on cooling are much less concordant and their interpretation has not been satisfactory. The study is further complicated by the fact that many investigators have reported the existence of a high temperature allotropic change in the range 850 to 1020°C, at which the cubic lattice reverts to the hexagonal modification. The transition on cooling, which has been reported as occurring at various temperatures from approximately 400 to 100°C, is of particular interest. Troiano and Greninger2 have recently suggested and considered the possibility of allotropic transformations occurring in pure metals by a shear-type, diffusionless (martensite) transformation. The case of cobalt was specifically discussed and certain observations of previous investigators evaluated in terms of this type of transformation. Table 1 briefly outlines the methods and results of previous investigators of the transformation temperatures of cobalt. MATERIALS AND METHODS The major portion of this investigation was performed with cobalt sheet containing a total of 0.2 pct impurities with carbon present to the extent of 0.1 pct. After melting in an induction furnace under an atmosphere of hydrogen, the carbon content analyzed 0.03 pct. Some observations were repeated with hydrogen reduced cobalt compresses analyzing 99.9 pct pure. No significant variations in results were observed employing the as-received sheet, the remelted stock, or the cobalt compresses. Filings for X ray diffraction analysis were sealed in evacuated glass ampoules. Pyrex glass tubing was used for temperatures below 600°C and for higher temperatures clear fused quartz was satisfactory. After appropriate heat treatment at various temperatures, the specimen ampoules were furnace cooled, air cooled or quenched by crushing under distilled water. This allowed a range of cooling velocities from less than one degree C per sec to greater than 1,000°C per sec. X ray diffraction patterns were taken with a Debye camera and filtered characteristic cobalt K-alpha radiation. The proportion of the existing phases was roughly approximated by visual examina-

Jan 1, 1948

By Francis C. Krauskopf, Carl E. Swartz

Metallurgists differ considerably in their opinions regarding the effect, if any, of small amounts of iron pyrites, or other iron compounds on zinc sulfide ores during the roasting operation. As a result, the literature on this subject expresses many conflicting ideas. The ore, previously crushed to pass through a 1-mm. screen, dries in the roasting kiln, losing water up to 200° to 300° C. At 150° C. iron pyrites begin to lose sulfur. As the temperature increases, while the ore is passing to the hotter part of the furnace, the sulfur burns to sulfur dioxide, leaving the metals as zinc oxide and ferric oxide. These two substances then interact to form zinc ferrite, a compound, yellow brown in color, having the general characteristics of a spinel. Like magnetite, another spinel, zinc ferrite is insoluble in alkalis and dilute acids. As a result, when leached with 10 per cent. sulfuric acid solution, zinc values tied up in this compound remain behind History In the electrolytic recovery of zinc from its ores, the roasted ores are usually leached with a 10 per cent. sulfuric acid solution. When the zinc ore contains iron pyrites as an impurity in an appreciable amount, the actual yield of metallic zinc is much lower than a theoretical calculation would indicate. Further, losses of zinc are, in a rough way, directly proportional to the amount of iron pyrites or other iron compounds present. When the iron is present in the ore in an isomorphous relation to the zinc, as in the case of a marmatite, a greater amount of zinc remains insoluble than when present as a true pyrite or marcasite. Work on the insoluble residues obtained from leaching of the calcines shows that the zinc lost is intimately tied up in this residue. Some investigators have suggested a definite compound, such as zinc ferrite; others merely a mixture of zinc and iron compounds. As early as 1851, Pelouze(')' prepared calcium ferrite by fusion of calcium oxide and ferric oxide. Ebelman, 2) about the same time, prepared

Jan 1, 1928

By James Johnston

Synopsis.-A description of the working of the mills of this company and the metallurgical practice in vogue, by which a remarkably. complex silver ore, averaging 54 oz. of silver per ton (run-of-mine ore), is treated to give a 95.66 per cent. extraction. The main features of the, processes are: The cyanide amalgamation of the high-grade ore. The cyanide treatment of the low-grade ore, after extremely fine grinding and close classification, in a caustic soda solution. The use of a wet desulphurizing process to break up refractory silver minerals. The substitution of aluminum dust for zinc dust as a precipitant. The recovery and shipment of over 13,000,000 oz. of silver in bullion at. 997 to 999 fine since this metallurgy was inaugurated, about 2.5 years ago. On the completion and successful operation of the mill to treat their . high-grade ore,1 the Nipissing Mining Co., under the general management of R. B. Watson, started a series of investigations of the possible treatment of the low-grade ore by the cyanide process, so that they would be in a position to market only silver bullion. These tests were run in July, 1911, on a large scale, by G. H. Clevenger, on an average mixture of Nipissing ore. The results obtained by a partial amalgamation followed by cyanide treatment gave an extraction varying from 90 to 93 per cent. and were sufficiently encouraging to warrant Charles Butters, the company's Consulting Metallurgist, in recommending that the new low-grade ore mill under contemplation should be a cyanide mill, instead of a concentrator. The cost of such a mill, capable of treating 200 tons per day, to obtain a 90 per cent. extraction at a working cost of $3 per ton of ore treated, was estimated at $250,000.

Jan 1, 1914

By Zay Jeffries

TUNGSTEN has the highest melting point of all the known metals, namely 3350° C.; it is one of the hardest of the metals; it has the highest equiaxing or recrystallization temperature after strain hardening, of any pure metal known. It is particularly distinguished because, when composed of small equiaxed grains, it is extremely. brittle and fragile at room temperature, and when possessing a fibrous structure it maybe ductile and pliable at room temperature. The common ductile metals act in exactly the opposite manner in this respect. The present paper will include a brief note regarding the manufacture of wrought and. ductile tungsten. The metallography of wrought and ductile tungsten in the various stages of manufacture will be considered more or less in detail. The general relationships between the properties of tungsten and other metals will also be considered. A discussion will be given explaining why fibrous tungsten is ductile at room temperature, even though past experience with other metals would indicate that it should be brittle. Finally, a brief note regarding some new fundamental metallographic propositions relating to all metals will be given.

Jan 6, 1918

By J. W. Hickman, E. A. Gulbransen

In a previous paper' the authors have investigated the structure of the oxide films formed on most of the metals that make up the alloys of this study. The metals were studied in order to provide basic information on the structures, both physical and chemical, of the oxide films and to determine how these structures are effected by the temperature, time of oxidation, and surface preparation. It was felt that an understanding of the physical and chemical structure as well as the stability of the oxide film might furnish clues as to the nature of the reaction process and the protective quality of the film. The oxidation of the metals was studied over the temperature range 300' to 7o0°C. except for copper, wherc the range selected was 100' to 500°C. The results of these studies were presented in graphical form as existence diagrams of the oxides on a time-temperature scale. For some of the metals the existence diagrams were simple and showed few chemical transitions, but there were numerous cases where the physical state of the oxide surface was a function of time and temperature. In general the physical state of the oxide surface changed with increasing temperature so as to increase the sharpness of the diffraction patterns and to cause orientation effects to be more pronounced. Deviatiois in lattice Darameters from X-ray values were noted. In general these deviations were of positive nature and may be due to solid solution of the metal in the oxide lattice. This effect might be expected in thin oxide films. In a study of the oxidation of alloys containing two or more metals, there may arise the complicating factor of identification of the oxides formed. A thorough understanding of the oxides formed on the pure metals, therefore, was, essential before investigation of the oxidation of alloys. In this paper it is our purpose to present a study of the following problems: 1. The existence diagrams of various alloys. 2. The effect of the structure of the alloying metal on the existence diagram of iron. 3. The effect of the percentage of chromium on the oxides formed on Fe-Cr alloys. 4. The relationships, if any, between the oxides formed and the protective quality of the oxides. The following alloys are included in this study: alloys of iron with body-centered cubic, face-centered cubic and other metals, 13 Cr-Fe, 18-8 stainless steel, K4²B, Nichrome V, Hipernik, Inconel, Stellite "²I," Refractaloy, Kovar, mild steel, a series of Cr-Fe alloys and a series of Co-Fe alloys. Since many of the commercial alloys in this list contain more than two metals, various complicating factors in the identification of the oxides formed may arise.

Jan 1, 1947

By E. A. Gulbransen, J. W. Hickman

In a previous paper' the authors have investigated the structure of the oxide films formed on most of the metals that make up the alloys of this study. The metals were studied in order to provide basic information on the structures, both physical and chemical, of the oxide films and to determine how these structures are effected by the temperature, time of oxidation, and surface preparation. It was felt that an understanding of the physical and chemical structure as well as the stability of the oxide film might furnish clues as to the nature of the reaction process and the protective quality of the film. The oxidation of the metals was studied over the temperature range 300' to 7o0°C. except for copper, wherc the range selected was 100' to 500°C. The results of these studies were presented in graphical form as existence diagrams of the oxides on a time-temperature scale. For some of the metals the existence diagrams were simple and showed few chemical transitions, but there were numerous cases where the physical state of the oxide surface was a function of time and temperature. In general the physical state of the oxide surface changed with increasing temperature so as to increase the sharpness of the diffraction patterns and to cause orientation effects to be more pronounced. Deviatiois in lattice Darameters from X-ray values were noted. In general these deviations were of positive nature and may be due to solid solution of the metal in the oxide lattice. This effect might be expected in thin oxide films. In a study of the oxidation of alloys containing two or more metals, there may arise the complicating factor of identification of the oxides formed. A thorough understanding of the oxides formed on the pure metals, therefore, was, essential before investigation of the oxidation of alloys. In this paper it is our purpose to present a study of the following problems: 1. The existence diagrams of various alloys. 2. The effect of the structure of the alloying metal on the existence diagram of iron. 3. The effect of the percentage of chromium on the oxides formed on Fe-Cr alloys. 4. The relationships, if any, between the oxides formed and the protective quality of the oxides. The following alloys are included in this study: alloys of iron with body-centered cubic, face-centered cubic and other metals, 13 Cr-Fe, 18-8 stainless steel, K4²B, Nichrome V, Hipernik, Inconel, Stellite "²I," Refractaloy, Kovar, mild steel, a series of Cr-Fe alloys and a series of Co-Fe alloys. Since many of the commercial alloys in this list contain more than two metals, various complicating factors in the identification of the oxides formed may arise.

Jan 1, 1947

By G. R. Love, C. C. Koch

The changes in superconducting properties with aging time have been studied ,for the pecipitation reaction in a Tc-30 at. pct V alloy. Superconducting critical temperature, upper critical field, and relative critical current density were determined by ac susceptibility techniques. Aging produces changes in critical temperature of both matrix and precipitate which can be rationalized by compositional effects. maximum flux pinning (critical current density) occurs at a time during aging when subgrain boundaries are completely decorated with precipitates and the subgrain centers remain precipitate -free. The particular effectiveness as barriers to flux motion of planar defects which enclose regions of low deject density is discussed. THE precipitation of a second phase can dramatically modify the superconducting properties of type I1 super-conductors. According to Livingston and Schadler1 one might expect changes in the primary, secondary, and tertiary superconducting properties of the material. Changes in matrix chemistry caused by precipitation can alter the fundamental superconducting parameters; critical temperature, Tc, and thermody-namic critical field, Hc. The concimitant changes in electron mean free path (reflected in normal state resistivity) can affect the critical fields Hc 1, IIc2, Hc3. Finally, the presence of precipitate particles may hinder the motion of flux lines and may considerably improve the current-carrying capacity in high-field superconductors. The influence of precipitation on superconducting properties has been studied in a number of systems.2 Magnetization measurements have been used to study the influence of precipitates on flux pinning in lead-base alloys by Livingston3 and Evetts et al4 In these alloys precipitates induced magnetic hysteresis and flux trapping. The amount of hysteresis increased with the volume fraction of precipitate and decreased with coarsening of the precipitate. Jn an Al-Zn alloy5 and an A1-Ag alloy6 the initial precipitate size was presumably smaller than a coherence length and coarsening increased magnetic hysteresis5 and critical current density.6 The influence of precipitation on superconducting properties has also been studied in several of the commercially interesting Ti-Nb7-10 and zr-Nb11 alloys. The maximum in critical current density for these alloys was confined to a narrow range of either isothermal aging time" or isochronal aging temperature7 during the precipitation reaction. Thus, experimental evidence and theoretical considerations suggest there is an optimum precipitate size, spacing, and density, and a critical composition with respect to the matrix for flux pinning. What these "optimum" values might be and the relative importance of each is still not clear, although a few generalizations can be made. It is generally accepted1' that particle sizes smaller than the coherence length or larger than the inter-flux line spacing are poor pinning centers. In high Hc2 materials, precipitate sizes for maximum values of critical current density lie in the range of 50 to 2000Å,9,7 and there are indications that increasing dissimilarity between precipitate and matrix produces increasing pinning force.13 Because of several interesting features of the aging reaction in a Tc-30 pct V alloy, we have chosen to study the influence of precipitation on the superconducting properties of this alloy. The physical metallurgy14 and a survey of the superconducting properties" of the Tc-V alloy system have been reported. The Tc-V phase diagram is presented in Fig. 1. At 1500°C the Tc-30 pct V alloy is in the single phase 6 field. Samples quenched from the 6-phase field have a CsCl structure X-ray diffraction pattern at room temperature and it has been proposed that the 6 structure is closely related to the bcc lattice.14 When held isothermally below the eutectoid temperature, 115O°C, the 6 phase decomposes into the CsCl and hcp phases.

Jan 1, 1970