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By B. C. Allen, W. D. Kingery

Surface tension and its temperature dependence have been determined for pure liquid Fe, Cu, Co, Ni, and Sn and for Fe-C, Co-C, and Ni-C alloys. The temperature coefficient of surface tension is negative for all these liquids. The surface tension and wetting behavior of tin and tin-titanium alloys on A120,, Si,N,, MoSi,, and Sic, as well as the behavior of titanium-containing nickel alloys on A1 20, have been determined over a wide temperature range. For all the solids investigated titanium additims markedly lower the contact angle. Some limits for the solid-surface energies have been calculated from liquid surface tension and wetting behavior. SURFACE tension and interface energy are important variables in a number of metallurgical and ceramic phenomena, and have been discussed at some length in connection with determining micro-structure of polyphase systems,' solid-state sintering,' thermal etching of grain boundaries, heats of solution and fine powders,'1 grain-growth phenomena,' the mechanical behavior of fine foils and fibers, nucleation, soldering and brazing,' and other phenomenz of academic or practical interest However, until recently few quantitative data have been available for high-temperature systems. Among available data are some indicating positive temperature coefficients for the surface tension of liquid copper,*,11,'2 cast iron,l3 and iron-carbon14 alloys. Although carbon was found to be not surface active in iron at 1570" some preliminary studies had indicated the possibility of a positive temperature coefficient for the eutectic composition at lower temperatures.16 One part of the present study has been largely concerned with determining the temperature coefficient of surface tension for several metals at elevated temperatures, In addition to surface-tension studies, the wetting behavior of alloys containing titanium has been investigated over a wide temperature range. Previous measurements indicated that titanium was selectively adsorbed from nickel at a liquid nickel-solid alumina interface,17 and the use of titanium hydride or titanium-alloy techniques for metal-ceramic soldering is well known. In the present study, previous data have been extended to new alloy systems, and measurements have been carried out with other oxidation-resistant ceramics. EXPERIMENTAL The sessile-drop method was employed to measure liquid surface tension and contact angle between liquid and solid, utilizing apparatus and techniques which have been described previously.'g The shape of a sessile drop depends on equilibrium between forces of surface tension tending to form a spherical surface of minimum area and forces of gravity tending to flatten the drop. Typical sessile drops are shown in Fig. 1. From precise measurements of maximum drop diameter and drop height the surface tension and drop volume were calculated. Four solid materials were employed as supporting plaques for the liquid-metal drops. Aluminum oxide (99.9 pct, J, T. Baker, reagent grade) was pressed and sintered at 1800°C. Molybdenum-disilicide powder (99.0 pct, Electro Metallurgical Co.) was pressed and sintered at 1650°C. Plaques were cut from silicon carbide (99.4 pct, hot-pressed at Alfred University) and silicon nitride (95.1 pct, with Al, Fe, 0 as major impurities, Norton Co.) rods. All plaques were polished, cleaned, and dried prior to use. A number of metals and alloys were employed. Chemical analyses of vacuum-melted ingots of iron, nickel, cobalt (National Research Corp.), commercial nickel-base alloys, electrolytic copper (International Smelting and Refining Co.), and tin (Mal-linckrodt Chemical Works) are given in Table I. Alloys were prepared in the laboratory by vacuum melting the base metal with either titanium hydride (Metal Hydrides, Xnc.) or spectroscopic-grade carbon (National Carbon Corp.). Nickel-titanium alloys contained between 0.001 and 0.005 pct oxygen and the ferromagnetic metal-carbon alloys contained 0.001 pct. Cylindrical metal specimens (1 to 2.5 g) were machined and bevelled at the bottom to insure a uniform advancing contact angle on melting. Before use the samples were acid-etched, cleaned with acetone, and rinsed in petrol ether.

Jan 1, 1960

Executive JOHN R. SUMAN, Chairman PAUL D. MERICA, Vice-Chairman CHESTER A. FULTON W. M. PEIRCE H. Y. WALKER Finance H. T. HAMIL'T'ON, Chairman ERLE V. DAVELER HENRY KRUMB Admissions FELIX E. WORMSER, Chairman GEORGE D. BARRON, Vice-Chairman PHILIP KRAFT EDWARD MEAGHER CLYDE E. WILLIAMS

Jan 1, 1941

By L. J. Howell, R. C. Sommer, H. H. Kellogg

WORK described herein was undertaken with the aim of determining some of the physical-chemical properties of electrolytes suitable for the electrodeposition of pure zirconium metal. In this paper the phase diagram, vapor pressure, and activities in the melt are considered. In a companion paper,' the electrolytic conductivity of some of these melts is reported. The melts studied were mixtures of NaCl and/or KC1 with ZrC1,. Chloride melts were chosen for study because 1) if the electrolyte is to be useful for industrial electrodeposition of zirconium, the chlorides will be preferred to the relatively costly bromides and iodides; 2) fluoride melts were being studied in another laboratory (Horizons Inc., Cleveland); and 3) melts containing oxygen, in any form, are unsuitable for preparation of pure zirconium, because of the great affinity of this metal for oxygen. Unlike electrodeposition from aqueous solution, the fundamental behavior of fused-salt electrolysis is poorly understood. In most cases, such basic electrochemical information as the phase diagram of the melt system, activities in the melt, conductivity, the nature of the current-carrying ions, the equilibrium electrode potentials, and the overvoltage behavior of the electrodes is unknown to the researcher who would develop a new electrodeposition process employing a fused salt. This research project was designed to supply information about some of these basic physical-chemical properties so that an intelligent choice of electrolyte for electrodeposition studies could be made. Experimental The experimental difficulties-encountered in this work result from the properties of zirconium metal and ZrC1,. ZrC1, is a solid which sublimes at 334°C. It is rapidly hydrolyzed by moist air to HC1, ZrOCl,, and ZrO,. Unusual precautions were exercised in this work to prevent hydrolysis of ZrC1, and rigidly to exclude oxygen, nitrogen, hydrogen, and carbon from the melts under study. These elements are known to react with and contaminate zirconium metal. All melts were studied in vacuum systems, i.e., in the presence of ZrC1, vapor only. Transfer of ZrC1, to or from the melts was accomplished entirely by vacuum sublimation. In this way, neither the melts nor the ingredients thereof were permitted to

Jan 1, 1958

26. G. H. S. Price, S. V. Williams, and G. J.O. Garrard: Heavy alloy, its production. properties and uses. Metal Industry (1941) 599 354s 372. 394. 27. R. Kieffer and W. Hotop: p. 320 of ref 12. 28. F. R. Hensel. E. I. Larsen, and E. F. Swazy: Physical properties of metal compositions with a refractory metal base. Chap. 42, 483, Powder Metallurgy, ed. by J. Wulff (1942) Cleveland. 29. R. Kieffer and W. Hotop: p. 290 of ref. 12. 30. H. Freundlich: Kapillarchemie. 211 (1923) Leipzig. 31. W. Ostwald: Zisch. f. Phys. Chemie. (1900) 34, 503. 32. G. A. Hulett: Zisch. f. Phys. Chemie. (1901) 37. 385; and (1904) 47, 357. 33. J C. Chaston: Discussion to Price, Smithells and Williams, p. 257 of ref. 4. 34. W. Dawihl: Untersuchungen ueber die Vorgaenge bei der Abnuetzung von Hartmetallwerkzeugen. Ztsch. f. techn. Phys. (1940) 21 336. 35. W. Dawihl and J. Hinnueber: Ueber den Aufbau der Hartmetallegierungen. Kol-loidzlsch. (1943) 104, 233. 36. F. Skaupy: Dispersoidchemische und verwandte Gesichtspunkte bei Sinter-hartmetallen. Kolloidzlsch. (1942) 98, 92; and (1943) 102, 269. 37. F. C. Kellcy: Cemented tantalum car- bide tools. Trans. ASST (1932) 19, 233. 38. E. W. Engle: Cemented carbides. Chap. 39, 436, Powder Metallurgy, ed. by J. Wulff (1942) Cleveland. 39. W. Dawihl: Zlsch. f. Melallkunde. (1940) 32, 320. 40. P. M. McKenna: Tool Materials (Ce- mented Carbides). Chap. 40. 454. Powder Metallurgy, ed. by J. Wulff (1942) Cleveland. 41. G. A. Meerson. G. L. Sverev, B. Y. Osinovskaja: Zhurnal Prikladnoi Khimii. (1930) 139 66. 42. A. G. Metcalfe: The mutual solid solubility of Tunesten Carbide and Titanium carbide- Metal Trealmenl (1946) 13, 127. 43. P. Schwarzkopf: Powder Metallurgy. 196-201 and 354-356 (1947) New York. 44. H. Burden: The manipulation and sintering of hard-metals. Special Rep. No. 38, p. 78. Iron and Steel Inst.. 1947. London. 45. W. D. Jones: Principles of powder metal- lurgy. 150. (1937) London. 46. J. E. Drapeau: Sintering of powdered copper-tin mixtures. Chap. 32. 332, Powder Metallurgy, ed. by J. Wulff (1942) Cleveland. 47. H. E. Hall: Sintering of copper and tin powder. Metals and Alloys (1939) 10, 297. 48. F. Sauerwald: Present status of powder metallurgy. -.Melallwirlschafl. (1941) 20, 649. 671. 49. H. L. Wain: Powder metallurgy; influence of some processing variables on the properties of sintered bronze. Report ACA-25. Australian Council for Aeronautics (1946) Melbourne. 50. S. L. Hoyt: Constitution of copper-tin alloys. Metals Handhook, 1364. (1939) Cleveland. 51. T. Ishikawa: Studies on the interdiffusion of copper, tin and graphite powders. Nippon Kinzoku Gakkai-Si (1937) I, 226. 52. A. Carter and A. G. Metcalfe. The struc- ture of porous bronze bearings. Special Rep. No. 38, p. 99. Iron and Stecl Inst. (1947) London. 53. R. P. Koehring: Sintering atmospheres for production purposes. Chap. 25, 278. Powder Metallurgy, ed. by J. Wulff (1942) Cleveland. 54. C. G. Goetzel: Some properties of sintcred and hotpressed copper tin compacts. Trans. AIME (1945) 161, 569. 55. J. W. Lennox: The production of some non ferrous engineering components by powder metallurgy. Special Rep. No. 38. p. 174. Iron and Steel Inst., 1947, London. . P. Duwez and H. E. Martens: The power metallurgy of porous metals and alloys having a controlled porosity. TP 2343, Metals Tech. April 1948. This volume. p. 848. 57. E. A. Owen and L. Pickup: X-ray study of the interdiffusion of copper and zinc. Proc. Royal Soc., London, Series A. (1935) 149, 283. 58. C. G. Goetzel: Sintered and hotpressed compacts of copper-zinc powder. Chap. 34. 352, Powder Metallurgy, ed. by J. Wulff (1942) Cleveland. 98, R. Chadwick. E. R. Broadfield, and S. F. Pugh: Observations on the pressing. sintering, and properties of iron-copper powder mixtures. Special Rep. No. 38, p. 151, Iron and Steel Inst. (1947) London. 60. A. Squire: The properties of iron-copper compacts. Watertown Arsenal Lab. Rep. WAL No. 67101. 61. F. C. Kelley: Properties of sintered iron- comer uowder. Iron Age (Aug. 15. 193) 158 57. 62. G. H. Howe: Sinterinn of Alnico. Iron Age (Jan. 11. 1940) 14.5, 27. 63. R. Kieffer and W. Hotop: p. 359 of ref. 12. 64. W. Hotop: Permanent magnets from sintered iron-nickel-aluminum. Stahl und Eisen (1941) 61, 1105. 65. P. R. Kalischer: Some experiments in the production of aluminum-nickel-iron alloys by powder metallurgy. Trans. AIME (1941) 145, 369. 66. S. J. Garvin: Production of sintered per- manent magnets. Special Rep. NO. 38. p. 67. Iron and Steel Inst. 1947, London. 67. F. C. Kelley: Discussion to P. R. Kalischer. p. 375 of ref. 65. 68. R. Kieffer and W. Hotop: p. 357 of ret, 12. 69. C. H. Howe: Sintered alnico. Chapter 48, 530, Powder Metallurgy, ed. by J. Wulff (1942) Cleveland. Powder Metallurgy Seminar (C. G. Goetzel presiding) C. G. Goetzel—The seminar has been opened by a man who has been active in the field for over fourteen years and has made, since then, some major contributions to the advancement of the art. After having been associated with the Moraine Products Division of General Motors Corporation for over ten

Jan 1, 1949

Jan 1, 1944

Jan 1, 1944

By Carl Henrich

Jan 1, 1893

By C. Wagner

When an alloy solidifies and the composition of the solid differs from the composition of the liquid, atoms of the alloying elements rejected at the solid-liquid interface have to diffuse toward the bulk liquid. Diffusion may be supported by convection. Theoretical calculations have been made for a liquid without convection, for a liquid involving natural convection, and for solidification of a liquid alloy at the surface of a rotating disk as an example of forced convection. WHEN an alloy solidifies, the equilibrium composition of the originating solid phase differs in general from the composition of the liquid phase. Thus, segregation may take place, i.e., the composition of the solid phase formed at different times differs from the bulk composition. The degree of segregation depends on several factors such as the partition ratio of the alloying elements between the liquid and the solid phase, the rate of solidification, and convection. To clarify, a theoretical analysis has been worked out. The following presuppositions are made: 1—Calculations are confined to the solidification of binary alloys in which the concentration of component A (solvent) is much greater than that of component B (solute). 2—The equilibrium concentration of the alloying element B is assumed to be lower in the solid phase than in the coexisting liquid phase. 3—At the solid-liquid interface, partition equilibrium is assumed. 4—The dependence of the partition ratio of the solute between the liquid and the solid phase on concentration and temperature is disregarded since only small concentrations of the solute are considered. 5—The concentration of the alloying element B in the solid phase is supposed to be lower than the saturation concentration for the formation of a second solid phase. 6—diffusion in the solid phase is disregarded, since diffusion rates in the solid state are comparatively low. When the partition ratio of the solute between the liquid and the solid phase is greater than unity, a part of the solute is rejected at the solid-liquid inter- face and has to diffuse toward the bulk liquid. Thus there is necessarily a concentration difference in the liquid between the solid-liquid interface and the bulk liquid as has been pointed out by Hayes and Chipman,' Rutter and Chalmers,' Tiller, Jackson, Rutter, and Chalmers, and others (see Fig. 1). In view of the concentration gradient in the liquid phase, the ratio of the concentration of the solute in the solid phase to that in the bulk liquid differs from the equilibrium ratio, although at the solid-liquid interface, partition equilibrium is assumed. Under certain limiting conditions, the solid may even have virtually the composition of the bulk liquid as is shown below. General Equations Let u be the linear crystallization velocity in cm per sec, D the diffusion coefficient of component B in the liquid phase in cm2 sec-', c',, and c", the concentrations of component B in the liquid and the solid phase, respectively, in mol per cm", and s the distance from the solid-liquid interface toward the bulk liquid at a given time t. The partition ratio is assumed to be equal to a partition constant K. Thus. The difference in the specific volume between the liquid and the solid phase may be disregarded. In view of the discontinuity of the concentration of the solute at the interface according to Eq. 1, u(c', — c",), , , = tic', (S = 0)(1 — K) gram-atoms B per unit area per unit time are rejected at the interface and have to diffuse toward the bulk liquid. From Fick's first law it follows that uc',,(s = 0) (1 ~K) == - D(dc',,/?>s). _-„. [2] The concentration profile in the liquid near the interface depends on the interplay of diffusion and convection as is discussed in the following sections. A schematic concentration profile is shown in Fig. 1. The "effective thickness of the diffusion boundary

Jan 1, 1955

By J. A. Heskett

NEW ZEALAND is dependent on the outside world for its ferro goods, yet it can boast of at least two well-defined iron-ore deposits; namely, Para Para limonite, 3 Fe203 + 21120 also found as lower hydrated oxides, and Taranaki iron-sand, a combined magnetite and ilmenite, 2FeO + 2Fe203 + FeO + Ti02. The former is of massive variety and the FIG. 1.-VIEW OF WORKS SHOWING IRON-SAND DEPOSITS, ALSO WHARF AND BREAK¬WATER IN THE DISTANCE. latter granular and mixed with various proportions of fine shell and siliceous sand well water-worn. This latter deposit forms the greater portion of the beach sands of the west coast of the North Island of New Zealand. It is so fine that the whole of a sample passed through a sieve of 40 meshes to the inch. The ilmenite cannot be detected by the microscope, as in the titaniferous ores of the Adirondacks, nor can it be magnetically separated, as in the titaniferous ore of Natashkwan, Canada. To all appearances it is a chemical compound of the double oxides of iron and titanium and not a mechanical mixture, as is the ore of the Adirondack deposits.

Jan 8, 1920

By L. W. Saperstein, D. Yeung, L. B. Phelps

Introduction The success of preventive methods for the mitigation of coal mine drainage formation will require a marriage of the minimization of initial coal mine drainage formation, the minimization of toxic fluid formation after toxic material disposal, the minimization of the mobilization and transpor¬tation of formed toxic fluids, and the maximization of the rate of diultion and attenuation of the formed toxic fluids. This paper contributes to the understanding of factors af¬fecting mobilization and dilution and attenuation of formed toxic fluids. When water containing a salt content different from in situ pore water in the soil is passed through a body of soil, the concentration of salts in the outflow will gradually change composition in a manner that depends on the kinds of hydraulic processes that occur in the soil. These processes are molecular diffusion, lateral dispersion, longitudinal dispersion, chemical reactions or exchange, physical adsorp¬tion, and biological retardation. This note considers only the first three processes. These three microscopic processes can be analyzed statistically on a probability basis. Such results, confirmed experimentally, indicate that a tracer introduced instantaneously as a point source will tend to form a Gaussian normal distribution as it moves downstream (Todd, 1964). Dilution During Flow The closed-form soltuion for pulse or instantaneous injec¬tion of a tracer during confined flow in a homogeneous porous medium shows that the maximum tracer concen¬tration at a point in space, x, after the time interval, t*, is given by [ ] where Aa is the effective flow cross-sectional area; A is the column cross-sectional area; a is soil porosity; M is mass of the injected tracer; C is concentration of the tracer in the permeating fluid and is a function of x and t*; D is the longitudinal dispersion coefficient; and va is the interstitial fluid velocity (Klotz and Moser, 1974). Therefore, the following conclusion can be made: • For a medium with a constant longitudinal dispersion coefficient, D, a constant soil porosity, a, a constant cross¬sectional area, A, and a fixed mass of injected tracer, M, Cmax will decrease as the time of peak outflow concen¬tration t* increases. • For a medium with a constant longitudinal dispersion coefficient, D, a constant soil porosity, a, a constant cross¬sectional area, A, a fixed mass of injected tracer, M, and a constant interstitial fluid velocity, va Cmax will decrease as the distance of travel, x, increases. • For a medium of constant cross sectional area, A, con¬stant soil porosity, a, a constant mass of injected tracer, M, and a fixed distance of travel, x, Cmax will decrease as D/va increases. Klotz and Moser (1974) concluded that D is about proportional to no.3 where r) is the kinematic viscosity; D is about proportional to a-3 where a is soil porosity; D in¬creases with increasing grain size; D increases as grains become less spherical; D increases with greater grain rough¬ness and angularity; D increases with increasing uniformity coefficient; and D is significantly affected by grain size and uniformity coefficient. The remaining parameters are not significant. Numerical Simulation Studies Numerical simulation studies were used to investigate the nature of flow and the optimum length of a toxic package within a saturated porous medium of fixed dimensions and configuration (Fig. 1). The width and position of the package was maintained constant (Phelps et al., 1981). Results indicate that if the package extends throughout the length of the model, the flow is vertically downward and

Jan 1, 1984

By Maurice K. Seguin

It is a difficult task to find enriched soft iron ore deposits in the central part of the Labrador Trough, New Quebec, Canada, when the areas investigated are covered by glacial drift. A qualitative interpretation of either a combined gravity-magnetic-seismic-resistivity survey or gravity-magnetic-seismic or gravity-magnetic-resistivity survey permits (with a low probability level) the detection of iron formations and ore zones as well as their delineation from most of the country rocks. This is possible because most of the altered iron formation underwent a slight increase in density through enrichment and because the accompanying geochemical alteration changed their magnetic properties. In order to increase the chances of success in finding ore bodies when using geophysical methods, different types of correlation were done for many deposits. These are: I) A quantitative correlation of the residual gravity anomaly intensities with the specific gravity, the iron content, the silica content, the porosity factor, and the dimensions of the underlying ore bodies. 2) A quantitative correlation of the ground magnetic intensity relative to a reference lithologic unit with the percentage of Fe.,O, recovery and with the volume ferromagnetic susceptibility. A few discoveries already have been made with this method. The details of the location, the description of the geology, and the history of previous geophysical surveys and their qualitative interpretation have already been given.', ' A very brief paragraph describing the regional and local geology is necessary in order to facilitate the understanding of this paper. The sedimentary iron formations of the Labrador Trough consist of a 700-mile geosynclinal segment composed of tightly folded and faulted Proterozoic sediments, volcanics, and intrusives that are rich in mineral deposits. The complex sequence rests unconformably on the basement of Archean granitic gneisses. The direct-shipping iron deposits are scattered along a northwest-trending strip, 5 to 10 miles wide and some 60 miles long in the facies rich in iron oxides and preferentially in localities where the original sedimentary environment favorized the deposition of a large concentration of magnetite associated with chert by physicochemical processes, e.g., oxidation-reduction potential, pH, temperature, pressure. Once leached of its silica and/or iron carbonate content and enriched with secondary a-hematite (occasionally goethite), this original magnetite associated with some primary hematite makes the blue direct-shipping ore which constitutes the important ore reserves in this mining district.

Jan 1, 1971

By George A. Packard

The experiments here described were made under my supervision while temporarily acting as head of the Department of Metallurgy at the Missouri School of Mines, at Rolla. The work was done by Messrs. W. E. Brown, W. C. Richards, and F. L. L. Wilson, and the description of the results forms a portion of a thesis presented for the degree of Bachelor of Science. These results are submitted because I have seen no description of the application of pot-roasting to the treatment of a copper-concentrate. This work followed that already described in the discussion of the Lime-Roasting of a Galena-Concentrate,' and was similarly occasioned by the lack of a furnace of the reverberatory type in which the copper-concentrates could be smelted. The material for the tests was a mixture of three lots available. The first consisted of 8-mm. ,jig-concentrates and the second of 0.5-mm. table-concentrates, from the San Juan district, Colo. Both contained pyrite, chalcopyrite, and galena. The third was a lot of copper-ore, found in the laboratory, which had been crushed through 8-mm. screen, and had at some previous time, before the laboratory roasting-furnace was torn down, received a partial roasting. The analyses of these ores are given in Table I. In order to determine the applicability of pot-roasting as to each lot of ore, and the effect of varying proportions of lime, six preliminary tests were made in a " size N " Battersea crucible, 9 in. high by 6 in. in diameter at top, with a 5/8-in. hole bored through the bottom. The crucible was set in the upturned elbow of a 2-in. pipe, the joint being luted with clay; and air was obtained from a receiver supplied by a compressor. The

Jan 1, 1908

By G. W. Thomas

A mathematical tnodel of forward combustion in an oil reservoir is treated in this paper. The model describes a radial system having a vertical section of essentially infinite thickness, all of which is permeable to gas flow. Combustion, however, is presumed initiated over a limited thickness of the total vertical section. In the interval supporting cotnbustion, the mechanisms of radial conduction, convection and heat generation are taken into account. Above and below the burning interval, heat transport in the radial direction is by cottduction and convection. Vertical heat losses from the ignited interval are accounted for by conduction alone. A general solution is presented for the temperature distribution caused by radial movement of the combustion front. The results show that no feedback of heat occurs into the ignited interval when convection and conduction are acting in the bounding media. Peak temperatures are also 5 to 10 per cent higher than in the case where heat transport in the bounding media is by conduction alone. We arbitrarily define vertical coverage to be that fraction of the total ignited interval which is at 600F above atnbient, or greater, at any given time. The radial distance at which the vertical coverage becomes zero is the propagation range of the combustion front. It was found that an increase in vertical coverage results when the oxygen concentration, fuel concentration or gas-injection rate is increased. Moreover, the combustion front can be propagated 10 to 15 per cent further than in the case where only conduction is acting above and below the ignited interval. INTRODUCTION In the theoretical treatment of forward combustion in a radial system, one of the problems encountered is the determination of the transient temperature distributions caused by an expanding cylindrical heat source. Bailey and Larkin' and Ramey' simultaneously presented analytical solutions to the problem assuming heat transport by conduction alone. In a subsequent publication, Bailey and Larkin3 included the effects of both conduction and convection while treating linear and radial models. In this latter work, however, vertical heat losses were largely neglected. Selig and Couch' dealt with a radial model in which both conduction and convection were acting. Only a limiting case involving vertical heat losses was considered, however. Namely, temperatures on the boundary of the bed of interest were set equal to zero. Solutions thus obtained were representative of a system having a maximum vertical heat flux. Chu5 recently treated a more general case in which a permeable bed was considered bounded by impermeable media. Conduction and convection took place within the bed, and only conduction outside of the bed. The effects of vertical heat losses were included in his study. Solutions were obtained by numerical techniques. This paper is an extension of the theoretical work of other authors pertaining to forward combustion in a radial system. In particular, a mathematical model of the process is treated in which heat generation occurs over a small vertical interval of a larger permeable section. In the interval supporting heat generation, and above and below this interval, the mechanisms of radial conduction and convection are also presumed acting. Heat losses from the ignited interval are accounted for by vertical conduction. An analytical solution for the temperature distribution caused by radial movement of the burning front is presented. The effects of certain process variables are indicated and comparisons with Chu's results are made. THEORY To render the mechanism of forward combustion tractable to mathematical treatment, we idealize the problem to the extent of assuming continuous reservoir media possessing homogeneous and isotropic properties. The following additional assumptions are implicit in this analysis. 1. The thermal parameters, i.e., heat capacities, thermal conductivities and thermal diffusivities are invariant with temperature and pressure. Moreover, the bounding media possess the same thermal properties as the bed of interest. 2. The temperatures of the porous media and its contained fluids at any point and at any time are equal. 3. The reaction rate between the oxidant gas and the fuel is infinite. This assumption implies that the incoming oxygen concentration instantaneously goes to zero within an infinitesimal distance, i.e., the width of the combustion zone is negligible. 4. The rate of gas injection is constant and corresponds to the average rate throughout the lifetime of the project. 5. The fuel concentration is constant throughout the volume of rock swept out by the burning zone. 6. There is complete burnoff of fuel. This assumption demands that the rate of propagation of the burning front equals the rate of fuel burnoff. In a radial system, with a

By John W. Cloud

IN 1877 the Pennsylvania Railroad Company removed an old bridge from its line at Duncannon, Pa., built intermediate piers and erected shorter spans of the Pratt truss type, which had previously been in use on another portion of the road. The design of this truss would not admit of diagonals larger than 1 5/8 inches diameter, and in order to stiffen the bridge somewhat steel rods were introduced for the main diagonals in the first and second panels, 1 5/8 inches and 1 3/8 inches diameter respectively. These rods were threaded without upsetting, and by the ordinary formulae the strains were of the same intensity upon both, viz., 16,000 pounds per square inch with the maximum loading. The other main diagonals in the truss are 1 5/8 inches diameter, and of iron. It was specified for the steel rods : Elastic limit, - 45,000 lbs. Tensile strength, - 80,000 lbs. Elongation, - 20 per cent. The steel was procured without difficulty, and it allowed a factor of safety of 2 3/4 at elastic limit, while a similar factor of 2 1/2 had for a long time been successfully used for iron. In the course of three years, from time to time, six of these steel rods broke, three of them being 1 3/8 inches in diameter, and three 1 5/8 inches in. diameter. The broken rods were tested, and three of them. analyzed at Altoona to ascertain the cause of failure, and what modi¬fications should be made in the steel for such service. Examination showed that all the rods were broken in detail close under the nut. The threads were well cut and properly rounded at the root. In testing the rods micrometer screws,. reading to .0001" with electric bell to signal the contact, were attached to the test pieces, and by this means the modulus of elasticity and elastic limit accurately obtained.

Jan 1, 1881

By James A. Barr

THE writer's first experience with flotation was during World War I, in the beneficiation of Alabama graphite schist ores. One plant used a cone with a peripheral overflow; dried ore was distributed by a rotating disk onto the surface of the water. No reagents were added. The flake-graphite film floated along with some fine silica. Dewatering screens separated the flake. Naturally unit capacities were low but results were satisfactory. Minerals Separation mechanical flotation machines were used in another graphite mill. Pine oil was added directly to the head cells, with very good results. All the graphite concentrates from both types of flotation were carefully refined after drying by passing through burr mills, followed by very close sizing on sifters. In March 1927, the writer ran a very successful flotation test on minus 28-mesh, deslimed, Tennessee brown phosphate "sand,"[t] using a mechanical laboratory machine built in the shops of the Anaconda Copper Mining Co., through the courtesy of Ernest Klepetko. The machine was soon converted to a subaeration type, with improved results. This phosphate research program was greatly enlarged and led to the formation of the Phosphate Recovery Corporation. The development of nonmetallic flotation followed rapidly. The first flotation machine for beneficiation of phosphate was installed in January 1928, in a pilot mill, by International Minerals and Chemical Corporation, at Mulberry, Florida. These machines were Minerals Separation, 24-in., subaeration types, with weir control of pulp between cells. The sand bleeders were very small-about 1 ¼ -in. diameter. As the feed contained 15 to 25 per cent plus 28-mesh material, the cells choked up frequently. This was corrected by cutting a 2 by 6-in. bleeder opening above the impellers, at grid level, which short-circuited the coarse fractions directly into the feed of the next cell. The matter of size classification and grinding was a considerable problem, which does not come within the scope of this article. Because of the troubles noted above, cascade-type roughers were installed in the second flotation plant, built about 1930. Experimental cells had been tried in 1928. General plant layout is shown in Fig. I and details of the cascade construction in Fig. 2. The cascade installation in plant No. 2 gave good results and eliminated troubles due to choke-ups and coarse feed. The capacities and metallurgical results equaled those of the modified 24-in. Minerals Separation flotation machines in plant No. I The objections to the cascade installation are the floor space and mill height required. In 1939 an improved Minerals Separation machine was tested in parallel with the cascades. Extensive tests indicated

Jan 1, 1945

By J. W. Freeman, J. P. Rowe, R. F. Decker

HEAT-to-heat variations in properties of an alloy of constant nominal chemical composition have been a perplexing problem to the metallurgist. These heat-to-heat differences have been especially baffling in high-temperature metallurgy. In order to establish fundamental reasons for these heat-to-heat variations, the National Advisory Committee for Aeronautics has sponsored and financially assisted an extended research program on heat-resistant alloys at the University of Michigan. As part of the program to find the contribution of processing variables, Frey, Freeman, and white' studied effects of heat treating on nickel-base alloys and Ewing and reeman' investigated effects of hot-working practice on N155 alloy. To extend the program to the study of effects of melting practice on high-temperature properties, a 55 Ni-20 Cr-15 Co-4 Mo-3 Ti-3 pct A1 composition was selected for experimentation. The objective of this program was to establish the melting-practice variables which influenced the hot-working characteristics and creep-rupture properties and, at the same time, establish the metallurgical mechanisms for the effects. During the course of the investigation of practices using vacuum melting, it became increasingly evident through chemical analyses supplied by industrial concerns that a major variable was melt reaction with the crucible. This paper is devoted to the results of this phase of the melting-practice study. EXPERIMENTAL PROCEDURES Experimental 10-lb heats were induction melted in the University of Michigan vacuum-melting unit with the melting practices outlined in Table I. Aim analysis for the basic alloy, in wt pct, for all heats was as follows: Cr Co Mo Ti Al 20.0 15.0 4.0 3.1 3.1 Mn Si C Ni 0.12 0.12 0.08-0.15 Bal. Small amounts of boron and zirconium were added to certain heats as listed in Table I. These additions

Jan 1, 1959

By H. V. Winchell

It seems to me that uniformity of mining law in North America must of necessity start with uniformity in each country. I understand that the Provinces of Canada have the right to make their own individual laws and conditions, to prescribe the terms under which the prospector or the applicant for mineral titles may secure the same. That is not true of the states in the United States. In this country, the Federal Mining Law was made applicable to the public domain, which, at the time of the adoption of this Act in 1872, was chiefly west of the Missouri River; it is impossible to locate a mining claim in most of our eastern states. It is true, however, that there are certain holdover rights, mostly obsolete, arising from the fact that at the time of the formation of the Confederation of States, the land that belonged to each state became the property of the Federal Government. I am not quite correc-t in that, it was sometime after the adoption of our Constitution, I think it was 1778, but those rights were largely, by agreement, surrendered to the Federal Government; but it is a fact that the great acquisitions of territory in the West, with the single exception of Texas, were of domain that came into the possession of the Federal Government and our Federal Mining Law applies to that territory. No state has the right to (by legislative enactment) enlarge upon the rights given by the Federal Mining Law, governing the acquisition of mining claims in its territory, within its boundaries. Each state, however, may, and some of them do, limit somewhat the rights given to the prospector. For instance, the Federal Mining Law provides that a claim may be taken, staked upon the public domain, of 600 ft. in width and 1500 ft. in length. Some of the states, like South Dakota and Colorado, have at times said "that is an excessive amount of land for a single mining claim; we will therefore limit it to 300 ft. or 200 ft. in width." There is, therefore, not any direct and immediate need for uniformity of mining laws in the United States, such as there might possibly be if it were considered at all desirable upon the whole in Canada. The initiation of mining rights under the Federal Mining Act is the act of discovery of valuable mineral in place, referring now to the lode mining claims, but the same is true of the placer claim. It is true that the emphasis has never been laid upon the word valuable and that

Jan 1, 1920

By R. O. Williams

Analytical representation of the thermodynamics of solutions is highly desirable from the standpoint of accuracy, compactness, and numerical manipulations. In particular, computer calculations are greatly implemented. Mathematical considerations show that previous expressions have one or more serious defects. This investigation shows a Fourier series to be satisfactory but that it is also possible to derive a new series which fits certain additional conditions. Included examples show the value of analytical expressions in giving a simple characterization of each system using some two to five parameters, the elimination of the Gibbs-Duhem integration, and the es timation of the error for the experimental function as well as derived functions. It is further shown that the present characterization provides easy comparison between systems. IN the past, thermodynamic calculations have depended to a considerable extent on tabular and graphical methods. As the volume and precision of such data increase such methods become less satisfactory. Specifically, the selection of the optimum representation and the estimation of errors require statistical methods which in turn require analytical representation. The utilization of such data require further manipulations which are best done analytically for maximum precision. For example, phase equilibria are determined by common tangents to free-energy curves: a graphical determination is normally of low accuracy. As computers are increasingly used analytical representations become almost mandatory. Insufficient mathematical consideration has been given previously to the selection of empirical expressions. Those expressions having some theoretical justification are generally too inflexible and mathematically unattractive. We consider the problem in some detail and show that a Fourier series can be effectively used. Also a new series is defined which has certain advantages. ANALYSIS We wish to consider the analytical representation of the heat of mixing, AH, the excess free energy, ?Gxs, and the excess entropy, ?sXS, as a function of composition, X, for binary solutions relative to the pure components in the same state. When a distinction is not required, we use W to denote any one of the above functions. One may use a Taylor expansion around X = 0 to generate a power series. As the derivatives are un- known we represent the series as W = A + BX + CX2 + DX3 + EX4 + ... [l] where the constants A , B, C , ..- are to be selected to provide some optimum fit. For the extremes of composition W is necessarily zero so it follows that A = 0 [2a] B +C + D + E +••• = 0 [2b] Nonelectrolytes, which we are considering, appear to satisfy the condition that d3W/dx3 = 0 [3] in the terminal regions. This is the basis of the a, ß, and Q functions used by Hultgren et al.' and others. While this condition does not have a strong theoretical basis it does appear desirable that any analytical relation should satisfy this condition. Darken2 and Turk-dogan and Darken3 have shown that many systems exhibit this behavior over an extended range from each terminal region, departure being restricted to a limited intermediate region. Since we have no a priori knowledge as to where this transition occurs we can require that this condition be satisfied only as a limit at the extreme compositions as a general condition. We will show later how more restricted conditions can be included in specific solutions. Darken2 has called this behavior the quadratic formalism; we call our application the limiting quadratic formalism, LQF. This condition applied to the above power series requires that D = 0 [4a] 4-3-2E +5-4-3_F + 6 • 5 . 4G + ••• =0 [4b] The form of the power series normally used, due to Margules,4 is W=X(1-X)(A + BX + CX2 + DX3 + EX4 + •••) [5] where A, B, C, --. are a new set of constants. (Guggenheim5 has given a variation of this expression in a more desirable form. Since, however, it is contained in the above expression it does not require separate consideration.) This form is precisely what results by incorporating the conditions in Eq. [2] into the power series and regrouping the constants. The LQF requires that B =C [6a] and 4.3.2(D-C) +5-4-3(E-D) + ••• =0 [6b] Thus, the correct form of the Margules expression with two adjustable parameters is w =X(1-X)[A + B +X2-2/3x3)] 171 and the EX4 term must be included before three adjustable parameters are permitted.

Jan 1, 1970

By A. R. Troiano, W. J. Barnett

The existence of a grain size stabilization effect on martensitic type reactions as shown by Scheill in an iron-29 pct nickel alloy and by Troiano and Tokich2 in cobalt prompted a review of other martensitic reactions to determine if this stabilization effect is characteristic of all martensite type reactions. Preliminary work has shown this effect to be present both in the gamma —+ epsilon transformation in an iron-20 pct manganese alloy and the martensite transformation of SAE 4140 and 3 pct Cr-O.40 pct steels. No appreciable effect was found in an SAE 2340 steel. The M, temperature for the gamma —+ epsilon transformation was lowered from 380°F to about room temperature by varying the annealing treatment following cold work as shown in Table I. The effect of austenitic grain size on the M, of three steels is shown in Table 2. M, was deter- mined by the conventional quench-temper method of Greninger and Troiano. In a single crystal the change in external shape concomitant with the homogeneous shear mechanism of the martensite transformation can take place unhindered. In a polycrystalline specimen a restraint of these changes must occur at the grain boundaries. Therefore, the smaller the grain size the greater the shear strain energy necessary for the formation of a martensite crystal. The degree of lowering of M, due to the reduction of grain size is much greater when the change in crystal structure involves only a small energy change, such as face-centered cubic —+ close packed hexagonal (that is, CO and Fe-20 pct manganese alloy). The maximum lowering of M, observed in the steels investigated was 50°F with a change in the ASTM austenitic grain size of 1-2 to 8-9. In comparison, the crystal structure change face-centered cubic —+ body-centered tetragonal involves a considerable energy change. There is little doubt that with much finer grain sizes the increased grain boundary restraint would greatly enhance this stabilization effect. The implications of this phenomenon are multifold. Undoubtedly. under certain conditions it offers a method of stabilizing high temperature phases for room temperature

Jan 1, 1949

By James M. Stapleton

IT has long been recognized by blast- furnace men that correct top distribution of materials is very important in efficient and economical furnace operation. Thousands of experiments on top design, filling, sizing, and other operations have been carried out to improving furnace performance by securing uniform distribution. Many of these experiments have worked out satisfactorily and have been passed along to the industry. Many of them have been discarded and forgotten. It has been the custom to judge the results of such experimentation by the results shown in improved or lowered furnace efficiency. While the effect on furnace practice will have to continue to be the final criterion of experimental changes, it has always been a desire of blast-furnace men to ascertain the reason for failure or success. Efficiency in the blast furnace approaching the maximum can be measured in several ways: (I) by actual operating results as revealed in the coke rate and tonnage figures, and (2), in the degree to which the top gas approaches the limiting ratio of CO/C02 for the reduction of iron oxide by CO gas. This ratio is shown in the equilibrium curve in Fig. I for the system Fe-O-C and CO2-CO-C. The closer the top gases approach this limiting ratio (set at 1.08 by Martin1 because of the effect of limestone calcination) the more efficiently we may expect a furnace to operate. The fact that low CO/C02 ratios parallel eficient operating performance caused us to investigate the cause of good or poor distribution and the effect of filling and other changes on furnace operation. Heretofore it has been possible to take a sample of furnace gas (usually from the dust catcher) and from it determine how closely the reducing gases were to the ideal or limiting value as set by the equilibrium diagram. However, to find just where in the top area the distribution was distorted and the top-gas CO/CO2 ratios were distant from equilibrium values has been a difficult and expensive investigational procedure. In an effort to overcome this difficulty, apparatus was designed to take gas samples and temperatures across the top radius of the furnace. It was hoped that with the aid of this apparatus traverse sampling of the ascending gases could be simplified, and the cost of sampling substantially lowered. Routine experimenting could then be maintained and results checked with furnace operation. It must be emphasized that a traverse sampling is necessary for a true picture, as single samples at any one point are unreliable. This statement can be verified by an examination of Tables 3 to 6, showing results obtained at our furnaces in a large number of tests. APPARATUS The design of the equipment for taking the samples was governed by the need for providing a simple, routine test that could be performed fairly quickly without adversely affecting normal furnace operation.

Jan 1, 1943