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By Arnulf Muan, Klaus Schwerdtfeger

Equilibrium ratios C02/C0 of a gas phase coexisting with selected phase assemblages of the system Fe-Mn-0 have been determined in the temperature range 1000" to 1300°C. The oxygen pressure for the "hfnO" +hfn30, equilibrium and for the "(Fe,hTn)O" + (Fe,Mnh 0* equilibrium at high manganese contents has been determined by electromotive force measurements using stabilized zirconia as a solid electrolyte. The notstoichometry 01' "hTnO" and of "(Fe, iM1z)O" solid solutions has been determined by ther-mog-/avi?netry and by wet-chemical analysis. The data obtained are used to derive activity-composition relations in "(Fe,hfn)O" and (Fe,Mn),O4 solid solutions. WUSTITE "FeO" and manganosite "MnO" form a continuous series of solid solution at high temperatures,' and so do magnetite Fe304 and the high-temperature, cubic modification of Mn304 (Ref. 2) (high hausmannite, -1170). The oxides "FeO" and "MnO" are cation-deficient phases.495 The nonstoi-chiometry of "(Fe,Mn)O" solid solutions has been studied by Engell and ~ohl' at two selected C02/C0 ratios at 1250°C. The two oxide end members of the spinel solid solution, FesO4 and Mn,04, however, are known to be close to stoichiometric under the experimental conditions used in the present investigation.''' The oxygen pressures of "(Fe,Mn)07' solid solutions in equilibrium with iron have been determined by Schenck and coworkers,8 by Foster and welch," and by ~n~e1l.l' The two former groups equilibrated the condensed phases in C02-CO atmospheres of lmown compositions, whereas Engell" used a galvanic cell with stabilized zirconia as a solid electrolyte. The results of these investigators are not in good agreement. Activities of FeO in manganowiistite as calculated from the results of Foster and Welch show ideal behavior, those of Engell yield a pronounced positive deviation, and those of Schenck et 01. show a moderate positive deviation from ideality. In the present work oxygen pressures for the iron + manganowiistite and manganowustite + spinel equilibria and the nonstoichiometry of manganowiistites have been measured. The data were used to calculate activities in the manganowiistite and spinel solid solutions. EXPERIMENTAL METHODS The COz/CO ratios at which manganowustite and iron are in equilibrium were determined by thermo-gravimetric and quenching methods. Experimental details are described in a previous publication.'2 In the thermogravimetric technique, incipient reduction of manganowiistite pellets to metallic iron was observed as a break in the weight vs log COZ/CO curve. In the quenching technique, manganowiistite samples were partially reduced to metallic iron, or the metallic iron of manganowustite + metallic iron mixtures was partially oxidized to manganowustite, in atmospheres of constant C02/CO ratios. After quenching the composition of the oxide phase was determined by X-ray lattice parameter measurements and comparison with a standard curve obtained from oxide solid solutions of known compositions. The nonstoichiometry of "MnO" and "(Fe,Mn)07' solid solutions was determined by chemical analysis of samples equilibrated in C02-CO atmospheres and quenched to room temperature, as well as thermo-gravimetrically by reducing (Fe,Mn),04 or Mn304 to manganowiistite or manganosite. The equilibrium between manganowiistite and (Fe,Mn),04 was measured thermogravimetrically by reducing (Fe,Mn),04 solid solutions having composition in the range of %„ l(NFe +NM) from 0 to 0.63. No experiments could be performed with this technique at higher manganese contents, because the equilibrium C02/C0 ratios are too large for accurate control. An additional difficulty arises at the higher manganese contents due to the strong increase in oxygen content of the manganowustite phase with increasing log Py near the manganowiistite-spinel boundary. Consequently a sharp break in the weight loss vs log C02/CO curve cannot be observed at the phase boundary. At high manganese contents of the manganowiistite, e.g., (NMn/(NF~ + NMn) > 0.9, electromotive force measurements with stabilized zirconia as a solid electrolyte were made to determine the equilibrium oxygen partial pressure. Experimental details are described in a previous paper.* Mixtures of "(Fe,Mn)O" and (Fe,Mn),04 were pressed to pellets, and the oxygen pressure of the equilibrated samples was compared to that of Ni + NiO mixtures in the cell The composition of the manganowiistite in the equilibrated two-phase mixture was determined by lattice parameter measurements and comparison with known standards. The oxygen pressure for the Ni + NiO equilibrium was taken from available data.l3~l4 No reliable results were obtained with the electromotive force technique on iron-rich oxides. The electromotive force drifted strongly with time in this composition range. An additional difficulty arises from the partial de-

Jan 1, 1968

By J. R. Cahoon, H. W. Paxton

The possibility of using unidirectionally solidified, two-phase alloys as an approximation to fiber composite materials is investigated. The short-term me.chanical properties and failure modes of unidirectionully solidified A1 (rich)-Cu alloys containing ap -Proximately 0, 17.5, and 27.7 vol pct of 0 phase 'fibers" are determined at temperatures from 25" to 500" and compared with those obtained for conventionul SAP alloys. In a previous publication,' hereafter referred to as I, the possibility of understanding some of the room-temperature mechanical properties of unidirectionally solidified castings was explored. For Al(rich)-Cu and Al(rich)-Mg two-phase alloys over a substantial range of compositions, the yield and ultimate strengths and common ductility measures were very adequately predicted from the principles of fiber strengthening4 and the analysis of ductility outlined by Gurland and Plateau." The results obtained in I suggest the possibility of using unidirectionally solidified, two-phase alloys to simulate fiber composite materials where the inter-dendritic second phase or constituent acts as the reinforcing material. Recent attempts concerning the fabrication of fiber conlposites have concentrated on producing composites with a good bond between fiber and matrix and with very long fibers so that their maximum contribution to the strength of the composite may be realized. However, these objectives are difficult to attain in practice and present fabrication processes are either extremely laborious or costly.13 The slow, unidirectional solidification of eutectics has received considerable attention as a method for producing composite materials. 5,6 This method can fulfill both of the above objectives but it is currently laborious, expensive, and has the additional disadvantage that the volume fraction of reinforcing phase cannot be easily varied. On the other hand, unidirectionally solidified, two-phase alloys, also with a good bond between the phases, are relatively easy to make and the volume fraction of reinforcing "fibers" can be easily varied by changing the average composition of the alloy. The disadvantage of the cast alloys is that the mechanical effectiveness of the "elongated interdendritic reinforcements" (EIR)* may be reduced due to their rela- tively short lengths, the w factor in Eq. [2] of I. However, if the EIR have a high strength their contribution can be considerable. For composite materials containing discontinuous cylindrical fibers of various lengths the ultimate strength is given by1 where it is assumed that the composite fractures when the fibers fail. In Eq. [I], a, is the stress in the matrix just prior to failure of the composite, Vf is the total volume fraction of fiber reinforcing constituent, Vf(l+) is the volume fraction of fibers whose lengths exceed the critical length, I,, which is defined as the shortest length of fiber in which the stress can build up sufficiently to break the fiber. af is the fracture strength of the fiber material, w is a factor accounting for the discontinuity of those fibers whose lengths exceed I,, 1-/d is the average aspect ratio of those fibers whose lengths are shorter than I,, and t is the shear stress in the matrix at the fiber-matrix interface. The factor w is dependent on the length of the fibers and also on whether deformation of the matrix occurs plastically or elastically. However, for a given length of fiber, w is smaller when elastic deformation of the matrix is assumed.' It is of interest to consider the properties of simple unidirectionally solidified, two-phase alloys at elevated temperatures in view of the possibility of using suitable modifications for high temperature service. Knowledge of the creep behavior of these materials is still rudimentary (although under active investigation) and the present paper concerns itself with short time tensile properties of some alloys similar to those investigated in I (i.e., unidirectionally solidified Al(rich)-Cu alloys). Unidirectionally solidified alloys containing 5.6, 17, and 23 wt pct Cu were tested parallel to the direction of solidification at temperatures from 25" to 500°C. In the present investigation, the alloys were homogenized for 2 days at 535°C giving a matrix of homogeneous a phase (5.2 wt pct Cu) and an interdendritic constituent (EIR) which was completely Q phase (53 wt pct Cu). EXPERIMENTAL Alloys of nominal composition 5.6, 17, and 23 wt pct Cu (containing approximately 0, 17.5, and 27.7 vol pct 8 phase, respectively, after homogenization at 535°C) were prepared by melting 1200 g of A1 (99.99 pct) in a high purity graphite crucible and adding the appropriate amount of freshly cleaned copper chips (99.9 pct). The molten alloy (at 700°C) was poured into a preheated graphite mold (also at 700°C) and the ingot unidirectionally solidified by impinging water on the steel baseplate of the mold. The alloy was degassed immediately

Jan 1, 1970

By L. C. Michels, O. G. Ricketts

The disorientations between s?nall grains, whose growth has been arrested at an early stage of recrys-tallization, and the deformed matrix in cold-rolled aluminum single crystals were determined using transmission Kikuchi line and electron diffraction patterns. The orientations of the recrystallized grains were found to be random, and the disorientations of these grains with the matrix weve found to be intermediate to large. This leads to the conclusion that the observed vecrystallization began in small areas of large disorientation present in the cold-worked structure. heavily cold-worked thin sections of aluminunz single crystals and of polycrystalline aluminum and nickel were produced directly by a mechanical technique. The specinlens thus prepared were heated with the electron beam to bring about vecrystallization during observation in the electron microscope. Motion pictures taken du.ring heating and the electvon, microg.raphs taken both before and aftev heating allowed the recrystallization process to be traced to its ovigin. Re cvystallized grains originated in very s,mall regions of the cold-worked structure and developed through rapid migration of high-angle boundaries. The boundaries either were present as such in the matrix or were formed out of dense dislocation networks. SIGNIFICANT advances have been made in recent years in the study of nucleation of recrystallization using the technique of transmission electron microscopy of thin metal foils. Bollman1 in a study of heavily rolled polycrystalline nickel found support for the Cahn-Cottrell2,3 theory of nucleation. According to this theory nuclei form by the initially slow growth of subgrains formed through polygonization. During this initial period of slow growth (the incubation period) the migrating boundary of the subgrain increases its disorientation with the cold-worked matrix and thereby increases its mobility to become a rapidly migrating high-angle boundary. Bailey4,5 investigated the annealing behavior of several metals deformed both in tension and by rolling and concluded that recrystallization took place through the migration of high-angle boundaries. With low deformations these boundaries were present in the metal before deformation. With high deformation it was not possible to tell whether the boundaries were pieces of the original grain boundaries or were produced either during deformation or by polygonization during ameal- ing. Direct observation during heating of metal foils indicated that subgrains form by polygonization and grow at an uneven rate. The grain size obtained decreased with decreasing foil thickness indicating that the foil surface resists boundary motion. Votava,6 in heating stage experiments on rolled copper, observed nuclei to appear suddenly and grow in jumps of differing magnitude. However, he found no special dislocation configurations where the nuclei appeared. Fujita,7 as a result of a study of subgrain growth in heavily worked aluminum, concluded that the boundary of a recrystallized grain initially forms from the boundary of a group of subgrains. This occurred by a process of deposition of vacancies and dislocations in the group boundary as the boundaries within the group disappear. HU8,9 directly observed a similar process in heating stage experiments on 70 pct rolled Si-Fe single crystals. The growth of subgrains appeared to proceed by a coalescence mechanism. The observed fading away of the boundary between two subgrains was explained by the moving out of dislocations from the disappearing boundary into the connecting or intersecting boundaries around the subgrains. The subgrain size and degree of disorientation with the surrounding structure were thus increased. With the increase in disorientation occurred a corresponding increase in boundary mobility, which eventually allowed the boundary to migrate rapidly. This process was observed to occur within "microbands" consisting of parallel narrow segments disoriented by a few degrees present in the as-rolled structure. The conclusion of Rzepski and Montuelle10 that growth is preceded by the coalescence of blocks through disappearance of their common boundaries supports this view. In contrast to Hu's coalescence model for nucleation were the conclusions of Walter and ~och.""~ Working with the same material as Hu, of the same orientation and rolled to the same reduction, they concluded that nucleation occurred by the Cahn-Cottrell mechanism. They observed, in agreement with Hu, that recrystallization began in the "microband" regions which they referred to as "transition" bands. Bartuska13 studied subgrain growth in heavily rolled nickel using a beam heating method in the electron microscope. He concluded that nuclei for recrystallization form from the largest most perfect subgrains present in the cold-worked structure by rapid intermittent migration of parts of subboundaries. In rare instances he observed subgrain growth by coalescence. EXPERIMENTAL PROCEDURE The materials used in this study were 99.999 pct A1 supplied by A.I.A.G. Metals, Inc., and 99.999 pct Ni supplied by Johnson and Matthey and Co., Ltd. The Hitachi HU-11 electron microscope, with uniaxial

Jan 1, 1968

By P. Chiotti, J. T. Mason

Ther?nal, X-ray, metallographic, and vapor pressure data were obtained to establish the phase diagram and standard free energy, enthalpy, and entropy of formation for the compounds in the Sw-Zn system. Four compounds, SmZn, SmZn2 , SmZn4.s, and SmZn8.5, melt congruently at 960°, 94Z°, 908°, and 940°C, respectively. The cornpounds SlnZns, Sm3Znll, and SnzZn7.3 undergo peritectic decomposition at 855", 870°, and 890C, respectively. Another compound of uncertain stoichiometry, SmZn11, undergoes peritectic decomposition at 760°C. Four entectics were observed with the following compositions in weight percent zinc and eutectic tenzperatures in degrees Centigrade: 12 pct, 680°C; 36 pct, 890°C; 58 pct, 850°C; and 72 pct, 900°C. An allotropic transformation and a composition range were observed for the SmZnz compound. The transfor)nation varies from 905" to 865°C as the zinc content increases from 16.0 to 48.5 wt pct, respectively. The free energy of formation of the compounds at 50PC varies between -15.9 kcal per mole for SmZn to -51.1 kcal per mole for SmZn,.,. Corresponding enthalpies vary between -19.2 to -78.3 kcal per mole. The ther-modynamic properties for the liquid alloys are described by the relations: A search of the literature revealed very little information on the Sm-Zn system. Chao et al.&apos; as well as Iandelli and palenzonai have reported the structure of SmZn to be cubic B2 type and Kuz&apos;ma et al3. have reported the structure of -sm2zn17 to be of the Th2Ni17 type. The purpose of this work was to establish the phase diagram of this system, to determine the zinc vapor pressure over the solid two-phase regions of the SYstem, and to calculate the thermodynamic properties of the compounds. MATERIALS AND EXPERIMENTAL PROCEDURES The metals used in this investigation were Bunker Hill slab zinc 99.99 wt pct pure and Ames Laboratory samarium. Analysis of the samarium by chemical, spectrographic, and vacuum-fusion methods gave the following average impurities in ppm: Nd, <200; Eu, <100; Gd, <100; Y, <50;Ca, 225; Ta, 400; Mg, 10; Cu, ~50; 0, 175; H, 20; and N, 15. The elements Fe, Si, Cr, Ni, Al, and W were not detected. The samarium was received as sponge metal and was kept under argon except when being cut with shears and when being weighed. Tantalum was found to be a suitable container for alloys with zinc contents up to the Sm2Znl, stoichio-metry. At higher zinc contents the grain boundaries of the tantalum containers were penetrated by the alloy and the containers failed during prolonged annealing. About 25 g of massive zinc and samarium sponge were sealed in tantalum crucibles equipped with thermocouple wells. These crucibles were in turn sealed in stainless-steel jackets. All closures were made by arc welding under an argon atmosphere. The samples were equilibrated in an oscillating furnace and in some cases were given various heat treatments in a soaking furnace. After appropriate heat treatment the steel jackets were removed and the alloy subjected to differential thermal analysis. The apparatus was calibrated against pure zinc and pure copper and found to reproduce the accepted melting points within 1°C. Alloys were subsequently subjected to metallographic examination and those of appropriate compositions were used for X-ray diffraction analysis and for zinc vapor pressure determinations. The vapor pressures were determined by the dewpoint method. Both the differential analysis and dewpoint measuring apparatuses have been described in earlier papers.4, 5 All alloy samples were etched with Nital (0.5 to 3 pct nitric acid in alcohol) except the samarium-rich alloys. These more reactive alloys were electro-polished in a 1 to 6 pct HClO4 in methanol solution at -700c at a potential of 50 v. EXPERIMENTAL RESULTS Phase Diagram. The results of thermal analysis are indicated by the points on the phase diagram, Fig. 1. Eight compounds and four eutectics were observed. The composition of the compounds and their melting or peritectic temperatures are given on the phase diagram. The four eutectic compositions in wt pct zinc and eutectic temperatures in % are: 12 pct,- 680°C; 36 pct, 890°C; 58 pct, 850°C; and 72 pct, 900°C. The stoichiometry of the most zinc-rich compound is still uncertain, but is very likely either SmZnll or SmZnlz. However, to simplify the presentation which follows it will be referred to as SmZnll. As shown on the phase diagram the phase regions for some of the samarium-rich alloys have not been unambiguously established. A sample of pure samarium was observed to transform at 924°C and to melt at 1074"C, in good agreement with corresponding val-

Jan 1, 1968

By David E. Jones, Dean K. Hunt, C. Y. Chen

INTRODUCTION Of all the numerous geological hazards that threaten the well-being of urban areas in the United States, probably none is so widespread, persistent, and diversified as surface subsidence (HRB-Singer, Inc., 1977). Simply defined, subsidence is the vertical displacement or sinking of the ground surface caused by either natural phenomena or man&apos;s activities. The downward movement, however, can be accompanied by horizontal movement, strain, tilt and even by a locally upward movement. Damage to structures and the environment can result from any of these movements. Extracting subsurface materials, fluids and solids, accounts for most man-induced subsidence in the United States. Among all the mining-related subsidences, the collapse of voids created by underground coal mining has been the major cause in inflicting surface damage (Comptroller General of the United States, 1979). Subsidence from coal mining may occur within a few weeks or be delayed for years, depending upon the mineral layer&apos;s depth below the surface, the overlying rock strata&apos;s characteristics, the extent and methods of mining that were employed, and the time deterioration of pillar and mine structure. Unless underground resources are not mined or control measures are implemented to prevent or minimize damage, some degree of surface subsidence and its accompanied deleterious effects are often inevitable. The ways to control the subsidence and minimize surface damage may include: 1. Precautionary measures built into new structures or surface features. 2. Preventive works applied to existing structures or surface features. 3. Mine design incorporating special underground layouts. 4. Any combination of the above measures. Upon the enactment of Public Law 95-87, the Secretary of the Interior, through the recently created Office of Surface Mining (OSM), was authorized to promulgate rules to regulate mining reclamation including subsidence control. Proposed on September 18, 1978, these rules were finalized, following public comment and hearings, on March 13, 1979, as part of the permanent regulatory program for the regulation of surface mining and reclamation operations which include the surface effects of underground mining. On January 28, 1981, Secretary Watt of the Department of the Interior issued an order to re- quire all agencies to identify with recommendations all regulations which are believed to be excessive, burdensome or counterproductive. Also on February 17, 1981. President Reagan issued Executive Order No. 12291 requiring all Federal agencies to conduct a regulatory review to make a determination that each promulgation of a regulation is clearly within the authority delegated by law and consistent with Congressional intent (Federal Register, 1981). As a result, OSM initiated the regulatory reform to revise the permanent regulatory program. Following a brief discussion of the technical aspects and the effects of subsidence on man and his environment, this paper presents a historical overview of how rules and regulations are used to govern the subsidence related problems. The development of the regulation of subsidence under Public Law 95-87, the Surface Mining Control and Reclamation Act of 1977 (SMCRA or the Act) are also discussed, including the new regulations being developed under the regulatory reform program. SOME TECHNICAL ASPECTS Am EFFECTS OF FINE SUBSIDENCE An extensive historical review of mining subsidence is given by Zwartendyk (1971) and Shadbolt (1978). Comprehensive technical presentations have been given by Henry (1956), King and Whetton (1957), Hall and Orchard (1963). Muller, et al. (1968). Grard (1969), Voight and Pariseau (1970). Kapp and Williams (1972), Cummins and Given (1973), Brauner (1973) , and NCB (1975). A theory of surface subsidence due to underground mining was perhaps first fundamentally stated by a French engineer, Toillez, in 1838, and formulated by a Belgian engineer, Gonot, in 1839 (Goldreich, 1913, cited by Zwartendyk, 1971). Since that time,

Jan 1, 1982

By Frank H. Skelding

Still the world&apos;s largest producer, consumer and importer/exporter of minerals, the United States has, in recent years, become more and more aware of the many diverse forces that increasingly affect its ability to maintain free access to and trade in minerals, both domestically and abroad. The nation&apos;s growing dependence upon foreign sources of minerals in the face of mounting competition is causing many changes, not only in the mineral industries, but in national attitudes and policies as well. This paper examines the position of the United States in the world mineral economy relative to the significant trends that have and are developing. It attempts to define and evaluate the major present and future impact of these trends and to anticipate the probable effects upon the U.S. and its mineral economy.

Jan 1, 1976

By F. H. Froes, D. H. Warrington

Electron microscope evidence which indicates that TaC may precipitate at random sites in the matrix is presented. Initially the particles are almost spherical and coherent with the matrix. However, as they grow in conditions in which there are insufficient vacancies to relieve lattice strain, the particles rapidly lose coherency in two directions and continue to grow as plates with approximately the full lattice mismatch strain present perpendicular to the plane of the plate. The necessary relief of strain comes from dislocations loops which do not become visible until the later stages of aging. The rapid decrease of apparent strain to low values of appoximately 1 pct at small particle sizes arises not from a complete incoherency but from applying a model wrong for the particle shape and strain distribution. PREVIOUS work has shown that MC-type carbides may precipitate intragranularly in austenitic stainless steel on dislocations,1&apos;2 in association with stacking faults,3&apos;4 and randomly through the matrix,5-7 In investigations of the matrix precipitate by thin-foil electron microscopy, considerable lattice strain has been found to occur around the precipitating phase.7&apos;8 Attempts have been made to evaluate the amount of lattice strain by using the methods developed by Ashby and brown.9,10 Values of the linear strain, much less than the 17 pct theoretical mismatch (for TaC), have been reported; it has been suggested that this is due to either a loss of coherency1&apos; or vacancy absorption which occurs during either the initial nucleation or growth of the precipitate." This report is an extension of earlier work7 that dealt with the precipitation of TaC from an 18Cr/12Ni/ 2Ta/O.lC alloy after it had been quenched from 1300°C and aged between 600" and 840°C. In particular, the shape of the precipitate particles and the amount of strain in the matrix, due to the precipitate, have been studied. The work described here is part of a wider investigation of factors that affect carbide precipitation in austenitic stainless steel," details of which are to appear elsewhere. RESULTS The present investigation can be conveniently split into two aspects of the strain-fields surrounding the matrix particles: 1) information derived from the strain-field which indicates the shape and habit plane of the precipitate particles and 2) the magnitude and sign of the strain-field. The Shape and Habit Plane of the TaC Precipitate. In the early stages of aging twin lobes (normally black F. H. FROES, formerly at the University of Sheffield, Sheffield, England, is Staff Scientist, Colt Industries, Crucible Materials Research Center, Pittsburgh, Pa. D. H. WARRINGTON is Lecturer, Department of Metallurgy, University of Sheffield. Manuscript submitted November 1, 1968. IMD on white background, i.e., for the deviation parameter, S > 0) that indicate the strained region of the matrix define the position of the particles by bright field transmission electron microscopy. The actual particles were not detected until they were approximately 120Å diam; below this size they were too small to be imaged in the electron microscope. This meant that particle growth that had occurred before this stage had to be inferred from the matrix strain-field contrast. In all cases when diffraction effects were observed from the precipitate particles, a cube-cube orientation relationship (i.e., (llO)ppt Il<llO>matrix and {1ll }ppt {III} matrix) existed between the precipitate and the matrix. From the matrix precipitate particles lying along edge-on {111} planes (e.g., at A, Fig. I), the precipitates are seen to be plate-like with their diameter being roughly 18 times their thickness after 5000 hr at 650°C. However, the exact shape of the particles cannot be determined because of the masking effect of the strain-field contrast. If a dark-field micrograph, using a precipitate reflection, is studied, Fig. 2, a number of the projected images of the TaC particles [on the (110) foil surface] apear to have straight edges parallel to projected f111) planes. Thus, it appears that in the later stages of aging the TaC particles are plate-like with some tendency for the edges of the plate to be bounded by the matrix close-packed {ill} planes (though the general shape of the particles in the plane of the plate is circular and thus the "diameter" of the particles has a real physical significance). It should be noted that the bands of fine discrete particles observed in Figs. 1 and 2 are not the matrix precipitate discussed in this paper but are precipitates associated with extrinsic stacking faults3j4 occurring on (111) matrix planes. **£** ****** \ *x 23 Fig. 1—18/12/2~a/0.1~ alloy. Solution treated at 1300°C for 1 hr, water quenched, and aged 5000 hr at 650°C. The (112) directions shown are the traces of the e&e-on (111) planes. Foil normal [110]; operating reflection (331); bright field micrograph.

Jan 1, 1970

By H. W. Morse

THE CHAIRMAN (H. W. MORSE).-Gentlemen, for the first time in the history of the American Institute of Mining Engineers, we have a full session on the subject of leaching-especially on the leaching of copper ores.. This branch of metallurgy is rather in its infancy. We have had one big plant running for a year or more, and pretty successfully; and another one which will be started in February or March, the New Cornelia. We have another one at Garfield for the Utah company, which is just designed and construction begun; and from several other points come reports of interesting test work. The first paper on the program this evening is one of some of the test work on the New Cornelia ore by myself and Mr. H. A. Tobelmann. LAWRENCE ADDICKS, New York, N. Y. (written discussion).-The Ajo proposition has had, as I understand it, two great advantages: it has not been obliged to measure leaching against flotation or some other metallurgical process, and it deals with a copper content high enough

Jan 12, 1916

AT the meeting of the Board of Directors held on June 25, 1926, and in response to numerous in-dividual suggestions for changes, a committee on Re-vision of the Constitution and By-Laws of the Insti-tute was appointed, consisting of C. F. Rand, Archi-bald Douglas and H. Foster Bain. Various confer-ences were held, much correspondence conducted and a preliminary draft was prepared. It proved imprac-ticable to complete the work in time to submit the matter to the membership for approval or disapproval at the annual meeting in 1927, and the Committee was continued with instructions to prepare a report as a basis of action in 1928. After Mr. Rand&apos;s death George Otis Smith was appointed in his place and the tentative draft herewith submitted has been pre-pared in its present form by Messrs. Smith, Douglas and Bain, though not differing in any material mat-ter from an earlier draft approved by Mr. Rand. In preparing this the Committee has kept in mind primarily the desirability of simplification and of making the By-Laws conform to the actual practice of the Institute as worked out through experience. The Constitution and By-Laws adopted in 1912, and which with minor amendments only still govern the Insti-tute, are full of specific provisions regarding pro-cedure; such as that laid down for guidance of the Papers and Publications Committee. Many of these have proved unworkable and in practice have not been always strictly followed. It now seems wise to write into the Constitution and By-Laws only the general fun-damental principles to he followed and to provide for such easy change in methods of following them out as will permit efficient conduct of the business. It is this thought that has guided the Committee in rewrit-ing many of the sections. With this in view also the Constitution, as such, has been shortened to the brief-est feasible statement of fundamentals. All matters relating to means of making these principles effec-tive have been put into the By-Laws or in the hands of committees whose work is subject to control and whose rules are subject to approval or disapproval by the Board of Directors. Many suggestions for changes have come to the Committee that have not been incorporated in this draft. Some of these are in themselves excellent but have not been incorporated here because the Commit-tee discovered no sentiment for them such as would be likely to secure their approval, or found them out of harmony with the general plan followed herein.

Jan 9, 1927

By S. B. Casey

[ ] IN 1880, an electric arc was struck over metal for the first time to experiment with controllable melting. The glare of this arc has reflected on the stacks of the steel industry and continued to light the path of steelmakers in their never ending quest -for faster, more economical, and better ways of producing steel. William Siemens is credited with first employing the electric arc to melt metal in a closed hearth and produce basic metallurgical reactions. By the turn of the century, an Italian, named Stassano, was experimenting with ore reduction by the electric arc. In 1899, Dr. Paul Heroult, in France, used the direct arc principle for producing ferro-chromium. His experiments quickly led him to develop a dosed-top arc furnace for the production of steel, and his first commercial shipment was recorded in December, 1900. American steelmakers, quick to sense the possibilities of this method of melting, invited Heroult to our shores, where, in 1905, he was responsible for installing the first arc furnace on the North American continent. This furnace, at Sault Ste. Marie, was built for ore reduction. But Charles Holcomb, founder of Holcomb Steel. Co. of Syracuse, N. Y. contacted Heroult in 1905 and contracted for the first American direct-arc electric furnace for steelmaking. On April 5, 1906, the first heat was tapped from this 3-ton unit. The furnace was basic lined and powered by a single-phase, 500 kw generator, -producing high amperage at low voltage. It is interesting to note that, although the first few heats were made with cold charges, subsequent heats were duplexed. R. H. Bully, first superintendent of Holcomb Steel, persuaded the directors to purchase the unit to effect a more economical and efficient means of making tool steel by duplexing prime melting in a combustion fired furnace, and transfer of hot metal to the arc furnace for temperature adjusting, refining, and adding carbon and alloying elements. Today, duplexing is foreseen by some as the steelmaking process of the future. The promise shown by America&apos;s first arc furnace for ingot production quickly led to the purchase of a similar unit by The Firth Sterling Steel Co., in 1909, and to the purchase of the first arc furnace for production of steel castings, by the Treadwell Engineering Co., in 1911. From its humble start in 1906, production of arc furnace steel has never ceased to increase its yearly percentage of total steel production in the U. S., although certain other methods have declined or almost disappeared. By its ability to be used intermittently, the arc furnace gained favor and enhanced its reputation during depression days. When the attack on Pearl Harbor plunged us headlong into the long days of World War II, the arc furnace stood ready, flexible enough to be overburdened hearth wise 30 pct and power wise 25 pct, pouring its endless flood of alloy for the guns, tanks, ships, and planes which ultimately brought victory. During the post war boom, the now, proven virtues of low initial cost, faster installation, better yield, improved availability, and lower operating cost, enabled industry-particularly the small, new, independent producers-to locate strategically and profitably to meet the demand of an America that had been starved for new homes, appliances, cars, and highways. In the Korean police action, the arc furnace again proved itself by providing the latest alloys metallurgists could develop to meet the demands that the jet age and the innovations of guided missiles required. In today&apos;s peacetime prosperity, the arc furnace is continuing to provide the economic flexibility required to meet an ever increasing demand for better steel in the face of mounting costs, scrap shortages, and pressure toward decentralized location of industry.

Jan 1, 1961

By C. H. Jr. Herty

DURING the past few years frequent reference has been made to a certain type of iron known generally as "bad iron," "dirty iron," etc., both by steelmakers and producers of iron castings.1 Open-hearth operators have claimed that such iron was entirely within the specified limits as to ordinary analysis but it was difficult to make good steel from it. It has been suggested that unreduced material in the iron is responsible, also that most trouble is experienced with the iron when the blast furnace is delivering a product whose analysis is more or less variable. Other reasons suggested are the use of scrap or borings, unsintered flue dust in the burden, a cold hearth, too high a proportion of unsuitable grade of ore, or the form of the carbon in the iron. Accordingly, a subcommittee was appointed at the fall meeting of the Open-hearth Committee of the American Institute of Mining and Metallurgical Engineers held in Pittsburgh in October, 1926, to investigate the reasons for the occurrence of this bad iron and suggest methods for preventing its appearance. This committee enlisted the cooperation of the U. S: Bureau of Mines Experiment Station at Pittsburgh in undertaking a study of pig-iron quality as affecting the open hearth. The following is a report of the findings to date:

Jan 1, 1929

By Charles H. Morgan

Jan 1, 1905

By A. W. Gauger

Coal as mined contains varying quantities of inorganic components (mineral matter) which, on combustion, produce the residue known as ash. It has long been realized that the weight of this residue does not equal the weight of the mineral matter originally in the coal, because of the chemical changes that take place during the ashing process. Moreover, the ordinary ash analysis presents the ash as a mixture of oxides with little or no clue to the identity of the mineral species originally present in the coal. It is only for pyritic sulfur that an attempt is made to determine a mineral component. So far as the authors are aware, there are practically no experimental data in the literature as to the percentages of the different mineral species present in coal. The oft-quoted table of Marson and Cobb1 cannot rightly be considered as data, since the authors merely state that the table "shows the probable forms in which these ash constituents exist in coal." In view of the attempts to calculate analyses and determinations of the calorific equivalent of coal to the mineral-matter-free basis, as well as the importance of the mineral species in clinkering, combustion and coking, it seems strange that so few data are available on this phase of coal technology. For example, numerous empirical corrections for use in the scientific classification of coal have been suggested to compensate for the losses from the mineral matter during ignition of the coal to ash. These include multiplication of the ash percentage by various factors such as l 1/10 and 156, the use of the Parr unit coal formula (1.08 A + 22/40 S, where S = total sulfur) as well as certain modifications of the Parr formula that attempt to correct for the organic sulfur present in the coal. Although many experiments have been made to determine the loss on ignition of the clays associated with the coal measures and correction

Jan 1, 1934

By R. A. Fitch, J. D. Griffith

A performance calculation method was used in conjunction with experimental studies to develop means of predicting and interpreting miscible floods and to explore possible methods. of improving their efficiency. The calculation method is based upon the division of reservoirs into multiple independent zones or strata. Comparison was made with some experimental floods and with a field project to obtain some measure of the applicability of the method. Two aspects of miscible flooding were considered: (I) the displacement of a miscible front through a reservoir, and (2) the distribution and utilization of the solvent volume injected to maintain miscibility. Calculations and experihental observations indicate that alternate gas-water injection behind a miscible front significantly improves miscible flood performance, both within a single stratum and in a multistrata reservoir. Calculations were made on the extent to which miscibiliry is maintained by a given solvent volume in a stratified reservoir. Two alternate criteria for determining the optimum volume of solvent for injection are discussed. The preinjection of a small volume of water ahead of the solvent is suggested as a method of obtaining more efficient utilization of solvent. Calculations and experiments were made to investigate the effects of water preinjection. INTRODUCTION Miscible fluid displacement as a possible means of recovering oil has been the subject of extensive research and numerous field tests over the past several years. This work has brought out both favorable and unfavorable features of the miscible recovery methods. Many tests have shown that a miscible fluid can displace all of the oil contacted, leaving no high residual oil saturation, as is characteristic of immiscible displacements. The miscible methods have proven dificult to control, however, as evidenced by early breakthrough of the displacing fluid and poor sweep efficiency in several field projects. It became apparent early in the investigation of miscible displacement that the development of improved techniques and better methods of control would be required to extend the range of applicability to any significant portion of our petroleum reservoirs. The purpose of this study was to consider the problem of designing miscible floods to obtain better performance. A performance calculation was used in conjunction with experimental studies to develop means of predicting and interpreting miscible floods and to explore possible methods of improving their efficiency. Two aspects of miscible floods were considered separately in this study and the results are presented in two parts. The first part concerns the manner in which the miscible front is displaced through the reservoir. In these calculations the condition of miscibility between the reservoir oil and the displacing fluid is assumed. In the second portion the distribution and utilization of the preinjected solvent in maintaining rniscibility is considered. This portion dealing with solvent utilization applies only to the enriched gas or LPG slug processes. CALCULATION METHOD AND EXPERIMENTAL STUDIES COMPUTATIONAL MODEL The calculations for expected reservoir performance are based upon the multi-strata concept of reservoir properties. The method assumes multiple, independent strata (no crossflow between strata) and explicitly includes variations in patterns, injectivity, areal sweep and displacement efficiency. Lateral variation in permeability within the strata (for example, directional permeability) may be considered in the calculations, provided the variations are similar in all strata. The calculations based on this model furnish the rates of injection and rates of production of both oil and the displacing fluid for the composite system of strata. To carry out calculations on the mathematical model described, information is required on the performance of the displacement process under consideration in a single stratum element of the pattern to be used. In particular, for a given pattern and displacement process, data are required relating injectivity and composition of the produced stream to the volume of fluid injected. Data on the variations in areal sweep must also be available if it is desired to track the areal sweeps in the multi-strata model. These data may be obtained from experimental work such as model studies or other suitable methods. This representation of reservoir properties is, of course, an approximation and may be inappropriate in some cases. But the representation is not an arbitrary one since most oil reservoirs are essentially successive layers of sediment with the net producing pay zone often comprising but a fraction of the gross formation thickness. The fact that permeabilities measured in the vertical direction are frequently but a fraction of the horizontal permeability adds some evidence to the validity of this model. This type cal-

Jan 1, 1965

By Vard H. Johnson

IN 1943 the U. S. Bureau of Mines undertook drilling in an effort to develop new reserves of coking coal in an area near Paonia, Colo., as a part of an attempt to alleviate the shortage of known coking coal of good quality in the western United States. Geologic mapping of the area was undertaken by the U. S. Geological Survey with the purpose of first furnishing guidance in location of drillholes and later aiding in interpreting the results of the drilling. The drilling program was under the general supervision of A. L. Toenges of the U. S. Bureau of Mines. J. J. Dowd and R. G. Travis were in charge of-the work in the field. Geologic mapping was started by D. A. Andrews of the Geological Survey in the summer of 1943 and was continued from the spring of 1944 to 1949 by the writer. The first few holes drilled failed to locate coking coal, but in the summer of 1944 coking coal was discovered by drilling 6 miles east of Somerset, Colo., the site of present mining. In the succeeding years, 1945 to 1948, 100 to 150 million tons of coal suitable for coking were blocked out by drilling. The ensuing discussion of the geologic controls on the distribution of coking coal in the area is based on the geologic mapping as well as the drilling done in the Paonia area, more complete descriptions of which have appeared or are in process of publication.1-5 In order that the possible geologic controls affecting the present distribution of coking coal may be considered, it is necessary to discuss briefly the indicators. of coking quality coals. Coking Coal Coal that cokes has the property of softening to form a pastelike mass at high temperatures under reducing conditions in the coke oven. This softening is accompanied by the release of the volatile constituents as bubbles of gas. After release of the contained gases and upon cooling, a hard gray coherent but spongelike mass remains that is referred to as coke. This substance varies greatly in physical properties and, to be suitable for industrial use, must be sufficiently dense and strong to withstand the crushing pressure of heavy furnace loads. Western coals have a generally high volatile content and therefore form a satisfactory coke only when they attain a rather high fluidity during the process of heating and distillation in-the coke oven. When this high degree of fluidity is developed, the volatile constituents escape and leave a finely porous coke. On the other hand, when the degree of fluidity is low the product is an excessively porous and therefore physically weak mass that is called char.6 Small quantities of oxygen present in coal are believed to decrease the fluidity of the material during the coking process and to favor the development of char rather than coke. In consequence, coal chemists have for some time considered the possibility of developing an index to coking. qualities by inspection of chemical analyses of coals.7 A formula has now been developed that does permit a rough preliminary estimate of the cokability of coal on the basis of the analysis on an ash and moisture-free basis. Coals may be eliminated as possible coking fuels if the oxygen content is greater than 11 pct. Similarly the ratio of hydrogen to oxygen must be greater than 0.5 and the ratio of fixed carbon to volatile constituents must be greater than 1.3. If the coal, on the basis of these limiting factors, appears to have possible coking qualities, the following formula permits determination of the coking index: Coking index =[ a+b+c+d 5] a equals 22/oxygen content on ash and moisture- free basis, . b equals two times the hydrogen content divided by oxygen content on moisture and ash-free basis, c equals fixed carbon/1.3 x volatile matter, and d equals the heating value on moist, ash-free basis/13,600. Coking indices higher than 1.0 suggest that the coal will coke, and indices above 1.1 indicate good coking tendencies. Although generally usable, this formula is not completely satisfactory because the percentage of oxygen shown in ultimate analyses is derived only by difference; i.e., by subtracting the sum of the percentages of the constituents determined analytically from 100 pct.8,9 Although the coking index indicates the coking tendencies of coal, it is necessary to make physical tests of coke before its industrial value can be determined. The U. S. Bureau of Mines has developed a standard procedure for determining the approximate strength of coke that would be formed from a given coal. In this test one part of ground coal, mixed with 15 parts of carborundum, is baked to form a standard briquette. The weight, in kilograms, necessary to crush the briquette is termed the agglutinating index. This test determines the relative fluidity attained in the coking process by measuring the cementing strength of the coal in the briquette. A

Jan 1, 1952

US 4,185,078-In the recovery of rhenium values from an aqueous sodium molybdate solution contained in the hydrometallurgical processing of roasted molybdenite, improved results are realized by using a described extractant consisting of a quaternary ammonium compound and benzene or other highly aromatic solvent which dissolves a quaternary ammonium-rhenium complex Essentially all rhenium is recovered from the solution and the extractant can be regenerated and recycled. This patent is a continuation-in-part of US Patent No. 4,049,771, dated Sept. 20, 1977. L R. Quatrini and M.B MacInnis, assigned to GTE Sylvania Inc. Jan 22, 1980. 6 pp (423-49). Flied. 7-19-78 (926,167).

Jan 1, 1982

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&apos; 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

By William Plank

IN PAST YEARS, engineering educators and others have been able to study the problems relating to en-gineering education in the United States with only inadequate and, frequently, inaccurate data at their command. For the first time there is now available fairly full and accurate information on this subject, gathered and compiled by the Board of Investigation and Coordination of the Society for the Promotion of Engineering Education. This board, of which W. E. Wickenden is the director, has for the past four years been carrying out fact-finding investigations into "the objects of engineering education and the fitness of the present day curriculum," under a grant of funds from the Carnegie Corporation of New York. Twelve bulle-tins have already been published by the board and others are in the process of preparation. The studies made, thus far, have been of the various phases of engineering education in general as well as of the major branches of engineering. Within the past year. the board has completed a study of mining engi-neering education by means of a questionnaire sent to members of the Institute. A special committee, con-sisting of Charles E. Locke, Allen H. Rogers and the writer, cooperated with the board in drafting certain parts of the questionnaire and in selecting the mailing list. Similar studies have been made through the mem-bers of the four other national societies. The results of these studies have been published only in mimeo-graphed form, therefore, in order to place the data before the members of the Institute an incomplete sum-mary of the replies to the A. I. M. E. questionnaire is here given. The full report will be available for distri-bution at the annual meeting in February. The questionnaire was sent to 306 members of the Institute, a proportion about equal to the proportion of the membership of the other national societies can-vassed; 152 members replied to the questionnaire, 55 per cent of whom had received college degrees in some branch of engineering connected with the mineral in-dustry. Forty-seven educational institutions were rep-resented in the replies. Seventeen different positions were held by the members who replied, with 24 con-sulting engineers at the head of the list, 20 managers, 16 superintendents, 11 presidents, 10 professors, 6 deans, and others.

Jan 1, 1928

By R. M. Caves

High-purity dense tungsten coating is obtained by means of a modified de Boer-van Arkel iodide process using tungsten bromides. The all-glass reaction system is pumped, baked, and sealed (pinched-off) at about 10-7 mm Hg pressure. The bromides then formed in situ are decomposed, depositing tungsten on heated tungsten surfaces. Heating of the specimen is done inductively in a novel arrangement that avoids electrodes of glass-to-metal seals. The tungsten, deposited at specimen temperatures from 2000° to 2800°F and bulb (halide) temperatures of 225" to 725°F, was adherent and uniform, and ranged in thickness to 1/8-in. REFRACTORY metals are of interest at NASA for use in hypersonic aircraft, in rocket engines, and in other thrust devices where very high temperatures are encountered. Tungsten, with a melting point about 6100° F, is potentially very useful for some of these applications. Considerable research on tungsten and its alloys is currently being conducted at the NASA Lewis Research Center. In this tungsten research program, there is need for a method of depositing high-purity, nonporous tungsten coatirlgs. Metallurgical bonding of the coating both to itself and to the substrate is required. In addition, it is necessary to be able to deposit thin, uniform coatings on substrates of a variety of shapes and sizes for laboratory test purposes. A survey of the methods previously used for depositing tungsten coatings indicated that none would likely meet these requirements for high purity, good uniformity, and high density except thermal decomposition of the halides. The method for coating that was selected for investigation was the thermal decomposition of tungsten bromide. This is a variation of the van Arkel and de Boer iodide process established years ago and recently reviewed.1,2 This process is applicable to the transition metals in general. More recently, the application and techniques were extended with chlorine3 and fluorine,4 and included the coating of tungsten. This is believed to be the first report on the use of the bromide for tungsten coating. Bromine was chosen over the other halogens because it promised a lower temperature for tungsten

Jan 1, 1962

Jan 1, 1909