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By N. J. Grant, B. C. Giessen, M. Morris

The slvuclures of alloys in the system In-Bi have been investigated after (levy vapid queuching from the mell (splat cooling) to -190°C. Tuo-phase fields could be suppressed over most of the tota1 concentvalion range; five melastable phases a1, a2, ?, ?1. and ß exisl, of which four have simple elementtike structures. For example, ß has the A5 struclure of white till. Crystal-tographic data and coordination numbers for these phases aye given, as well as addilional information on the equilibrium diagram, where a new phase In5Bi3 teas found. THE phase diagrams of binary combinations of B elements from the groups B2, B3, B4, and B5 are usually of a simple type and show considerably fewer intermediate phases than combinations of these elements with A metals, transition metals, or the B1 noble metals. Aside from phases such as the typical B3-B5 compounds with the ZnS-B3 structure type, few stoichiometric phases are known; among them are In2Bi and 1nBi.l Nonstoichiometric phases include ß (In-Sn), a1, (In-Pb), and the tin-rich ? phases in the In-Sn, Cd-Sn, and Hg-Sn systems.' The first two phases have a close relationship to indium, while the latter group are known to be structurally related to a Sn. Thus, there are generally no immediate experimental data for the correlation of the crystal structures of B metals and B metal combinations with certain monotonously varying parameters, such as the valence electron concentration (VEC), or the average atomic size. Such parameters have been recognized as structure determining, e.g., for the transition 4 Sn — y phase,2,3 where nonintegral valence electron concentrations are encountered. It should be possible to extend such correlations to other binary systems, if nonequilibrium single-phase alloys could be produced over broad valence electron concentration ranges, and if their crystal structures could be regarded as being imposed by their electronic states. It has been shown in the case of the tin-rich 7 phases3 that alloy phases with typical crystal structures can be produced in B metal alloys rapidly quenched from the liquid to -190°C by the splat cooling technique due to Duwez,3-8 and reviewed in Refs. 5 and 6. The In-Bi system was selected because it extends over a valence electron concentration range in which several metastable, nonstoichiometrir phases could be expected to occur. Further, the low melting points of the known intermediate phases, In2Bi and InBi, Fig. 1(a), indicated low binding energies and thus possibly low driving forces for the formation Of the equilibrium structures. EXPERIMENTAL TECHNIQUES AND RESULTS The preparation of the quenched foils followed the practice described in Ref. 3. Master alloys were produced by melting of indium (99.97+) and bismuth (99.99+) in evacuated Vycor capsules or in an inert gas arc furnace; quantities of 20 mg were splat-cooled onto copper and silver substrates held at - 190°C; and crystal structures and lattice parameters were determined on a GE XRD-5 diffractometer using Cu Ka, radiation at -190°C and at room temperature. The duplication of each run with both substrates permitted the elimination of overlap of the substrate diffraction pattern and that of the investigated substance. The XRD patterns were usually taken from sin2 " = 0.03 to 0.35; the substrate was used as a means of internal calibration. The fractional accuracy of the lattice parameters of metastable phases is approximately 10-3 In the following, all percentages are in atomic percent. The stable and metastable phases found after rapid quenching to -190°C are listed in Table I, together with estimated concentration ranges and crystallographic data. The investigated alloys and phases present in them are given in Table 11. Except for the region between indium with 33 and 50 pct Bi, where a revision of the equilibrium phase diagram became necessary to include a new stoichiometric phase In5Bi3, the diffraction patterns taken after heating to room temperature agreed with those expected from the phase diagram, Fig. l(a). This suggests that the new nonstoichiometric phases are not stable at room temperature, thus following the observations made for the y phases based on tin.3 Results concerning the equilibrium phases In2Bi and In5Bi3 and the revision of the equilibrium phase diagram which is made necessary by the inclusion of In5Bi3 will be treated first. The Crystal Structure of In2Bi. Makarov7 had identified In2Bi as belonging to the AlB2-C32 type ; however, in a later paper the structure was revised.8 In2Bio was found to be of the Ni21n-B8ß type,21 with a = 5.496A, c = 6.57.9A, and N = 6 atoms per unit cell.9 This crystal structure was confirmed in the present work; definite evidence for the doubling of the c axis, as compared to the A1B2-C32 type, and for the proposed order structure, was found in the powder pattern. The observed lattice parameters agree well with those of Ref. 8; those measured at -190°C are given- in Table I. The Crystal Structure of In5Bi3. A new, equilibrium, intermediate phase was identified in slow-cooled, as-cast alloys; it was identified as In5Bi3. The structure has been worked out by Giessen and Grant;" lattice parameters at -190°C are given in Table I. This phase is probably identical with "In3Bi2", produced by vapor deposition techniques, but not recognized as an equilibrium phase by Palatnik et a1.11 After completion of the present work, the existence of In5Bi3 has also been demonstrated by superconductivity measurements on In-Bi alloys.20

Jan 1, 1968

By S. M. Marshall

FOR a number of years European investigators have used laboratory methods of predicting the probable strength of coke made from coal, and recently several investigators in the United States have reported the use of various tests for this purpose. There is at present no method accepted as standard, however, nor is there even agreement as to the general type of test that should be used. Furthermore, because the details of most of the tests have not been worked out carefully, one investigator can not hope to duplicate the work of another. The extension of coke manufacture to new localities in the United States, and the increasing need for cokes of exceptional qualities made from the most economical mixtures, made it desirable to have some simple laboratory test which will determine whether given coals, alone or blended with other coals, are more satisfactory from the standpoint of coke strength than others of different cost. The work described herein has resulted in the development of a simple laboratory test which, it is believed, can be generally adopted in coal laboratories, and which will give concordant results even though performed by different investigators in different laboratories. The general method of predicting whether a coal or a mixture of coals will produce a strong coke, resistant to crushing and shattering, has been to correlate the known strengths of the cokes produced in commercial ovens with some measurable constituent or with some property of the coals, and then to use the relationship so found for forming an estimate of the coking strengths of coals unknown. Several such correlations have utilized the percentages of the various ultimate constituents of coal, such as the oxygen content and the hydrogen-oxygen ratio;(39)§ other correlations have involved the proportion of a, (3 and y compounds, (17'21,30 or of "oil and solid bitumens."(16,30) Also a relationship has been traced between the coking properties of coal and the rate of change of the resistance offered to the flow of an inert gas by fine particles of the coal while being slowly heated. (11,17b) But the most general corre-

Jan 1, 1929

By G. N. Goldberg, Robert A. Rapp

The steady-state kinetics and microstructures of simultaneous internal oxidation and external scale formation were investigated for the oxidation of Cb-Zr and Ch-Zr-Re alloys in pure oxygen at 1000°C. For each binary alloy, a constant rate of scale formation was observed at steady state; the internal oxidatton zone reached a steady-state, time-independent thickness. The dependence of the scaling rate on zirconium content exhibited a maximum at a low zirconium colttent; more concentrated alloys oxidized at a slower rate than pure columbium. This composition dependence of the scaling rate may be partially attributed to the effect of the internal oxidation process as an intenla1 sink for oxygen, with the formation of voluminous, and relatively impermeable ZrO2 precipitates. However, the morphologies of the ZrO2 internal oxide precipitates also affected the scaling rate. The internal oxide precipitates were distributed uniformly in the external scale. The steady-state thicknesses of the internal oxidation zones were not in agreement with those predicted theoretically from an idealized simple model. However, in this particular alloy systen1 the ideal model is not satisfied experitmentally. For ternary Cb- Zr - Re alloys with Nr10e = 0.02 or 0.05, the steady-state thicknesses of the internal oxidation zones were less than those for the corresponding binary Cb-Zr alloys. For ternary alloys with NRe(0) - 0.05, a more adherent and much less porous external scale was formed, and a reduction in the kinetics of scale formation was observed. A number of authors'-7 have reported linear oxidation kinetics for the reaction of pure columbium at 1000°C in air or in oxygen of about 1 atm pressure. A thin and tightly adherent oxide layer is found at the metal/oxide interface beneath a porous external layer of scale. Although the suboxides CbO and CbO2 represent thermodynamically stable phases at 100O°C, generally only Cb2O5* is identified as a reaction product in quenched specimens. Studies at 1000°C at lower oxygen pressures8,10 (Po2 - 10-4 Torr) show that both CbO and CbO2 do form and that CbO2 is a protective oxide. The growth of CbO2 results in parabolic kinetics until Cb2O5 is nucleated and grows. Apparently because of the large volume change associated with its formation, Cb2O5 is porous and does not serve as a diffusion barrier; linear kinetics prevail after the surface is covered with Cb2o5. On the basis of these observations, several authors5,9,10 have suggested that the linear oxidation of pure columbium at 1000°C in air or oxygen of 1 atm is limited by a Loriers-type mechanism,11 whereby the total rate or reaction is controlled by ionic diffusion through a thin layer of CbO2 which is maintained at a constant thickness throughout the linear oxidation. However, the concept of a Loriers model for a three-phase CbOlCbO2 Cb2O5 scale, with the only oxygen activity gradient across the NbO2 phase, is not self-consistent. Further, the suboxides CbO and CbO2 were not observed in the high-temperature X-ray diffraction study of columbium oxidation by Goldschmidt.8 From investigations in which the large PO2, dependence of the linear scaling rate was demonstrated, the importance of an oxygen adsorption or dissolution step has been suggested.4,5,7,10,12 Thus the mechanism for the linear oxidation of pure columbium remains quite controversial. Since further insight into the oxidation mechanism of pure columbium is not provided by this investigation, the authors wish to emphasize at the outset that their experimental results are not interpreted in terms of a particular rate controlling step for the oxidation of pure columbium. Previous investigations13-18 of the oxidation of Cb-Zr solid-solution alloys in air or oxygen at 1000°C suggest a remarkable dependence upon zirconium content. For an alloy of bulk zirconium mole fraction, N2r(0) equal to 0.05 or 0.10, the oxygen uptake is reported to be as high as four times greater than that for pure columbium;13,14 for alloys with NZr(0) 0.05 or 0.10 the oxygen uptake is reported to decrease with increasing NZr(0); to a minimum uptake of about one quarter that for pure columbium at NZr(0): = 0.50.13-15Since zirconium forms a more stable oxide (ZrO2) than the lowest columbium oxide (CbO), and since columbium exhibits a high solubility19,20 and diffusivity21,23 for oxygen, the internal oxidation of the zirconium component to ZrO2 is expected at a reaction front ahead of the advancing metal/scale interface. The external scale is then formed at the metal/scale interface by the inward migration of oxygen through the scale, probably through a series combination of molecular and ionic diffusion. Internal oxidation in conjunction with external scale formation has been investigated by Maak24 for the oxidation of dilute Cu-Be alloys in pure oxygen at 850°C. For cu-Be and many other binary alloys,24-27 very small, essentially uniaxial internal oxide particles are formed in the most dilute compositions; for somewhat more concentrated alloys. the internal oxide particles precipitate as platelets or needles. From pertinent solutions to the diffusion equation, Maak28

Jan 1, 1967

By S. W. Miller

DURING the examination of welds made in steel by the oxy-acetylene and electric-arc processes, the writer has met with some unusual structures, which he has not encountered elsewhere. They seem to be quite closely associated with the welding methods used, and characteristic of them, and would seem to be worth noting, especially as the references to them in the literature are few, and their explanation not clear or complete. An introductory word or two about fusion welding may not he out of place. The oxy-acetylene process is based on the great and very local heat generated by the burning of acetylene in the presence of commercially pure oxygen, the two gases being thoroughly mixed before combustion. The theoretical temperature is somewhat under 4000° C., but on account of various losses, the actual maximum temperature is probably about 3000° C. 1 The electric-arc process, using a metal electrode, which is also the filling rod, generates a still higher and more local temperature. The actual temperature of the positive crater of the carbon arc is given as 3500° C.2 No figures have been found for the temperature of the arc using a metal electrode, but it would probably not be very different from that of the carbon arc, and probably higher than that of the oxy-acetylene flame. The greater localization of the electric arc is due to the fact that it is not surrounded by a large envelope flame as well as to its higher temperature; while the oxy-acetylene white cone, or welding flame, in which the carbon of the acetylene is burned to CO, is surrounded and preceded by -a long envelope flame, itself of quite high temperature, in which the CO is burned to C02, and the hydrogen of the acetylene to

Jan 2, 1918

By B. C. Allen

The interface energies of chronzium, molybdenunz. hugsten, and their solid-solution alloys Cv-35Re, MO-33Re, and UJ-25Re were studied at 0.6 to 1.0 of the absolllte liquidus ter)zpe,vature using fiz&apos;e )izethods. Liquid surface tension, yv , was deter mined clsing the pendant-drop and drop-weight methods. Results are, respectizlely, 1700, 2370, and 2480 +100 dynes per ct for the rhernium -containing alloys and essentially the same as tlwse reported for liquid chro)riln, trolybdenum, and tungsten. Average solid slrjace energy, rsv< xias ))zeasured using tlre fiber-extetlsion method. The ratio of ysS, the acerage high-angle grain-boundary energy, to ySV cclas jolnd fronz grain-bolzdary grooue angles fort)zed at the surface in an inert atrfizosphere. Absolllte iute?:face energies were deterawined using ?nultip/rase equilibria involzing suitable liquids of known surface tension (tin, silver). Interpretation of the experimented results in view of pvobable tenzperatzcre, orientation, and purity effects giz,e the follouling approximations in ergs per sq ctn: ysv (i2lo. Mo-33Re) - 2100, ySS (Mo, Mo-33Re) - 800, rr (defornzation twins in MO-33Re at 1200"C) - 800. ysV (Cr. Cr-35Re) - 2400. YSS (CY, Cr-35Re) - 1000. Probably Ylv- YSV- 2500 for tungsten and W-25Re, giving yss (It&apos;, W-25Re) - 900. The interface energies of solid and liqid ch?&apos;omiu?.z, nolybdenu?rr, and tungsten are not geatly aff&apos;ected by rhenium and therefore are not a ttlajor factor in the ductili zing rhenium effect in Croup VI-A metals. THE interface energies of the refractory Group VI-A metals, chromium, molybdenum, and tungsten, are not well-established. The objective of this investigation was to study the liquid surface tension, solid surface energy, and grain-boundary energy of these metals and compare them to those found for the bcc solid-solution alloys, Cr-35e,&apos; 0-33e,&apos; and -25e. Five techniques were used to measure interface energies in high-purity polycrystal rod, wire, and sheet at 0.6 to 1.0 of the absolute liquidus temperature. The alloys were chosen to see if there was any connection between interface-energy behavior and the ductilizing rhenium effecL4j5 EXPERIMENTAL WORK Materials. A description of the materials used is presented in Table I. Chromium rod was prepared by arc melting iodide process crystals supplied by Chromallo Cor., hot extruding, and warm swaging to 0.63-cm-diam rod.6 The sheet was prepared by rolling as-extruded rod to 95 pct reduction in area from a hydrogen furnace at 800" to 900°C and surface grinding off 0.02 cm from each face. Cr-35Re rod was prepared by arc melting sintered rhenium powder and iodide chromium crystals, warm rod rolling to 50 pct reduction in area in cans, and swaging to 60 pct reduction in area at 1100" to 1200°C. Some of the rod was warm-rolled to sheet and then surface-ground. Portions of swaged chromium and Cr-35Re were further reduced by swaging and drawing to 0.013-cm-diam wire by the General Electric Co. Mo-33Re and W-25Re rod, sheet, and wire were provided by Chase Brass and Copper Co. The molybdenum sheet consisted of two lots, both essentially the same except for the carbon content. Liquid Surface Tension. The liquid surface tension of Cr-35Re, Mo-33Re, and W-25Re was measured by a combination of pendant-drop and drop-weight methods using techniques already decribed." Following out-gassing, molten drops were formed on the ends of centerless-ground Mo-33Re and W-25Re rods by electron bombardment at 5 x 106 mm. Similar drops were formed on outgassed Cr-35Re rods by induction heating under 1 atm of 99.995 pct Ar. Solid Surface Energy. Solid surface energy was measured by conducting microcreep experiments on molybdenum, Mo-33Re, chromium, and Cr-35Re wires at 2350°, 2306, 1550°, and 180O°C, respectively. In preparation, gage marks -2.5 cm apart and -0.001 cm deep were circumferentially scribed on the wire with a razor blade. Weights of the wire material were then attached. Five to seven reasonably straight wires were hung in a container made out of the wire material. The free end was placed through a small hole in the removable top and secured by bending a small portion 90 deg. The containers not only tended to provide vapor-solid equilibrium for the wires but also protected them from gaseous impurities. They were nominally 2.5 cm in diam by 5 cm high and were made from extruded chromium rod, Cr-35Re arc casting, molybdenum bar stock, or welded Mo-33Re sheet. After deg re as ing, the assembly was outgassed at a relatively low temperature to 2 x 10"5 mm and then recrystallized 2 to 8 hr at the creep temperature in a rhenium-element resistance furnace. The static argon atmosphere was gettered by tantalum radiation shielding. Specimen temperature was measured optically to 25"C using calibration with known melting points and blackbody conditions. The wires generally developed a stable bamboo-type structure according to Fig, l(b), (c), and (d) and retained their gage marks [upper portion of Fig. l(d)]. One or two of the weights were clipped off to provide a low load for the creep anneal. To minimize the possibility of bending or breakage, the wires remained attached to the top of the annealing container which was held to keep the wires vertical. The distance between gage marks was

Jan 1, 1967

By Francis Lucas

A microscope objective of given numerical aperture, whew used with light of given wave length, has some fixed limit of resolution. This may be expressed as potential resolving ability-the ability to resolve is inherent in the lens but whether this limit is achieved in practice is quite another matter. Nearly 50 years ago Abbe evolved theoretical considerations which indicated that the ability of a lens to resolve detail is directly proportional to twice the numerical aperture of the objective and inversely proportional to the wave length of the light used. It is true, unquestionably, that as the numerical aperture of the objective is increased the potential resolving ability of the lens is increased and likewise whew the wave length of the light used is decreased, the degree of resolution is increased. Whether Abbe&apos;s formula expresses the exact relationship is not a matter of great concern. It suffices to know that to improve resolution, other things being equal, two avenues of approach are available. Either the numerical aperture of the objective may be increased or the wave length of the light decreased. With the apochromatic system it is possible to employ successfully wave lengths from 400 to 500, µµ and still secure reasonably short exposures. The present limit for numerical aperture is 1.40 N. A. although objectives of 1.65 N. A. are wow an experimental possibility for metallurgical work. Thus certain well defined limits are set for those who work within the range of the visible spectrum. In order to take advantage of the increase in resolving power which accompanies a decrease in the wave length of light employed, Dr. A. Köhler and Dr. M. Vow Rohr of the Zeiss Scientific Staff developed the "monochromats." These are quartz objectives corrected for the single wave length 275 µµ which lies in the ultra-violet region of the spectrum. They also developed a series of quartz oculars and a complete photo-micrographic equipment with which to use the quartz optics. Quartz must be used for the optical parts because glass absorbs ultra-violet light almost completely. Thus there was made available about 20 years

Jan 6, 1926

Jan 1, 1967

By J. H. L. Vogt

TABLE OF COKTENTS. [ ]

Jan 1, 1902

By Homer W. Riley, C S. Jenkins

SMALL power-driven, toothed, cast-iron rolls were used first to break anthracite in 1844. Prior to that time, men with hammers, who stood on perforated cast-iron- plates, .broke the large lumps into commercial sizes. In order to convert run-of-mine into the various sizes required by the anthracite industry, about 20 million tons must be broken, annually, [ ] into smaller sizes. This phase of anthracite preparation is of major importance, because the degradation accompanying reduction in coal sizes should be kept at a minimum. The exclusive use of toothed rolls for that purpose indicates that comminution by rolls is the best solution of the problem. Many improvements have been made in tool design, but the most important was a reduction of the peripheral speed of the rolls from 1000 to 300 ft. per minute. The higher speed was based upon and approximated the velocity of a falling piece of coal when it entered the rolls. Exhaustive roll tests at the slower speed showed that the same size reduction could be affected with less degradation. The adoption, there- fore, of slow-speed, compound geared rolls, especially for breaking the

Jan 1, 1943

By William E. Ford, Edward Salisbury Dana

Examination in the Wet Way Examination by Means of the Blowpipe 479. The complete investigation of the chemical composition of a .mineral includes, first, the identification of the elements present by qualitative analysis, and, second, the determination of the relative amounts of each by quantitative analysis, from which last the formula can be calculated. Both processes carried out in full call for the equipment of a chemical laboratory. An approximate qualitative analysis, however, can, in many cases, be made quickly and simply with .few conveniences. The methods employed involve either (a) the use of acids or other reagents " in the wet way," or (b) the use

Jan 1, 1922

By Robert R. Abbott

The practice of carbonizing steel for the purpose of case-hardening has assumed great commercial importance within the past 10 years. Formerly, case-hardened steel was held in more or less contempt, since it was considered a cheap substitute for tool-steel. This is no longer the case. The development of the motor-car industry, and coincidentally that of modern alloy-steels, has resulted in overcoming many difficulties formerly experienced in case-hardening. This result has been accomplished by increased knowledge regarding the analysis of the steel which would respond most readily to case-hardening, and by more careful methods of treatment of the carbonized steel. The ordinary method of carbonizing consists in packing the steel with the carbonizing-material in cast-iron boxes and placing them in a furnace at a temperature of from 1,500° to 1,900° F. for a time sufficient to give the required depth of " case." The steel is then either quenched directly from the box, or is allowed to cool without unpacking, and finally given a single hardening-heat, or, for special work, two or three heats. During the year 1911, more than 100,000 tons of carbonizing-material was sold in the United States, at an average price of probably $55 per ton. More than 85 per cent. of this material consisted of granulated bone. Within the past four years, many manufactured compounds have been placed on the market, consisting largely of some form of carbon or carbonaceous material, with or without the addition of chemicals. Steel will absorb carbon placed in contact with it at the temperature of the atmosphere. The reaction is exceedingly slow, but increases rapidly with increasing temperature. Below

Jan 1, 1913

By G. Y. Chin, M. T. Dolan, W. L. Mammel

The least work analysis of constrained deformation, first proposed by Taylor and recently modified by Chin, Hosford, and Mendorf to include twinning, has been applied to the problem of axisynmetric flow. Calculations were made, for the case of (111}(110) slip and {111}(112) twinning applicable to fcc deformation. The solutions were obtained by linear programming techniques and with the aid of computer methods. The results show that in axisymnzetric tension the onset of twinning tends to decrease the plastic strength anisotropy as compared with the case of defortnation by slip alone. In compression, however, the strength anisotropy is increased as a result of twinning. The [100] and 11111 orientations and their vicinity are unfavorable for twinning in tension and compression, respecticely. With slight modifications, the present results may be applied to bcc metals deform ing by {110}(111j slip and (112} (111) twinning. Implications of present results to wire texture development of low stacking fault energy fcc materials arc discussed. PREVIOUSLY we&apos; have applied linear programming techniques to obtain solutions to Taylor&apos;s least work analysis2 of constrained deformation of single crystals undergoing axisymmetric flow, such as occurs in an axially loaded polycrystalline aggregate. These solutions yielded values of the parameter M = o/.r = Y/w which relates the external stress-strain (u-c) curve to the shear stress-shear strain (7-y) curve for the crystal. The value of M is dependent on crystal orientation and hence enters significantly in texture strengthening considerations.3&apos;4 Recently the Taylor hypothesis was modified by Chin, Hosford, and Mendorf&apos; to include mechanical twinning. The latter has now been applied to the problem of axisymmetric flow and the results are reported in this paper. Calculations have been made for {111 )( 110) slip and {111 )(112) twinning applicable to fcc crystals. With minor changes in the indices of the slip and twin systems, the present results are also applicable to bcc crystals which slip on (110) (111) and twin on {112)(111) systems.

Jan 1, 1970

DISCUSSION, G. Derge and D. J. Girardi presiding N. A. Gokcen (Michigan College of Mining and Technology, Houghton, Mich.)—While the authors present very interesting results on the effect of sulphur upon the solubility of oxygen, they have not established convincingly the lines of two-fold saturation (the valleys in Fig. 2) and the ternary eutectic point. Their contention that sample S-7, upon melting at

Jan 1, 1954

By P. A. Larssen, P. R. Gage, R. W. Bartlett

The kinetics of formation of intermediate sili-cide compounds from MoSi2/Mo and WSi2/W couples were studied using a cylindrical sample configuration. Concentration profiles of the constituent metals were deter mined from electron-microprobe analysis of cross-sectioned samples after isotlzernzal diffusion annealing. These data also yielded hand widths of phases. Growth of intermediate phases depends on diffusionin them and obeys a parabolic rate law. The rates of formation of the intermediate phases decrease in the order Mo5Si3 > W5Si3 > Mo3Si. Crowth rates. for the isomorphous phases Mo5Si3 and W5Si3 had the same activation energy. 43 kcal per mole. SILICIDE coatings employed to protect refractory metals from high-temperature oxidation are usually formed by a diffusion process requiring concurrent transfer of silicon to the refractory metal surface. For a simple binary system and a coating thickness of one or two mils, the coatings on molybdenum and tungsten are primarily the disilicides WSi2 and MoSi2, respectively. During use of the coated re- fractory-metal system at high temperatures, in the absence of the silicon source, further diffusion causes growth of lower silicide compounds and depletion of the disilicides. Recent investigations have shown that the lower silicides are less effective than the disilicides in forming a glassy oxide film which impedes oxidation.&apos; Consequently, failure of coatings at high temperatures may coincide with complete conversion of the disilicide phase. The purpose of this part of the study is to investigate the growth kinetics of the intermediate compounds in the W-Si and Mo-Si systems. There are three intermetallic compounds in the Mo-Si system: MoSi2 with a tetragonal structure

Jan 1, 1964

By Delbert E. Gann, Richard D. Hagni

Ore microscopic study of copper-bearing shale at the Creta mine in southwestern Oklahoma reveals a variety of copper sulfide grains and shows that each has originated by replacement of original constituents In the Permian Flowerpot Shale at Creta. The largest grains, about 120 pm in diameter, are replacements of megaspores with triletes morphology. Their interiors are shown by Auger microprobe analyses to be organic matter. The interior organic matter and the spore exines have been replaced by anilite and djurleite. Digenite and anilite replace collomorphic pyrite averaging 40 pm in diameter. Grains 10 pm or less in d~ameter are mostly euhedral, six-sided, platy crystals that have anllite compositions and are pseudomorphous after pyrrhotzte. Other 10 pm copper sulfide grains are pseudomorphous after octahedra and cubes of pyrite. The results of this study indicate that the copper minerals are epigenetic and were deposited from fluids introduced into the Creta shale when it was relatively uncompacted and permeable. The shale served as a favorable reducing environment that contained a source of sulfur in the form of pyrite and pyrrhotite.

Jan 1, 1985

By Earl Bardwell

THE structural relations existing between cuprous oxide and copper -were first systematically studied by Heyn1&apos;, who suggested that a study of the microstructure of refined copper might be substituted for the analytical methods in vogue for determining the oxygen content of copper coming from the refining furnace. Hofman, Green and Yerxa,2 in their paper A Laboratory Study of the Stages in the Refining of Copper, working along the lines suggested by Heyn, showed that a study of the microstructure could be made to yield a correct estimate of the oxygen content of the specimen of refined copper under examination. In order to determine the oxygen content of the specimen of refined copper under. examination a photomicrograph was first made. From the relative areas of copper and eutectic, the percentage of cuprous oxide and the corresponding percentage of oxygen were then readily calculated. It was found that the values for oxygen thus obtained corresponded closely with the analytical results. With the idea of utilizing this method of determining the oxygen content of each charge dipped from the refining furnaces at the Boston & Montana Reduction Plant, the physical testing laboratory was equipped with suitable apparatus for carrying out the work. It may be of interest to describe certain of the methods which have been worked out in this connection and give such data as have been obtained bearing on the effect of the oxygen content of refined copper upon its conductivity. Apparatus.-For the benefit of those who may be unfamiliar with metallographical apparatus and methods and may be interested to know what equipment is required, a few words with regard to the apparatus is in place at this point.

Jan 7, 1913

By S. R. Goodman, Hsun Hu

The rolling texture of an 18-8 stainless steel (Type 304L or 304) has been found to change gradu -allv from the (110)[112] brass type to the (123)[412] copper type as the rolling temperature increases from 200° to 800°C. This texture transition is accompanied by a change in the stacking-fault frequencv or probability, similar to those found pre- In a series of previous publications, it was shown that the rolling texture of high-purity silver changes gradually from the brass type to the copper type with increasing temperature of deformati~n. A similar temperature dependence of rolling texture transition was found in electrolytic copper3—by lowering the temperature of deformation, the normally observed rolling texture of copper changed gradually viously in nonferrous fcc metals—the stacking-fault frequency decreases rapidly with the formation of the copper type texture. These results strongly indicate that the temperature dependence of copper type == brass type texture transition and its correlation with stacking-fault frequency is a general phenomenon in fcc lattices. to the brass type.* In both of these metals, the

Jan 1, 1964

By Charles W. Goodale

The ores of the Butte district present a variety of combinations, and their treatment by concentration is an interesting study. They may be classified in general as follows: 1. Copper-silver ores, which are produced by the mines of the Anaconda group, and by the Mountain View, Colusa, Silver Bow and Parrot. The high-grade ores from these properties are roasted and then smelted; but a large proportion of the output is low-grade and siliceous, and hence requires concentration. The copper-bearing minerals are chalcocite, bornite, enargite and chalcopyrite, in varying proportions in the different mines, the gangue, which breaks readily into grains, being quartz and feldspar. 2. Silver-copper ores, of which the Gagnon vein is the largest producer. The grade of the ores from this mine is such that nine-tenths of the output requires concentration. The silver- and copper-bearing minerals of this vein are massive wurtzite, sphalerite, bornite, chalcopyrite, pyrite, tetrahedrite, enargite, tennantite and galenite, with a quartz gangue associated with feldspar and small quantities of barite and fluorite. The gangue is very hard and not at all granular. 3. Silver-ores containing a small amount of gold, embracing the product of the Alice, Magna Charta and Moulton claims, on what is known as the Rainbow lode, and that of the Lexington, Blue Bird, Nettie, Burlington and other mines. The gangue is quartz, carrying pyrite, sphalerite, galenite, tetrahedrite and argentite, with manganese in the form of rhodochrosite and rhodonite. Good results on ores of this class cannot be obtained by concentration, because large percentages of the silver-bearing minerals are disseminated through the gangue in such minute grains that even the finest practicable crushing

Jan 1, 1897

By R. W. Guard, W. R. Hibbard

As part of a program to determine the deformation characteristics of pure metals, the tensile creep properties of high purity aluminum (99.994 pct Al) have been determined using a constant stress loading. The effects of prior annealing temperature, stress, and temperature were studied. These data have been examined on the basis of present-day theories. None of the methods was found to give an accurate representation of the data over all conditions studied. The structures of several specimens after creep were examined by optical and X-ray metallography. Marked changes in the grain size were found and it was substantiated that the magnitude of these changes was greatly influenced by the applied stress (or creep strain). The changes in fiber texture which occur on creep deformation are shown to be consistent with those observed on deformation at lower temperatures. UNDERSTANDING the properties of new mate-*-J rials under different experimental conditions must be based on considerable knowledge of the mechanisms involved in plastic flow and how to control them. Tension and creep tests have been carried out on a number of pure metals in order to document their deformation characteristics. It is hoped that a comparison of these data with theory will indicate those areas where work on mechanisms and their relation to metallurgical variables may be most fruitful. Since aluminum has often been used for studying the qualitative aspects of creep behavior, it was chosen for detailed study. The effects of annealing temperature, stress, and test temperature on the constant stress creep behavior were studied. Although most of the tests were made above one half the absolute melting temperature, a few tests were made at lower temperatures to give qualitative comparisons. Some specimens were examined metallo-graphically and by X-ray diffraction techniques after creep. Since only a limited number of specimens could be made from the available material, no effort was made to study detailed changes in sub-grain structure or other metallographic features. Servi and Grant3 nd Dushman et al.&apos; have previously published studies of high temperature creep of high purity aluminum. In both cases, a great deal of emphasis was placed on the minimum creep rate.

Jan 1, 1957

By Robert D. Pehlke, Kazuhisa Okajima

The activity of zinc in dilute liquid lead alloys containing small additions of silver and gold has been measured using a multielectrode galvanic cell with a fused chloride salt electrolyte. The range of temperatures studied in the Pb-Zn-Ag system was 550" to 670°C and in the Pb-Zn-Au system was 680" to 800°C. The interaction parameters between zinc and the precious metals in the respective temperature ranges are ThE lead-rich corners of the Pb-Zn-Ag and Pb-Zn-Au ternary systems are of considerable industrial importance. The use of zinc additions for the desilvering The results of this investigation have Provided a senzi-quantitative determination of the liquidus phase boundaries in the lead-rich corner of these ternary diagrams. of liquid lead either by the Parkes process or by the more recent Williams continuous process is an important refining phase of lead production.1 Several in-ve~ti~ations~-~ have been carried out on the Pb-Zn-Ag system with the hope of improving the efficiency of refining lead in this manner. The addition of zinc also provides a means for separating gold from lead. Since gold is eliminated more easily than silver, a two-stage removal of gold and silver is possible.8&apos;7 The thermodynamic interactions between zinc and these precious metals in dilute solution in liquid lead

Jan 1, 1968